Rapid growth of new atmospheric particles by nitric acid and ammonia condensation.

A list of authors and their affiliations appears at the end of the paper New-particle formation is a major contributor to urban smog1,2, but how it occurs in cities is often puzzling3. If the growth rates of urban particles are similar to those found in cleaner environments (1-10 nanometres per hour), then existing understanding suggests that new urban particles should be rapidly scavenged by the high concentration of pre-existing particles. Here we show, through experiments performed under atmospheric conditions in the CLOUD chamber at CERN, that below about +5 degrees Celsius, nitric acid and ammonia vapours can condense onto freshly nucleated particles as small as a few nanometres in diameter. Moreover, when it is cold enough (below -15 degrees Celsius), nitric acid and ammonia can nucleate directly through an acid-base stabilization mechanism to form ammonium nitrate particles. Given that these vapours are often one thousand times more abundant than sulfuric acid, the resulting particle growth rates can be extremely high, reaching well above 100 nanometres per hour. However, these high growth rates require the gas-particle ammonium nitrate system to be out of equilibrium in order to sustain gas-phase supersaturations. In view of the strong temperature dependence that we measure for the gas-phase supersaturations, we expect such transient conditions to occur in inhomogeneous urban settings, especially in wintertime, driven by vertical mixing and by strong local sources such as traffic. Even though rapid growth from nitric acid and ammonia condensation may last for only a few minutes, it is nonetheless fast enough to shepherd freshly nucleated particles through the smallest size range where they are most vulnerable to scavenging loss, thus greatly increasing their survival probability. We also expect nitric acid and ammonia nucleation and rapid growth to be important in the relatively clean and cold upper free troposphere, where ammonia can be convected from the continental boundary layer and nitric acid is abundant from electrical storms4,5.

Photoactivation of Chlorine and Its Catalytic Role in the Formation of Sulfate Aerosols.

We present a novel mechanism for the formation of photocatalytic oxidants in deliquescent NaCl particles, which can greatly promote the multiphase photo-oxidation of SO2 to produce sulfate. The photoexcitation of the [Cl--H3O+-O2] complex leads to the generation of Cl and OH radicals, which is the key reason for enhancing aqueous-phase oxidation and accelerating SO2 oxidation. The mass normalization rate of sulfate production from the multiphase photoreaction of SO2 on NaCl droplets could be estimated to be 0.80 × 10-4 µg·h-1 at 72% RH and 1.33 × 10-4 µg·h-1 at 81% RH, which is equivalent to the known O3 liquid-phase oxidation mechanism. Our findings highlight the significance of multiphase photo-oxidation of SO2 on NaCl particles as a non-negligible source of sulfate in coastal areas. Furthermore, this study underscores the importance of Cl- photochemistry in the atmosphere.

An Alternative Calibration Method for Measuring N2O5 with an Iodide-Chemical Ionization Mass Spectrometer and Influencing Factors.

In this work, we developed an alternative calibration method for measuring N2O5 with an iodide adduct mass spectrometer (I-CIMS). In this calibration method, N2O5 is heated and then quantified based on the decrease in the amount of NO due to its reaction with the pyrolysis product (NO3). This alternative calibration method was compared with the commonly used method utilizing NOx analyzers equipped with a photolytic converter, which gauge NO2 reduction as a result of its reaction with O3 to quantify N2O5. It is notable that the two methodologies demonstrate favorable consistency in terms of calibrating N2O5, with a variance of less than 10 %. The alternative calibration method is a more reliable way to quantify N2O5 with CIMS, considering the instability of the NO2 conversion efficiency of photolytic converters in NOx analyzers and the loss of N2O5 in the sampling line. The effects of O3 and relative humidity (RH) on the sensitivity toward N2O5 were further examined. There was minimal perturbation of N2O5 quantification upon exposure to O3 even at high concentrations. The N2O5 sensitivity exhibited a nonlinear dependence on RH as it initially rose and then fell. Besides I(N2O5)-, the collisional interaction between I(H2O)- and N2O5 also forms I(HNO3)-, which may interfere with the accurate quantification of HNO3. As a consequence of the pronounced dependence on humidity, it is advisable to implement humidity correction procedures when conducting measurements of N2O5.

Revealing the Contribution of Interfacial Processes to Atmospheric Oxidizing Capacity in Haze Chemistry.

