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Wildfire smoke, consisting primarily of organic aerosols, has profound impacts on air quality, climate and human health. Wildfire organic aerosol evolves over long-time photochemical oxidation due to the formation and ageing of secondary organic aerosol, which substantially changes its magnitude and properties. However, there are large uncertainties in the long-time ageing of wildfire organic aerosol because of the distinct ageing behaviours of the complex organic emissions. Here we developed an oxidation model that simulates the ageing of wildfire organic emissions in the full volatility range on a precursor level and integrated insights from single-species ageing and wildfire emissions ageing experiments and field plume observations to constrain the long-time ageing of wildfire organic aerosol. The model captured the enhancement of organic aerosol mass (2–8 times) and oxygen-to-carbon ratio (1–4 times) in the wildfire ageing experiments. It also reconciled a long-standing discrepancy between field and laboratory observations of the magnitude of secondary organic aerosol formation. The model indicated large emissions-driven variations in precursor contributions to secondary organic aerosol, which further evolve with long-time ageing. The estimated global wildfire secondary organic aerosol production (139 ± 34 Tg per year) was much higher than previous studies omitting or under-constraining long-time ageing.

Biomass burning is an important source of primary and secondary organic aerosol (POA, SOA, and together, OA) to the atmosphere. The photochemical evolution of biomass burning OA, especially over long photochemical ages, is highly complex and there are large uncertainties in how this evolution is represented in models. Recently, Lim et al.(2019) performed and reported on photooxidation experiments of biomass burning emissions using a small environmental chamber (∼150 L) to study the OA evolution over multiple equivalent days of photochemical aging. In this work, we use a kinetic, process-level model (SOM-TOMAS; Statistical Oxidation Model-TwO Moment Aerosol Sectional) to simulate the photochemical evolution of OA in 18 chamber experiments performed on emissions from 10 different fuels. A base version of the model was able to simulate the time-dependent evolution of the OA mass concentration and its oxygen-to-carbon ratio (O : C) at short photochemical ages (0.5 to 1 equivalent days). At longer photochemical ages (>1 equivalent day), the model exhibited poor skill in predicting the OA mass concentration and significantly underestimated the OA O : C. The modeled OA after several equivalent days of photochemical aging was slightly dominated by SOA (average of 57% across all experiments) with the remainder being POA (average of 43% across all experiments). Semi-volatile organic compounds, oxygenated aromatics, and heterocyclics accounted for the majority (89%, on average) of the SOA formed. Experimental artifacts (i.e., particle and vapor wall losses) were found to be much more important in influencing the OA evolution than other processes (i.e., dilution, heterogeneous chemistry, and oligomerization reactions). Adjustments to the kinetic model seemed to improve model performance only marginally indicating that the model was missing precursors, chemical pathways, or both, especially to explain the observed enhancement in OA mass and O : C over longer photochemical ages. While far from ideal, this work contributes to a process-level understanding of biomass burning OA that is relevant for its extended evolution at regional and global scales.

Atmospheric models of secondary organic aerosol (OA) (SOA) typically rely on parameters derived from environmental chambers. Chambers are subject to experimental artifacts, including losses of (1) particles to the walls (PWL), (2) vapors to the particles on the wall (V2PWL), and (3) vapors to the wall directly (VWL). We present a method for deriving artifact-corrected SOA parameters and translating these to volatility basis set (VBS) parameters for use in chemical transport models (CTMs). Our process involves combining a box model that accounts for chamber artifacts (Statistical Oxidation Model with a TwO-Moment Aerosol Sectional model (SOM-TOMAS)) with a pseudo-atmospheric simulation to develop VBS parameters that are fit across a range of OA mass concentrations. We found that VWL led to the highest percentage change in chamber SOA mass yields (high NOx: 36–680%; low NOx: 55–250%), followed by PWL (high NOx: 8–39%; low NOx: 10–37%), while the effects of V2PWL are negligible. In contrast to earlier work that assumed that V2PWL was a meaningful loss pathway, we show that V2PWL is an unimportant SOA loss pathway and can be ignored when analyzing chamber data. Using our updated VBS parameters, we found that not accounting for VWL may lead surface-level OA to be underestimated by 24% (0.25 μg m−3) as a global average or up to 130% (9.0 μg m–3) in regions of high biogenic or anthropogenic activity. Finally, we found that accurately accounting for PWL and VWL improves model-measurement agreement for fine mode aerosol mass concentrations (PM2.5) in the GEOS-Chem model.

