Aerosol Precursors Research Articles

Atmospheric Chemistry of CH2OO: The Hydrolysis of CH2OO in Small Clusters of Sulfuric Acid.

The hydrolysis of CH2OO is not only a dominant sink for the CH2OO intermediate in the atmosphere but also a key process in the formation of aerosols. Herein, the reaction mechanism and kinetics for the hydrolysis of CH2OO catalyzed by the precursors of atmospheric aerosols, including H2SO4, H2SO4···H2O, and (H2SO4)2, have been studied theoretically at the CCSD(T)-F12a/cc-pVDZ-F12//B3LYP/6-311+G(2df,2pd) level. The calculated results show that the three catalysts decrease the energy barrier by over 10.3 kcal·mol-1; at the same time, the product formation of HOCH2OOH is more strongly bonded to the three catalysts than to the reactants CH2OO and H2O, revealing that small clusters of sulfuric acid promote the hydrolysis of CH2OO both kinetically and thermodynamically. Kinetic simulations show that the H2SO4-assisted reaction is more favorable than the H2SO4···H2O- (the pseudo-first-order rate constant being 27.9-11.5 times larger) and (H2SO4)2- (between 2.8 × 104 and 3.4 × 105 times larger) catalyzed reactions. Additionally, due to relatively lower concentration of H2SO4, the hydrolysis of CH2OO with H2SO4 cannot compete with the CH2OO + H2O or (H2O)2 reaction within the temperature range of 280-320 K, since its pseudo-first-order rate ratio is smaller by 4-7 or 6-8 orders of magnitude, respectively. However, the present results provide a good example of how small clusters of sulfuric acid catalyze the hydrolysis of an important atmospheric species.

Observations Confirm that Volatile Chemical Products Are a Major Source of Petrochemical Emissions in U.S. Cities.

Despite decades of declining air pollution, urban U.S. areas are still affected by summertime ozone and wintertime particulate matter exceedance events. Volatile organic compounds (VOCs) are known precursors of secondary organic aerosol (SOA) and photochemically produced ozone. Urban VOC emission sources, including on-road transportation emissions, have decreased significantly over the past few decades through successful regulatory measures. These drastic reductions in VOC emissions have led to a change in the distribution of urban emissions and noncombustion sources of VOCs such as those from volatile chemical products (VCPs), which now account for a higher fraction of the urban VOC burden. Given this shift in emission sources, it is essential to quantify the relative contribution of VCP and mobile source emissions to urban pollution. Herein, ground site and mobile laboratory measurements of VOCs were performed. Two ground site locations with different population densities, Boulder, CO, and New York City (NYC), NY, were chosen in order to evaluate the influence of VCPs in cities with varying mixtures of VCPs and mobile source emissions. Positive matrix factorization was used to attribute hundreds of compounds to mobile- and VCP-dominated sources. VCP-dominated emissions contributed to 42 and 78% of anthropogenic VOC emissions for Boulder and NYC, respectively, while mobile source emissions contributed 58 and 22%. Apportioned VOC emissions were compared to those estimated from the Fuel-based Inventory of Vehicle Emissions and VCPs and agreed to within 25% for the bulk comparison and within 30% for more than half of individual compounds. The evaluated inventory was extended to other U.S. cities and it suggests that 50 to 80% of emissions, reactivity, and the SOA-forming potential of urban anthropogenic VOCs are associated with VCP-dominated sources, demonstrating their important role in urban U.S. air quality.

Association of cardiorespiratory hospital admissions with ambient volatile organic compounds: Evidence from a time-series study in Taipei, Taiwan

As important precursors of ozone and secondary organic aerosols, the harmful impact of exposure to ambient volatile organic compounds (VOCs) is of public health interest. However, few studies have investigated the health risks of numerous individual VOC species. This study linked the daily concentrations of 54 C2–C11 VOC species monitored from the Wanhua Photochemical Assessment Monitoring Station and hospital admissions for cardiorespiratory diseases in Taipei, Taiwan, from the National Health Insurance Research Database. A standard time-series approach entailing a series of sensitivity analyses was applied to investigate the short-term health risks of exposure to VOC subgroups and species. Consistent associations of all VOC subgroups and main species with chronic obstructive pulmonary disease (COPD) hospitalizations were demonstrated. In addition, associations of the C5–C6 alkanes, C2–C3 alkenes, toluene, and xylene with asthma hospitalizations were found, as were associations of aromatic hydrocarbons with hospitalizations for heart failure. An interquartile range increase in total VOC exposure at lag0 day (102.6 parts per billion carbon) was associated with increments of 1.84% (95% confidence interval: 0.54%–3.15%), 1.65% (0.71%–2.60%), and 1.21% (0.36%–2.07%) in hospitalizations for asthma, COPD, and heart failure, respectively. The effect estimates were robust with data excluding extreme values, the second pollutant adjustment for PM2.5 and O3, and the Bonferroni correction. The associations of ambient VOC exposure with cardiorespiratory hospitalizations in Taipei serve as a reference for VOC regulations and ozone control strategies.