The atmospheric oxidizing capacity is the most important driving force for the chemical transformation of pollutants in the atmosphere. Traditionally, the atmospheric oxidizing capacity mainly depends on the concentration of O3 and other gaseous oxidants. However, the atmospheric oxidizing capacity based on gas-phase oxidation cannot accurately describe the explosive growth of secondary particulate matter under complex air pollution. From the chemical perspective, the atmospheric oxidizing capacity mainly comes from the activation of O2, which can be achieved in both gas-phase and interfacial processes. In the heterogeneous or multiphase formation pathways of secondary particulate matter, the enhancement of oxidizing capacity ascribed to the O2/H2O-involved interfacial oxidation and hydrolysis processes is an unrecognized source of atmospheric oxidizing capacity. Revealing the enhanced oxidizing capacity due to interfacial processes in high-concentration particulate matter environments and its contribution to the formation of secondary pollution are critical in understanding haze chemistry. The accurate evaluation of atmospheric oxidizing capacity ascribed to interfacial processes is also an important scientific basis for the implementation of PM2.5 and O3 collaborative control in China and around the world.

Insights into the Formation Mechanism of Reactive Oxygen Species in the Interface Reaction of SO2 on Hematite.

The interplay between sulfur and iron holds significant importance in their atmospheric cycle, yet a complete understanding of their coupling mechanism remains elusive. This investigation delves comprehensively into the evolution of reactive oxygen species (ROS) during the interfacial reactions involving sulfur dioxide (SO2) and iron oxides under varying relative humidity conditions. Notably, the direct activation of water by iron oxide was observed to generate a surface hydroxyl radical (•OH). In comparison, the aging of SO2 was found to markedly augment the production of •OH radicals on the surface of α-Fe2O3 under humid conditions. This augmentation was ascribed to the generation of superoxide radicals (•O2-) stemming from the activation of O2 through the Fe(II)/Fe(III) cycle and its combination with the H+ ion to produce hydrogen peroxide (H2O2) on the acidic surface. Moreover, the identification of moderate relative humidity as a pivotal factor in sustaining the surface acidity of iron oxide during SO2 aging underscores its crucial role in the coupling of iron dissolution, ROS production, and SO2 oxidation. Consequently, the interfacial reactions between SO2 and iron oxides under humid conditions are elucidated as atmospheric processes that enhance oxidation capacity rather than deplete ROS. These revelations offer novel insights into the mechanisms underlying •OH radical generation and oxidative potential within atmospheric interfacial chemistry.

Dark NO2 Reduction on a Graphene Surface with Implications for Soot Aging and HONO Formation.

Soot, primarily composed of elemental carbon (EC) and organic carbon (OC), is ubiquitous in PM2.5. In the atmosphere, the heterogeneous interaction between NO2 and soot is not only an important pathway driving soot aging but also of central importance to nitrous acid (HONO) formation. It is commonly believed that the surface redox reaction between reductive OC and NO2 dominates the night aging of soot and the conversion of NO2 to HONO. However, completely differing from the currently popular explanation, we find here that the redox reaction between EC and NO2 can also drive the conversion of NO2 to HONO during soot aging. By combining in situ experiments with density functional theory (DFT) calculations, we proposed that the surface carbon vacancy defects on graphite/graphene-like EC should be a type of potential primary adsorption and reactive sites inducing the heterogeneous reduction of NO2. We suggested a new mechanism that NO2 is reduced to form HONO on surface vacancy defects through the splitting of H2O molecules, and the carbon atoms adjacent to surface vacancy are simultaneously oxidized to form hydroxyl-functionalized EC. This novel finding provides insights into the chemical mechanism driving the NO2-to-HONO conversion and rapid soot aging, which expands our knowledge of the heterogeneous chemistry of soot in the atmosphere.

Additional HONO and OH Generation from Photoexcited Phenyl Organic Nitrates in the Photoreaction of Aromatics and NOx.

HONO acts as a major OH source, playing a vital role in secondary pollutant formation to deteriorate regional air quality. Strong unknown sources of daytime HONO have been widely reported, which significantly limit our understanding of radical cycling and atmospheric oxidation capacity. Here, we identify a potential daytime HONO and OH source originating from photoexcited phenyl organic nitrates formed during the photoreaction of aromatics and NOx. Significant HONO (1.56-4.52 ppb) and OH production is observed during the photoreaction of different kinds of aromatics with NOx (18.1-242.3 ppb). We propose an additional mechanism involving photoexcited phenyl organic nitrates (RONO2) reacting with water vapor to account for the higher levels of measured HONO and OH than the model prediction. The proposed HONO formation mechanism was evidenced directly by photolysis experiments using typical RONO2 under UV irradiation conditions, during which HONO formation was enhanced by relative humidity. The 0-D box model incorporated in this mechanism accurately reproduced the evolution of HONO and aromatic. The proposed mechanism contributes 5.9-36.6% of HONO formation as the NOx concentration increased in the photoreaction of aromatics and NOx. Our study implies that photoexcited phenyl organic nitrates are an important source of atmospheric HONO and OH that contributes significantly to atmospheric oxidation capacity.