Light-absorbing organic aerosols, commonly referred to as “brown carbon” (BrC), have important climate effects. The primary source of BrC is biomass burning, but additional BrC can be formed by less constrained secondary atmospheric reactions, such as photooxidation of aromatic volatile organic compounds (VOCs) and reactions of carbonyl compounds in secondary organic aerosols (SOAs) with ammonia (NH3). As NH3and VOC emissions increase globally, these insufficiently understood BrC production pathways may gain in importance relative to the primary BrC sources. This study examines the effects of NH3, NOx, and relative humidity (RH) on the optical and molecular properties of naphthalene (NAP) photooxidation SOAs. NAP SOAs were prepared by OH-initiated oxidation in a smog chamber at high and low levels of NOx, RH, and NH3. SOA hygroscopicity and optical properties were monitored online, and SOA samples were collected on filters for offline analysis. UV-visible spectroscopy and high-resolution mass spectrometry were used to determine mass absorption coefficients and molecular composition, respectively. Of the three parameters studied, RH exhibited the largest effects on both composition and optical properties – with an increase in the 〈O/C〉 ratio, relative dimer abundance, and absorption at wavelengths longer than 350 nm. Elevated NOxand NH3concentrations increased the amount of nitrogen incorporated into the SOA, and NOxincreased the amount of absorption at wavelengths longer than 350 nm while NH3had little effect. The combination of elevated humidity and NOxled to the formation of 6-nitro-2-naphthol, a strong chromophore with a distinct peak at 400 nm in the absorption data. We find that RH, NOx, and NH3all affect the characteristics of NAP SOAs in different ways: NOxand RH control both molecular composition and optical properties, while NH3has a stronger effect on composition and a minor effect on the absorption coefficient.

The ocean provides a nearly continuous source of certain primary particles emitted as sea spray from bubble bursting that are active as ice nucleating particles. They can impact ice formation, radiative transfer and precipitation processes in regions overlain by supercooled clouds. However, factors affecting their efficacy over time in the marine boundary layer are unresolved. One factor not previously evaluated is the impact of photochemical aging on the ice nucleating ability of emitted particles. We explore this factor for sea spray particles for the first time viameasurements of aerosols produced in a wave flume during a mesocosm experiment and using an oxidation flow reactor for exposing particles to oxidation by hydroxyl radicals. It is found that any amount of aging (here from 3 to 8 days equivalent) can often lead to degradation in ice nucleating particles concentrations, by factors of 2 to 5 times. By using an aerosol concentrator to enhance collection of ice nucleating particles (INPs) from a continuous flow chamber for offline analyses by transmission electron microscopy, atomic force microscopy, and Raman spectroscopy, compositional and morphological analyses of particles on different days suggested that so-called core–shell type sea salt INPs are particularly sensitive to oxidation. Raman libraries of the compositions of sea spray produced INPs were augmented herein, but a comprehensive understanding of the large range of INP compositions active at different temperatures remains elusive. Losses of particles with diameters above 2 μm in the flow reactor prevented full assessment of oxidation impacts at those sizes, and these losses secondarily confirmed supermicron sea spray as a predominant INP size class. While mechanisms for oxidative losses remain to be resolved, results imply that these reduce the ice nucleating activity of sea spray produced INPs by an equivalent temperature depression of ∼2 K during times of solar insolation over oceans.

Organic emissions from coastal waters play an important but poorly understood role in atmospheric chemistry in coastal regions. A mesocosm experiment focusing on facilitated biological blooms in coastal seawater, SeaSCAPE (Sea Spray Chemistry and Particle Evolution), was performed to study emission of volatile gases, primary sea spray aerosol, and formation of secondary marine aerosol as a function of ocean biological and chemical processes. Here, we report observations of aerosol-phase benzothiazoles in a marine atmospheric context with complementary measurements of dissolved-phase benzothiazoles. Though previously reported dissolved in polluted coastal waters, we report the first direct evidence of the transfer of these molecules from seawater into the atmosphere. We also report the first gas-phase observations of benzothiazole in the environment absent a direct industrial, urban, or rubber-based source. From the identities and temporal dynamics of the dissolved and aerosol species, we conclude that the presence of benzothiazoles in the coastal water (and thereby their emissions into the atmosphere) is primarily attributable to anthropogenic sources. Oxidation experiments to explore the atmospheric fate of gas-phase benzothiazole show that it produces secondary aerosol and gas-phase SO2, making it a potential contributor to secondary marine aerosol formation in coastal regions and a participant in atmospheric sulfur chemistry.