Is the efficacy of satellite-based inversion of SO2 emission model dependent?

Satellite-based inverse modeling has the potential to drive aerosol precursor emissions, but its efficacy for improving chemistry transport models (CTMs) remains elusive because of its likely inherent dependence on the error characteristics of a specific CTM used for the inversion. This issue is quantitively assessed here by using three CTMs. We show that SO2 emissions from global GEOS-Chem adjoint model and OMI SO2 data, when combined with spatial variation of bottom-up emissions, can largely improve WRF-Chem and WRF-CMAQ forecast of SO2 and aerosol optical depth (in reference to moderate resolution imaging spectroradiometer data) in China. This suggests that the efficacy of satellite-based inversion of SO2 emission appears to be high for CTMs that use similar or identical emission inventories. With the advent of geostationary air quality monitoring satellites in next 3 years, this study argues that an era of using top-down approach to rapidly update emission is emerging for regional air quality forecast, especially over Asia having highly varying emissions.

Influence of aromatics on tropospheric gas-phase composition

Abstract. Aromatics contribute a significant fraction to organic compounds in the troposphere and are mainly emitted by anthropogenic activities and biomass burning. Their oxidation in lab experiments is known to lead to the formation of ozone and aerosol precursors. However, their overall impact on tropospheric composition is uncertain as it depends on transport, multiphase chemistry, and removal processes of the oxidation intermediates. Representation of aromatics in global atmospheric models has been either neglected or highly simplified. Here, we present an assessment of their impact on gas-phase chemistry, using the general circulation model EMAC (ECHAM5/MESSy Atmospheric Chemistry). We employ a comprehensive kinetic model to represent the oxidation of the following monocyclic aromatics: benzene, toluene, xylenes, phenol, styrene, ethylbenzene, trimethylbenzenes, benzaldehyde, and lumped higher aromatics that contain more than nine C atoms. Significant regional changes are identified for several species. For instance, glyoxal increases by 130 % in Europe and 260 % in East Asia, respectively. Large increases in HCHO are also predicted in these regions. In general, the influence of aromatics is particularly evident in areas with high concentrations of NOx, with increases up to 12 % in O3 and 17 % in OH. On a global scale, the estimated net changes of trace gas levels are minor when aromatic compounds are included in our model. For instance, the tropospheric burden of CO increases by about 6 %, while the burdens of OH, O3, and NOx (NO+NO2) decrease between 3 % and 9 %. The global mean changes are small, partially because of compensating effects between high- and low-NOx regions. The largest change is predicted for the important aerosol precursor glyoxal, which increases globally by 36 %. In contrast to other studies, the net change in tropospheric ozone is predicted to be negative, −3 % globally. This change is larger in the Northern Hemisphere where global models usually show positive biases. We find that the reaction with phenoxy radicals is a significant loss for ozone, on the order of 200–300 Tg yr−1, which is similar to the estimated ozone loss due to bromine chemistry. Although the net global impact of aromatics is limited, our results indicate that aromatics can strongly influence tropospheric chemistry on a regional scale, most significantly in East Asia. An analysis of the main model uncertainties related to oxidation and emissions suggests that the impact of aromatics may even be significantly larger.

Importance of Hydroxyl Radical Chemistry in Isoprene Suppression of Particle Formation from α-Pinene Ozonolysis

Monoterpenes and isoprene, emitted primarily by vegetation, represent a globally dominant source of secondary organic aerosol (SOA) precursors. Previous studies have shown that isoprene suppresses ...