Spontaneous Molecular Bromine Production in Sea-Salt Aerosols.

Bromine chemistry is responsible for the catalytic ozone destruction in the atmosphere. The heterogeneous reactions of sea-salt aerosols are the main abiotic sources of reactive bromine in the atmosphere. Here, we present a novel mechanism for the activation of bromide ions (Br-) by O2 and H2O in the absence of additional oxidants. The laboratory and theoretical calculation results demonstrated that under dark conditions, Br-, O2 and H3O+ could spontaneously generate Br and HO2 radicals through a proton-electron transfer process at the air-water interface and in the liquid phase. Our results also showed that light and acidity could significantly promote the activation of Br- and the production of Br2. The estimated gaseous Br2 production rate was up to 1.55×1010 molecules cm-2 ⋅ s-1 under light and acidic conditions; these results showed a significant contribution to the atmospheric reactive bromine budget. The reactive oxygen species (ROS) generated during Br- activation could promote the multiphase oxidation of SO2 to produce sulfuric acid, while the increase in acidity had a positive feedback effect on Br- activation. Our findings highlight the crucial role of the proton-electron transfer process in Br2 production; here, H3O+ facilitates the activation of Br- by O2, serves as a significant source of atmospheric reactive bromine and exerts a profound impact on the atmospheric oxidation capacity.

Synergistic Effects of SO2 and NH3 Coexistence on SOA Formation from Gasoline Evaporative Emissions.

Vehicular evaporative emissions make an increasing contribution to anthropogenic sources of volatile organic compounds (VOCs), thus contributing to secondary organic aerosol (SOA) formation. However, few studies have been conducted on SOA formation from vehicle evaporative VOCs under complex pollution conditions with the coexistence of NOx, SO2, and NH3. In this study, the synergistic effects of SO2 and NH3 on SOA formation from gasoline evaporative VOCs with NOx were examined using a 30 m3 smog chamber with the aid of a series of mass spectrometers. Compared with the systems involving SO2 or NH3 alone, SO2 and NH3 coexistence had a greater promotion effect on SOA formation, which was larger than the cumulative effect of the two promotions alone. Meanwhile, contrasting effects of SO2 on the oxidation state (OSc) of SOA in the presence or absence of NH3 were observed, and SO2 could further increase the OSc with the coexistence of NH3. The latter was attributed to the synergistic effects of SO2 and NH3 coexistence on SOA formation, wherein N-S-O adducts can be formed from the reaction of SO2 with N-heterocycles generated in the presence of NH3. Our study contributes to the understanding of SOA formation from vehicle evaporative VOCs under highly complex pollution conditions and its atmospheric implications.

Combined Smog Chamber/Oxidation Flow Reactor Study on Aging of Secondary Organic Aerosol from Photooxidation of Aromatic Hydrocarbons.

Secondary organic aerosol (SOA) is a significant component of atmospheric fine particulate matter (PM2.5), and their physicochemical properties can be significantly changed in the aging process. In this study, we used a combination consisting of a smog chamber (SC) and oxidation flow reactor (OFR) to investigate the continuous aging process of gas-phase organic intermediates and SOA formed from the photooxidation of toluene, a typical aromatic hydrocarbon. Our results showed that as the OH exposure increased from 2.6 × 1011 to 6.3 × 1011 molecules cm-3 s (equivalent aging time of 2.01-4.85 days), the SOA mass concentration (2.9 ± 0.05-28.7 ± 0.6 µg cm-3) and corrected SOA yield (0.073-0.26) were significantly enhanced. As the aging process proceeds, organic acids and multiple oxygen-containing oxidation products are continuously produced from the photochemical aging process of gas-phase organic intermediates (mainly semi-volatile and intermediate volatility species, S/IVOCs). The multigeneration oxidation products then partition to the aerosol phase, while functionalization of SOA rather than fragmentation dominated in the photochemical aging process, resulting in much higher SOA yield after aging compared to that in the SC. Our study indicates that SOA yields as a function of OH exposure should be considered in air quality models to improve SOA simulation, and thus accurately assess the impact on SOA properties and regional air quality.