Particle phase state is a property of atmospheric aerosols that has important implications for the formation, evolution, and gas/particle partitioning of secondary organic aerosol (SOA). In this work, we use a size-resolved chemistry and microphysics model (Statistical Oxidation Model coupled to the TwO Moment Aerosol Sectional (SOM-TOMAS)), updated to include an explicit treatment of particle phase state, to constrain the bulk diffusion coefficient (Db) of SOA produced from α-pinene ozonolysis. By leveraging data from laboratory experiments performed in the absence of a seed and under dry conditions, we find that the Dbfor SOA can be constrained ((1–7) × 10–15cm2s–1in these experiments) by simultaneously reproducing the time-varying SOA mass concentrations and the evolution of the particle size distribution. Another version of our model that used the predicted SOA composition to calculate the glass-transition temperature, viscosity, and, ultimately, Db(∼10–15cm2s–1) of the SOA was able to reproduce the mass and size distribution measurements when we included oligomer formation (oligomers accounted for about a fifth of the SOA mass). Our work highlights the potential of a size-resolved SOA model to constrain the particle phase state of SOA using historical measurements of the evolution of the particle size distribution.

Secondary organic aerosols (SOA) constitute an important fraction of fine-mode atmospheric aerosol mass. Frameworks used to develop SOA parameters from laboratory experiments and subsequently used to simulate SOA formation in atmospheric models make many simplifying assumptions about the processes that lead to SOA formation in the interest of computational efficiency. These assumptions can limit the ability of the model to predict the mass, composition, and properties of SOA accurately. In this work, we developed a computationally efficient, process-level model named simpleSOM to represent the chemistry, thermodynamic properties, and microphysics of SOA. simpleSOM simulates multigenerational gas-phase chemistry, phase-state-influenced kinetic gas/particle partitioning, heterogeneous chemistry, oligomerization reactions, and vapor losses to the walls of Teflon chambers. As a case study, we used simpleSOM to simulate SOA formation from the photooxidation of α-pinene. This was done to demonstrate the ability of the model to develop parameters that can reproduce environmental chamber data, to highlight the chemical and microphysical processes within simpleSOM, and discuss implications for SOA formation in chambers and in the real atmosphere. SOA parameters developed from experiments performed in the chamber at the California Institute of Technology (Caltech) reproduced observations of SOA mass yield, O : C, and volatility distribution gathered from other experiments. Sensitivity simulations suggested that multigenerational gas-phase aging contributed to nearly half of all SOA and that in the absence of vapor wall losses, SOA production in the Caltech chamber could be nearly 50% higher. Heterogeneous chemistry did not seem to affect SOA formation over the short timescales for oxidation experienced in the chamber experiments. Simulations performed under atmospherically relevant conditions indicated that the SOA mass yields were sensitive to whether and how oligomerization reactions and the particle phase state were represented in the chamber experiment from which the parameters were developed. simpleSOM provides a comprehensive, process-based framework to consistently model the SOA formation and evolution in box and 3D models.

Marine aerosols play a critical role in impacting our climate by seeding clouds over the oceans. Despite decades of research, key questions remain regarding how ocean biological activity changes the composition and cloud-forming ability of marine aerosols. This uncertainty largely stems from an inability to independently determine the cloud-forming potential of primary versus secondary marine aerosols in complex marine environments. Here, we present results from a unique 6-day mesocosm experiment where we isolated and studied the cloud-forming potential of primary and secondary marine aerosols over the course of a phytoplankton bloom. The results from this controlled laboratory approach can finally explain the long-observed changes in the hygroscopic properties of marine aerosols observed in previous field studies. We find that secondary marine aerosols, consisting of sulfate, ammonium, and organic species, correlate with phytoplankton biomass (i.e., chlorophyll-a concentrations), whereas primary sea spray aerosol does not. Importantly, the measured CCN activity (κapp= 0.59 ± 0.04) of the resulting secondary marine aerosol matches the values observed in previous field studies, suggesting secondary marine aerosols play the dominant role in affecting marine cloud properties. Given these findings, future studies must address the physical, chemical, and biological factors controlling the emissions of volatile organic compounds that form secondary marine aerosol, with the goal of improving model predictions of ocean biology on atmospheric chemistry, clouds, and climate.