Molecular mechanism for rapid autoxidation in \u03b1-pinene ozonolysis

Aerosol affects Earth’s climate and the health of its inhabitants. A major contributor to aerosol formation is the oxidation of volatile organic compounds. Monoterpenes are an important class of volatile organic compounds, and recent research demonstrate that they can be converted to low-volatility aerosol precursors on sub-second timescales following a single oxidant attack. The α-pinene + O3 system is particularly efficient in this regard. However, the actual mechanism behind this conversion is not understood. The key challenge is the steric strain created by the cyclobutyl ring in the oxidation products. This strain hinders subsequent unimolecular hydrogen-shift reactions essential for lowering volatility. Using quantum chemical calculations and targeted experiments, we show that the excess energy from the initial ozonolysis reaction can lead to novel oxidation intermediates without steric strain, allowing the rapid formation of products with up to 8 oxygen atoms. This is likely a key route for atmospheric organic aerosol formation.

Surprisingly long lifetime of methacrolein oxide, an isoprene derived Criegee intermediate, under humid conditions

Ozonolysis of isoprene, the most abundant alkene, produces three distinct Criegee intermediates (CIs): CH2OO, methyl vinyl ketone oxide (MVKO) and methacrolein oxide (MACRO). The oxidation of SO2 by CIs is a potential source of H2SO4, an important precursor of aerosols. Here we investigated the UV-visible spectroscopy and reaction kinetics of thermalized MACRO. An extremely fast reaction of anti-MACRO with SO2 has been found, kSO2 = (1.5 ± 0.4) × 10−10 cm3 s−1 (±1σ, σ is the standard deviation of the data) at 298 K (150 − 500 Torr), which is ca. 4 times the value for syn-MVKO. However, the reaction of anti-MACRO with water vapor has been observed to be quite slow with an effective rate coefficient of (9 ± 5) × 10−17 cm3 s−1 (±1σ) at 298 K (300 to 500 Torr), which is smaller than current literature values by 1 or 2 orders of magnitude. Our results indicate that anti-MACRO has an atmospheric lifetime (best estimate ca. 18 ms at 298 K and RH = 70%) much longer than previously thought (ca. 0.3 or 3 ms), resulting in a much higher steady-state concentration. Owing to larger reaction rate coefficient, the impact of anti-MACRO on the oxidation of atmospheric SO2 would be substantial, even more than that of syn-MVKO.

Explosive Secondary Aerosol Formation during Severe Haze in the North China Plain.

Severe haze events with exceedingly high-levels of fine aerosols occur frequently over the past decades in the North China Plain (NCP), exerting profound impacts on human health, weather, and climate. The development of effective mitigation policies requires a comprehensive understanding of the haze formation mechanisms, including identification and quantification of the sources, formation, and transformation of the aerosol species. Haze evolution in this region exhibits distinct physical and chemical characteristics from clean to polluted periods, as evident from increasing stagnation and relative humidity, but decreasing solar radiation as well as explosive secondary aerosol formation. The latter is attributed to highly elevated concentrations of aerosol precursor gases and is reflected by rapid increases in the particle number and mass concentrations, both corresponding to nonequilibrium chemical processes. Considerable new knowledge has been acquired to understand the processes regulating haze formation, particularly in light of the progress in elucidating the aerosol formation mechanisms. This review synthesizes recent advances in understanding secondary aerosol formation, by highlighting several critical chemical/physical processes, that is, new particle formation and aerosol growth driven by photochemistry and aqueous chemistry as well as the interaction between aerosols and atmospheric stability. Current challenges and future research priorities are also discussed.

Real-time tracing VOCs, O3 and PM2.5 emission sources with vehicle-mounted proton transfer reaction mass spectrometry combined differential absorption lidar

Owing to rapid economic development and urbanization, environmental problems caused by PM2.5 and O3 have been occurring frequently. Volatile organic compounds (VOCs) are significant precursors of O3 and secondary organic aerosols that contribute to PM2.5. The study of VOC pollution characteristics is of great significance for providing a reference to guide its reduction policy formulation. Proton transfer reaction mass spectrometry has been widely used to study the emissions, distributions, and chemical evolution of VOCs in the atmosphere. A differential absorption lidar is often used to detect O3 concentration profiles and aerosol extinction coefficient profiles in low troposphere. In this study, a novel vehicle-mounted differential absorption lidar combined with a PTR-MS system is used to track environmental VOCs, particulate matter and O3 emission sources in real time. Plane scanning results can determine the contaminated areas on a large scale. The results of particulate matter navigation and fixed vertical detection both showed that local pollution and high-altitude input pollution together lead to poor air quality. Navigation experimental results show that the pollution sources are mainly concentrated in the vicinity of traffic intersections, polluting enterprises and residential areas. O3, particulate matter and VOCs have the same high value region.

New Insights into Secondary Organic Aerosol Formation: Water Binding to Limonene.

Limonene is an abundant monoterpene in the atmosphere and one of the main precursors of secondary organic aerosol. Understanding its interactions with atmospheric molecules is crucial to explain aerosol formation and the various products obtained from competing reaction pathways. Here, using broadband rotational spectroscopy in combination with computational calculations, we show that limonene effectively interacts with water, forming a variety of complexes. Seven different isomers of limonene-H2O, where water and limonene are connected by O-H···π and C-H···O interactions, have been unambiguously identified. Water has been found to preferentially bind to the endocyclic double bond of limonene. Our findings demonstrate a striking ability of water to attach to limonene and enrich our knowledge on the possible interactions of limonene in the atmosphere.

Long-term measurement of sub-3 nm particles and their precursor gases in the boreal forest

Abstract. The knowledge of the dynamics of sub-3 nm particles in the atmosphere is crucial for our understanding of the first steps of atmospheric new particle formation. Therefore, accurate and stable long-term measurements of the smallest atmospheric particles are needed. In this study, we analyzed over 5 years of particle concentrations in size classes 1.1–1.7 and 1.7–2.5 nm obtained with the particle size magnifier (PSM) and 3 years of precursor vapor concentrations measured with the chemical ionization atmospheric pressure interface time-of-flight mass spectrometer (CI-APi-ToF) at the SMEAR II station in Hyytiälä, Finland. The results show that there are significant seasonal differences in median concentrations of sub-3 nm particles, but the two size classes behave partly differently. The 1.1–1.7 nm particle concentrations are highest in summer, while the 1.7–2.5 nm particle concentrations are highest in springtime. The 1.7–2.5 nm particles exhibit a daytime maximum in all seasons, while the 1.1–1.7 nm particles have an additional evening maximum during spring and summer. Aerosol precursor vapors have notable diurnal and seasonal differences as well. Sulfuric acid and highly oxygenated organic molecule (HOM) monomer concentrations have clear daytime maxima, while HOM dimers have their maxima during the night. HOM concentrations for both monomers and dimers are the highest during summer and the lowest during winter following the biogenic activity in the surrounding forest. Sulfuric acid concentrations are the highest during spring and summer, with autumn and winter concentrations being 2 to 3 times lower. A correlation analysis between the sub-3 nm concentrations and aerosol precursor vapor concentrations indicates that both HOMs (particularly their dimers) and sulfuric acid play a significant role in new particle formation in the boreal forest. Our analysis also suggests that there might be seasonal differences in new particle formation pathways that need to be investigated further.

The production and hydrolysis of organic nitrates from OH radical oxidation of <i>β</i>-ocimene