Biomass burning is the largest combustion-related source of volatile organic compounds (VOCs) to the atmosphere. We describe the development of a state-of-the-science model to simulate the photochemical formation of secondary organic aerosol (SOA) from biomass-burning emissions observed in dry (RH <20%) environmental chamber experiments. The modeling is supported by (i) new oxidation chamber measurements, (ii) detailed concurrent measurements of SOA precursors in biomass-burning emissions, and (iii) development of SOA parameters for heterocyclic and oxygenated aromatic compounds based on historical chamber experiments. We find that oxygenated aromatic compounds, including phenols and methoxyphenols, account for slightly less than 60% of the SOA formed and help our model explain the variability in the organic aerosol mass (R2= 0.68) and O/C (R2= 0.69) enhancement ratios observed across 11 chamber experiments. Despite abundant emissions, heterocyclic compounds that included furans contribute to ∼20% of the total SOA. The use of pyrolysis-temperature-based or averaged emission profiles to represent SOA precursors, rather than those specific to each fire, provide similar results to within 20%. Our findings demonstrate the necessity of accounting for oxygenated aromatics from biomass-burning emissions and their SOA formation in chemical mechanisms.

On behalf of the journal, AGU, and the scientific community, the editors of Geophysical Research Letters would like to sincerely thank those who reviewed manuscripts for us in 2023. The hours reading and commenting on manuscripts not only improve the manuscripts, but also increase the scientific rigor of future research in the field. With the advent of AGU's data policy, many reviewers have also helped immensely to evaluate the accessibility and availability of data, and many have provided insightful comments that helped to improve the data presentation and quality. We greatly appreciate the assistance of the reviewers in advancing open science, which is a key objective of AGU's data policy. We particularly appreciate the timely reviews in light of the demands imposed by the rapid review process at Geophysical Research Letters. We received 4,512 submissions in 2023 and 5,112 reviewers contributed to their evaluation by providing 8,587 reviews in total. We deeply appreciate their contributions. Individuals in italics provided three or more reviews for GRL in 2023. The editors thank the 2023 peer‐reviewers The editors thank the 2023 peer‐reviewers

The mixing state of black carbon (BC) affects its environmental fate and impacts. This work investigates particle diversity and mixing state for refractory BC (rBC) containing particles in an urban environment. The chemical compositions of individual rBC-containing particles were measured, from which a mixing state index and particle diversity were determined. The mixing state index (χ) varied between 26% and 69% with the average of 48% in this study and was slightly enhanced with the photochemical age of air masses, indicating that most of the rBC-containing particles cannot be simply explained by fully externally and internally mixed model. Clustering of single particle measurements was used to investigate the potential effects of different primary emissions and atmospheric processes on rBC-containing particle diversity and mixing state. The average particle species diversity and the bulk population species diversity both increased with primary traffic emissions and elevated nitrate concentrations in the morning but gradually decreased with secondary organic aerosol (SOA) formation in the afternoon. The single particle clustering results illustrate that primary traffic emissions and entrainment of nitrate-containing rBC particles from the residual layer to the surface could lead to more heterogeneous aerosol compositions, whereas substantial fresh SOA formation near vehicular emissions made the rBC-containing particles more homogeneous. This work highlights the importance of considering particle diversity and mixing state for investigating the chemical evolution of rBC-containing particles and the potential effects of coating on BC absorption enhancement.

Stay-at-home policies invoked in response to COVID-19 have led to well-publicized drops in some air pollutants. The extent to which such reductions translate to improved air quality is dictated by not only emissions and meteorology, but also chemical transformations in the atmosphere.