Abstract. Biogenic volatile organic compounds (BVOCs) emitted by plants represent the largest source of non-methane hydrocarbon emissions on Earth. Photochemical oxidation of BVOCs represents a significant pathway in the production of secondary organic aerosol (SOA), affecting Earth's radiative balance. Organic nitrates (RONO2), formed from the oxidation of BVOCs in the presence of NOx, represent important aerosol precursors and affect the oxidative capacity of the atmosphere, in part by sequestering NOx. In the aerosol phase, RONO2 hydrolyze to form nitric acid and numerous water-soluble products, thus contributing to an increase in aerosol mass. However, only a small number of studies have investigated the production of RONO2 from OH oxidation of terpenes, and among those, few have studied their hydrolysis. Here, we report a laboratory study of OH-initiated oxidation of β-ocimene, an acyclic, tri-olefinic monoterpene released during the daytime from vegetation, including forests, agricultural landscapes, and grasslands. We conducted studies of the OH oxidation of β-ocimene in the presence of NOx using a 5.5 m3 all-Teflon photochemical reaction chamber, during which we quantified the total (gas- and particle-phase) RONO2 yield and the SOA yields. We sampled the organic nitrates produced and measured their hydrolysis rate constants across a range of atmospherically relevant pH. The total organic nitrate yield was determined to be 38(±9) %, consistent with the available literature regarding the dependence of organic nitrate production (from RO2 + NO) on carbon number. We found the hydrolysis rate constants to be highly pH dependent, with a hydrolysis lifetime of 51(±13) min at pH = 4 and 24(±3) min at pH = 2.5, a typical pH for deliquesced aerosols. We also employed high-resolution mass spectrometry for preliminary product identification. The results indicate that the ocimene SOA yield (< 1 %) under relevant aerosol mass loadings in the atmosphere is significantly lower than reported yields from cyclic terpenes, such as α-pinene, likely due to alkoxy radical decomposition and formation of smaller, higher-volatility products. This is also consistent with the observed lower particle-phase organic nitrate yields of β-ocimene – i.e., 1.5(±0.5) % – under dry conditions. We observed the expected hydroxy nitrates by chemical ionization mass spectrometry (CIMS) and some secondary production of the dihydroxy dinitrates, likely produced by oxidation of the first-generation hydroxy nitrates. Lower RONO2 yields were observed under high relative humidity (RH) conditions, indicating the importance of aerosol-phase RONO2 hydrolysis under ambient RH. This study provides insight into the formation and fate of organic nitrates, β-ocimene SOA yields, and NOx cycling in forested environments from daytime monoterpenes not currently included in atmospheric models.

Long-term Trends of Volatile Organic Compounds over the Texas, USA in the Past Two Decades

Volatile organic compounds (VOCs) are organic compounds in the air that have low vapor pressure. VOCs can be emitted from a variety of sources including biogenic, anthropogenic and pyrogenic processes. VOCs are precursors of aerosols and tropospheric 03. which harm human health. However, the potential of VOCs forming secondary air pollutants varies by species. Here, we analyze the long-term trends of soiu'ce. concentration and reactivity of six classes of VOCs from 1995 to 2018 over Texas. USA. VOCs emission from petroleum and related companies in Texas kept increasing these years. Among the VOCs tracers of oil and gas companies, the concentration of ethane kept increasing until 2015. Despite the increase of oil and gas related VOCs. the concentration of total VOCs and reactivity-weighted VOCs have decreased in the past two decades. We further investigate the seasonality of VOC reactivities, which depend on both temperature and VOC concentration. We find that VOC reactivity generally is highest in fall and lowest in spring, and such seasonality does not change over the two decades.

Area-selective aerosol jet fog deposition: Advancing large-area and sustainable fabrication

In this work, we demonstrate controlled area-selective deposition of aluminum oxide phosphate (AlPO) at room temperature and near atmospheric pressure using a potentially zero-waste aerosol jet fog (ajFOG) deposition system. Octyl-trichlorosilane (OTS-8) self-assembled monolayers (SAMs) are coated on SiO2/Si substrates to form a blanket hydrophobic functionalization. Next, ultraviolet/ozone exposure through a shadow mask removes OTS-8 in the exposed regions, creating a pattern of hydrophobic and hydrophilic regions. AlPO is selectively deposited onto the hydrophilic regions from an aqueous aerosol precursor fog of aluminum phosphate inorganic clusters. Smooth films with sharp boundaries are deposited. The AlPO features and defects in the hydrophobic areas are investigated as a function of feature size, SAM type/application method/exposure time, ajFOG process parameters, and underlying substrate.

Bias in CMIP6 models as compared to observed regional dimming and brightening

Abstract. Anthropogenic aerosol emissions have increased considerably over the last century, but climate effects and quantification of the emissions are highly uncertain as one goes back in time. This uncertainty is partly due to a lack of observations in the pre-satellite era, making the observations we do have before 1990 additionally valuable. Aerosols suspended in the atmosphere scatter and absorb incoming solar radiation and thereby alter the Earth's surface energy balance. Previous studies show that Earth system models (ESMs) do not adequately represent surface energy fluxes over the historical era. We investigated global and regional aerosol effects over the time period 1961–2014 by looking at surface downwelling shortwave radiation (SDSR). We used observations from ground stations as well as multiple experiments from eight ESMs participating in the Coupled Model Intercomparison Project Version 6 (CMIP6). Our results show that this subset of models reproduces the observed transient SDSR well in Europe but poorly in China. We suggest that this may be attributed to missing emissions of sulfur dioxide in China, sulfur dioxide being a precursor to sulfate, which is a highly reflective aerosol and responsible for more reflective clouds. The emissions of sulfur dioxide used in the models do not show a temporal pattern that could explain observed SDSR evolution over China. The results from various aerosol emission perturbation experiments from DAMIP, RFMIP and AerChemMIP show that only simulations containing anthropogenic aerosol emissions show dimming, even if the dimming is underestimated. Simulated clear-sky and all-sky SDSR do not differ greatly, suggesting that cloud cover changes are not a dominant cause of the biased SDSR evolution in the simulations. Therefore we suggest that the discrepancy between modeled and observed SDSR evolution is partly caused by erroneous aerosol and aerosol precursor emission inventories. This is an important finding as it may help interpret whether ESMs reproduce the historical climate evolution for the right or wrong reason.