Observations from a wintertime and summertime field campaign are used to assess the relationship between black and brown carbon (BC and BrC, respectively) optical properties and particle composition and coating state. The wintertime campaign, in Fresno, CA, was impacted by primary emissions from residential wood burning, secondary organic and inorganic particle formation, and BC from motor vehicles. Two major types of BrC were observed in wintertime. One occurred primarily at night—the result of primary biomass burning emissions. The second was enhanced in daytime and strongly associated with particulate nitrate and the occurrence of fog. The biomass‐burning‐derived BrC absorbed more strongly than the nitrate‐associated BrC but had a weaker wavelength dependence. The wintertime BC‐specific mass absorption coefficient (MACBC) exhibited limited dependence on the ensemble‐average coating‐to‐BC mass ratio (Rcoat‐rBC) at all wavelengths, even up to Rcoat‐rBCof ~5. For the summertime campaign, in Fontana, CA, BC dominated the light absorption, with negligible BrC contribution even after substantial photochemical processing. The summertime MACBCexhibited limited dependence on Rcoat‐rBC, even up to ratios of >10. Based on the four classes of BC‐containing particles identified by Lee et al. (2017, https://doi.org/10.5194/acp‐17‐15055‐2017) for the summertime measurements, the general lack of an absorption enhancement can be partly—although not entirely—attributed to an unequal distribution of coating materials between the BC‐containing particle types. These observations demonstrate that in relatively near‐source environments, even those impacted by strong secondary aerosol production, the ensemble‐average, mixing‐induced absorption enhancement for BC due to coatings can be quite small. Particles in the atmosphere can scatter light, which has a cooling effect, or absorb light, which can contribute to localized atmospheric warming. Black carbon is a highly absorbing yet short‐lived climate pollutant that when coated with other materials can in theory have enhanced absorption. Organic compounds in particles can also absorb light, although tend to absorb less strongly than black carbon. Absorbing organic compounds are collectively referred to as brown carbon. We measured the composition and light absorption properties of atmospheric particles in wintertime Fresno, CA, and summertime Fontana, CA. In Fresno, we found two types of brown carbon contributed significantly to the overall light absorption by particles, in addition to absorption by black carbon. One of the brown carbon aerosol types in Fresno was emitted during wood burning, and the other was produced from chemical reactions in the atmosphere. In summertime Fontana, black carbon particles dominated the light absorption, with little contribution from brown carbon. Overall, at both sites the coating of materials onto black carbon particles had a limited impact on the absorption by black carbon, except to the extent that the materials themselves were absorbing. Two co‐located types of ambient brown carbon were characterized, one from biomass combustion and one from secondary aerosol formationLimited mixing‐induced absorption enhancement observed in two distinct environments, despite substantial average coatings on black carbon

Organic aerosol mass (OM) components were investigated at Fresno in winter and at Fontana in summer by positive matrix factorization of high‐resolution time‐of‐flight aerosol mass spectra and of Fourier Transform infrared spectra, as well as by k‐means clustering of light‐scattering (LS) aerosol single‐particle spectra. The results were comparable for all three methods at both sites, showing different contributions of primary and secondary organic aerosol sources to PM1. At Fresno biomass burning organic aerosol contributed 27% of OM on low‐fog days, and nitrate‐related oxidized OA (NOOA) accounted for 47% of OM on high‐fog days, whereas at Fontana very oxygenated organic aerosol (VOOA) components contributed 58–69% of OM. Amine and organosulfate fragment concentrations were between 2 and 3 times higher on high‐fog days than on low‐fog days at Fresno, indicating increased formation from fog‐related processes. NOOA and biomass burning organic aerosol components were largely on different particles than the VOOA components in Fresno, but in Fontana both NOOA and VOOA components were distributed on most particle types, consistent with a longer time for and a larger contribution from gas‐phase photochemical secondary organic aerosol formation in summer Fontana than winter Fresno. Uncommon trace organic fragments, elevated inorganic, and alcohol group submicron mass concentrations persisted at Fontana for more than 5 days after 4 July fireworks. These unique aerosol chemical compositions at Fresno and Fontana show substantial and extended air‐quality impacts from residential burning and fireworks. Oxidized organic and amine fragment concentrations were higher on high‐fog days than on low‐fog days at FresnoUncommon trace organic fragments (m/z27 and m/z63), nitrate, sulfate, and single‐particle types associated with fireworks persisted at high concentrations at Fontana for 5 days after emissionNitrate‐related and other organic aerosol mass factors were largely on different particle types at Fresno but were mixed at Fontana