Role of ammonia in European air quality with changing land and ship emissions between 1990 and 2030

Abstract. The focus of this modeling study is on the role of ammonia in European air quality in the past as well as in the future. Ammonia emissions have not decreased as much as the other secondary inorganic aerosol (SIA) precursors – nitrogen oxides (NOx) and sulfur dioxide (SO2) – since the 1990s and are still posing problems for air quality and the environment. In this study, air quality simulations were performed with a regional chemical transport model at decadal intervals between 1990 and 2030 to understand the changes in the chemical species associated with SIA under varying land and ship emissions. We analyzed the changes in air concentrations of ammonia, nitric acid, ammonium, particulate nitrate and sulfate as well as changes in the dry and wet deposition of ammonia and ammonium. The results show that the approximately 40 % decrease in SIA concentrations between 1990 and 2010 was mainly due to reductions in NOx and SO2 emissions. The ammonia concentrations on the other hand decreased only near the high-emission areas such as the Netherlands and northern Italy by about 30 %, while there was a slight increase in other parts of Europe. Larger changes in concentrations occurred mostly during the first period (1990–2000). The model results indicate a transition period after 2000 for the composition of secondary inorganic aerosols due to a larger decrease in sulfate concentrations than nitrate. Changes between 2010 and 2030 – assuming the current legislation (CLE) scenario – are predicted to be smaller than those achieved earlier for all species analyzed in this study. The scenario simulations suggest that if ship emissions will be regulated more strictly in the future, SIA formation will decrease especially around the Benelux area, North Sea, Baltic Sea, English Channel and the Mediterranean region, leaving more ammonia in the gas phase, which would lead to an increase in dry deposition. In the north of the domain, the decrease in SIA would be mainly due to reduced formation of particulate nitrate, while the change around the Mediterranean would be caused mainly by decreased sulfate aerosol concentrations. One should also keep in mind that potentially higher temperatures in the future might increase the evaporation of ammonium nitrate to form its gaseous components NH3 and HNO3. Sensitivity tests with reduced NOx and NH3 emissions indicate a shift in the sensitivity of aerosol formation from NH3 towards NOx emissions between 1990 and 2030 in most of Europe except the eastern part of the model domain.

Biogenic particles formed in the Himalaya as an important source of free tropospheric aerosols

Aerosols of biogenic and anthropogenic origin affect the total radiative forcing of global climate. Poor knowledge of the pre-industrial aerosol concentration and composition, in particular of particles formed directly in the atmosphere from gaseous precursors, constitutes a large uncertainty in the anthropogenic radiative forcing. Investigations of new particle formation at pre-industrial-like conditions can contribute to the reduction of this uncertainty. Here we present observations taken at the remote Nepal Climate Observatory Pyramid station at 5,079 m above sea level, a few kilometres from the summit of Everest. We show that up-valley winds funnel gaseous aerosol precursors to higher altitudes. During this transport, these are oxidized into compounds of very low volatility, which rapidly form a large number of aerosol particles. These are then transported into the free troposphere, which suggests that the whole Himalayan region may act as an ‘aerosol factory’ and contribute substantially to the free tropospheric aerosol population. Aerosol production in this region occurs mainly via organic precursors of biogenic origin with little evidence of the involvement of anthropogenic pollutants. This process is therefore likely to be essentially unchanged since the pre-industrial period, and may have been one of the major sources that contributes to the upper tropospheric aerosol population during that time. Newly formed biogenic particles in the Himalaya increase free-tropospheric background aerosol concentration by a factor of up to two.