We developed a parametrizable box model to empirically derive the yields of semivolatile products from VOC oxidation using chamber measurements, while explicitly accounting for the multigenerational chemical aging processes (such as the gas-phase fragmentation and functionalization and aerosol-phase oligomerization and photolysis) under different NOxlevels and the loss of particles and gases to chamber walls. Using the oxidation of isoprene as an example, we showed that the assumptions regarding the NOx-sensitive, multigenerational aging processes of VOC oxidation products have large impacts on the parametrized product yields and SOA formation. We derived sets of semivolatile product yields from isoprene oxidation under different NOxlevels. However, we stress that these product yields must be used in conjunction with the corresponding multigenerational aging schemes in chemical transport models. As more mechanistic insights regarding SOA formation from VOC oxidation emerge, our box model can be expanded to include more explicit chemical aging processes and help ultimately bridge the gap between the process-based understanding of SOA formation from VOC oxidation and the bulk-yield parametrizations used in chemical transport models.

Inorganic and organic coatings on black carbon (BC) particles can enhance light absorption and affect atmospheric lifetimes of BC‐containing particles and thus have significant implications for climate. To study the physical and chemical characteristics of atmospheric BC and BC‐associated coatings, a soot particle‐aerosol mass spectrometer was deployed during the winter of 2014–2015 in Fresno, a city located in the San Joaquin Valley of California, to selectively analyze BC‐containing particles. Comparing soot particle‐aerosol mass spectrometer measurements to those from the collocated single‐particle soot photometer (SP2) and high‐resolution aerosol mass spectrometer, we found that 17% of total submicrometer aerosol mass was associated with BC‐containing particles, suggesting that a majority of the fine particles in Fresno contained no BC. Most BC‐containing particles appeared to be associated with residential wood burning and vehicular traffic. These particles typically had a bulk‐average mass ratio of coating to BC (Rcoat/rBC) less than 2. However, during periods of persistent fog larger Rcoat/rBCvalues were observed, with the coatings primarily composed of secondary inorganic and organic components that likely resulted from aqueous‐phase processing. Specifically, compared to periods with less fog, the BC coating increased in concentration and contained a larger fraction of nitrate and oxidized organic matter. The size distributions of BC and associated organic coating were generally centered around 300 nm in vacuum aerodynamic diameter. However, during foggy periods BC had an additional peak at ~400 nm and organics and nitrate displayed a prominent mode in the accumulation size range. Various combustion processes can emit soot, or black carbon (BC), particles with properties highly relevant to climate change and respiratory health. Often, BC particles are coated with other materials derived from the same combustion source or added in the atmosphere as these particles age. This coating material can have profound effects on the behavior, properties, and longevity of BC. In this study we deployed an instrument called a soot particle‐aerosol mass spectrometer to selectively analyze particles containing BC and investigate their coating, concentration, and composition in real time in Fresno, CA, in wintertime. The properties of BC particles were found to be mainly controlled by emission sources but were also significantly influenced by humid meteorological conditions. Black carbon (BC)‐containing particles and associated coatings were analyzed, and their composition and size were influenced by meteorologyBC sources during winter included residential wood burning and vehiclesBC‐containing particles were generally thinly coated, but aqueous‐phase processing significantly enhanced the secondary coating amount

Anthropogenic emissions and land use changes have modified atmospheric aerosol concentrations and size distributions over time. Understanding preindustrial conditions and changes in organic aerosol due to anthropogenic activities is important because these features (1) influence estimates of aerosol radiative forcing and (2) can confound estimates of the historical response of climate to increases in greenhouse gases. Secondary organic aerosol (SOA), formed in the atmosphere by oxidation of organic gases, represents a major fraction of global submicron‐sized atmospheric organic aerosol. Over the past decade, significant advances in understanding SOA properties and formation mechanisms have occurred through measurements, yet current climate models typically do not comprehensively include all important processes. This review summarizes some of the important developments during the past decade in understanding SOA formation. We highlight the importance of some processes that influence the growth of SOA particles to sizes relevant for clouds and radiative forcing, including formation of extremely low volatility organics in the gas phase, acid‐catalyzed multiphase chemistry of isoprene epoxydiols, particle‐phase oligomerization, and physical properties such as volatility and viscosity. Several SOA processes highlighted in this review are complex and interdependent and have nonlinear effects on the properties, formation, and evolution of SOA. Current global models neglect this complexity and nonlinearity and thus are less likely to accurately predict the climate forcing of SOA and project future climate sensitivity to greenhouse gases. Efforts are also needed to rank the most influential processes and nonlinear process‐related interactions, so that these processes can be accurately represented in atmospheric chemistry‐climate models. Secondary organic aerosol (SOA), formed in the atmosphere by oxidation of organic gases, often represents a major fraction of global submicron‐sized atmospheric organic aerosol. Myriad processes affect SOA formation, several of which relate to interactions between natural biogenic emissions and predominantly anthropogenic species such as SO2, NOx, sulfate, nitrate, and ammonium. Many of these key processes are nonlinear and can be synergistic or act to compensate each other in terms of climate forcing. Current atmospheric chemistry‐climate models mostly do not treat these processes. We highlight a number of process‐level mechanisms related to the interactions between anthropogenic and biogenic SOA precursors, for which the corresponding impacts on the radiative effects of SOA need to be investigated in atmospheric chemistry‐climate models. Ultimately, climate models need to capture enough important features of the chemical and dynamic evolution of SOA, in terms of both aerosol number and aerosol mass, as a function of atmospheric variables and anthropogenic perturbations to reasonably predict the spatial and temporal distributions of SOA. A better understanding of SOA formation mechanisms and physical properties is needed to improve estimates of the extent to which anthropogenic emissions and land use changes have modified global aerosol concentrations and size distributions since preindustrial times. We review some important developments in secondary organic aerosol (SOA) that could impact aerosol radiative forcing and response of climate to greenhouse gasesWe highlight some of the important processes that involve interactions between natural biogenic emissions and anthropogenic emissionsWe discuss fundamental SOA properties volatility and viscosity and their relation to evolution of aerosol mass and number concentrations in the atmosphere

We report simultaneous, underway eddy covariance measurements of the vertical flux of isoprene, total monoterpenes, and dimethyl sulfide (DMS) over the Northern Atlantic Ocean during fall. Mean isoprene and monoterpene sea‐to‐air vertical fluxes were significantly lower than mean DMS fluxes. While rare, intense monoterpene sea‐to‐air fluxes were observed, coincident with elevated monoterpene mixing ratios. A statistically significant correlation between isoprene vertical flux and short wave radiation was not observed, suggesting that photochemical processes in the surface microlayer did not enhance isoprene emissions in this study region. Calculations of secondary organic aerosol production rates (PSOA) for mean isoprene and monoterpene emission rates sampled here indicate that PSOAis on average <0.1 μg m−3d−1. Despite modest PSOA, low particle number concentrations permit a sizable role for condensational growth of monoterpene oxidation products in altering particle size distributions and the concentration of cloud condensation nuclei during episodic monoterpene emission events from the ocean. Sea‐to‐air fluxes of dimethyl sulfide were observed to be factor of 10 larger than either isoprene or monoterpenes over the North Atlantic Ocean during fallThe production rate of secondary organic aerosol, stemming from marine isoprene and monoterpene emission, is calculated to be small compared to primary emissionsRare, intense ocean emission of monoterpenes can have a sizeable impact on particle size distributions and in turn the number concentration of cloud condensation nuclei

The composition and concentrations of water‐soluble gases and ionic aerosol components were measured from January to February 2013 in Fresno, CA, with a particle‐into‐liquid sampler with ion chromatography and annular denuders. The average (±1σ) ionic aerosol mass concentration was 15.0 (±9.4) µg m−3, and dominated by nitrate (61%), followed by ammonium, sulfate, chloride, potassium, nitrite, and sodium. Aerosol‐phase organic acids, including formate and glycolate, and amines including methylaminium, triethanolaminium, ethanolaminium, dimethylaminium, and ethylaminium were also detected. Although the dominant species all came from secondary aerosol formation, there were primary sources of ionic aerosols as well, including biomass burning for potassium and glycolate, sea spray for sodium, chloride, and dimethylamine, and vehicles for formate. Particulate methanesulfonic acid was also detected and mainly associated with terrestrial sources. On average, the molar concentration of ammonia was 49 times greater than nitric acid, indicating that ammonium nitrate formation was limited by nitric acid availability. Particle water was calculated based on the Extended Aerosol Inorganics Model (E‐AIM) thermodynamic prediction of inorganic particle water and κ‐Köhler theory approximation of organic particle water. The average (±1σ) particle water concentration was 19.2 (±18.6) µg m−3, of which 90% was attributed to inorganic species. The fractional contribution of particle water to total fine particle mass averaged at 36% during this study and was greatest during early morning and night and least during the day. Based on aqueous‐phase concentrations of ions calculated by using E‐AIM, the average (±1σ) pH of particles in Fresno during the winter was estimated to be 4.2 (±0.2). Ionic aerosol mass in Fresno, CA, during the winter is dominated by NH4NO3, and NH4NO3production is limited by HNO3availabilityParticulate amines and organic acids were quantified, and their sources were discussedParticle water is an important component of ambient fine PM, and the concentration is primarily controlled by inorganic composition and RH