The potential role of organics in new particle formation and initial growth in the remote tropical upper troposphere

Abstract. Global observations and model studies indicate that new particle formation (NPF) in the upper troposphere (UT) and subsequent particles supply 40 %–60 % of cloud condensation nuclei (CCN) in the lower troposphere, thus affecting the Earth's radiative budget. There are several plausible nucleation mechanisms and precursor species in this atmospheric region, which, in the absence of observational constraints, lead to uncertainties in modeled aerosols. In particular, the type of nucleation mechanism and concentrations of nucleation precursors, in part, determine the spatial distribution of new particles and resulting spatial distribution of CCN from this source. Although substantial advances in understanding NPF have been made in recent years, NPF processes in the UT in pristine marine regions are still poorly understood and are inadequately represented in global models. Here, we evaluate commonly used and state-of-the-art NPF schemes in a Lagrangian box model to assess which schemes and precursor concentrations best reproduce detailed in situ observations. Using measurements of aerosol size distributions (0.003 < Dp < 4.8 µm) in the remote marine troposphere between ∼0.18 and 13 km altitude obtained during the NASA Atmospheric Tomography (ATom) mission, we show that high concentrations of newly formed particles in the tropical UT over both the Atlantic and Pacific oceans are associated with outflow regions of deep convective clouds. We focus analysis on observations over the remote Pacific Ocean, which is a region less perturbed by continental emissions than the Atlantic. Comparing aerosol size distribution measurements over the remote Pacific with box model simulations for 32 cases shows that none of the NPF schemes most commonly used in global models, including binary nucleation of sulfuric acid and water (neutral and ion-assisted) and ternary involving sulfuric acid, water, and ammonia, are consistent with observations, regardless of precursor concentrations. Through sensitivity studies, we find that the nucleation scheme among those tested that is able to explain most consistently (21 of 32 cases) the observed size distributions is that of Riccobono et al. (2014), which involves both organic species and sulfuric acid. The method of Dunne et al. (2016), involving charged sulfuric acid–water–ammonia nucleation, when coupled with organic growth of the nucleated particles, was most consistent with the observations for 5 of 32 cases. Similarly, the neutral sulfuric acid–water–ammonia method of Napari (2002), when scaled with a tuning factor and with organic growth added, was most consistent for 6 of 32 cases. We find that to best reproduce both nucleation and growth rates, the mixing ratios of gas-phase organic precursors generally need to be at least twice that of SO2, a proxy for dimethyl sulfide (DMS). Unfortunately, we have no information on the nature of oxidized organic species that participated in NPF in this region. Global models rarely include organic-driven nucleation and growth pathways in UT conditions where globally significant NPF takes place, which may result in poor estimates of NPF and CCN abundance and contribute to uncertainties in aerosol–cloud–radiation effects. Furthermore, our results indicate that the organic aerosol precursor vapors may be important in the tropical UT above marine regions, a finding that should guide future observational efforts.

Theoretical analysis for bacteria participating in atmospheric nucleation

Particulate Matter with aerodynamic diameter smaller than 2.5 μm (PM2.5) especially those with toxic bacteria can heavily damage the human physiological system, and lead to respiratory and cardiovascular disease. Although the biological species is widely observed in aerosol particles, the current knowledge has not clearly clarified why and how that happens. Herein, the ab initio calculation of the interaction between bacteria molecule and inorganic aerosol precursors (i.e., Sulfuric Acid SA, Nitrite Acid NA and Ammonia AM) is conducted, to investigate the potential role of bacteria in atmospheric nucleation. Typical bacteria Gram-positive (G+) bacteria and Gram-negative (G-) bacteria are usually with diameter at ~1 μm, which can initiate heterogeneous nucleation with SA, NA or AM by serving as pre-existing surface. Hydrogen bond (H-bond) is found to be formed and represents the driven force for the heterogeneous nucleation. The enhanced heterogeneous nucleation by bacterium can contribute to secondary aerosol particles. Geometrical analysis shows that the aggregation between bacteria molecule and the SA is the most stable, which bears two H-bond and processes a cyclic structure. Thermochemical analysis indicates no matter the bacteria molecule belongs to G+ or G-, it would prefer to aggregate with the SA, followed by the NA and AM. And the G+ bacteria is relatively more active to aggregate with inorganic precursors compared to G- bacteria.