On behalf of the journal, AGU, and the scientific community, the editors of Geophysical Research Letters would like to sincerely thank those who reviewed manuscripts for us in 2022. The hours reading and commenting on manuscripts not only improve the manuscripts, but also increase the scientific rigor of future research in the field. With the advent of AGU's data policy, many reviewers have also helped immensely to evaluate the accessibility and availability of data, and many have provided insightful comments that helped to improve the data presentation and quality. We greatly appreciate the assistance of the reviewers in advancing open science, which is a key objective of AGU's data policy. We particularly appreciate the timely reviews in light of the demands imposed by the rapid review process at Geophysical Research Letters. We received 6,687 submissions in 2022 and 5,247 reviewers contributed to their evaluation by providing 8,720 reviews in total. We deeply appreciate their contributions in these challenging times. Individuals in italics provided three or more reviews for GRL in 2022. The editors thank the 2022 peer reviewers The editors thank the 2022 peer reviewers

With the oceans covering 71% of the Earth, sea spray aerosol (SSA) particles profoundly impact climate through their ability to scatter solar radiation and serve as seeds for cloud formation. The climate properties can change when sea salt particles become mixed with insoluble organic material formed in ocean regions with phytoplankton blooms. Currently, the extent to which SSA chemical composition and climate properties are altered by biological processes in the ocean is uncertain. To better understand the factors controlling SSA composition, we carried out a mesocosm study in an isolated ocean-atmosphere facility containing 3,400 gallons of natural seawater. Over the course of the study, two successive phytoplankton blooms resulted in SSA with vastly different composition and properties. During the first bloom, aliphatic-rich organics were enhanced in submicron SSA and tracked the abundance of phytoplankton as indicated by chlorophyll-a concentrations. In contrast, the second bloom showed no enhancement of organic species in submicron particles. A concurrent increase in ice nucleating SSA particles was also observed only during the first bloom. Analysis of the temporal variability in the concentration of aliphatic-rich organic species, using a kinetic model, suggests that the observed enhancement in SSA organic content is set by a delicate balance between the rate of phytoplankton primary production of labile lipids and enzymatic induced degradation. This study establishes a mechanistic framework indicating that biological processes in the ocean and SSA chemical composition are coupled not simply by ocean chlorophyll-a concentrations, but are modulated by microbial degradation processes. This work provides unique insight into the biological, chemical, and physical processes that control SSA chemical composition, that when properly accounted for may explain the observed differences in SSA composition between field studies.

Aerosol particles influence global climate by determining cloud droplet number concentrations, brightness, and lifetime. Primary aerosol particles, such as those produced from breaking waves in the ocean, display large particle–particle variability in chemical composition, morphology, and physical phase state, all of which affect the ability of individual particles to accommodate water and grow into cloud droplets. Despite such diversity in molecular composition, there is a paucity of methods available to assess how particle–particle variability in chemistry translates to corresponding differences in aerosol hygroscopicity. Here, an approach has been developed that allows for characterization of the distribution of aerosol hygroscopicity within a chemically complex population of atmospheric particles. This methodology, when applied to the interpretation of nascent sea spray aerosol, provides a quantitative framework for connecting results obtained using molecular mimics generated in the laboratory with chemically complex ambient aerosol. We show that nascent sea spray aerosol, generated in situ in the Atlantic Ocean, displays a broad distribution of particle hygroscopicities, indicative of a correspondingly broad distribution of particle chemical compositions. Molecular mimics of sea spray aerosol organic material were used in the laboratory to assess the volume fractions and molecular functionality required to suppress sea spray aerosol hygroscopicity to the extent indicated by field observations. We show that proper accounting for the distribution and diversity in particle hygroscopicity and composition are important to the assessment of particle impacts on clouds and global climate.