Secondary Organic Aerosol Formation Potential from Vehicular Non-tailpipe Emissions under Real-World Driving Conditions.

Traffic emissions are a dominant source of secondary organic aerosol (SOA) in urban environments. Though tailpipe exhaust has drawn extensive attention, the impact of non-tailpipe emissions on atmospheric SOA has not been well studied. Here, a closure study was performed combining urban tunnel experiments and dynamometer tests using an oxidation flow reactor in situ photo-oxidation. Results show a significant gap between field and laboratory research; the average SOA formation potential from real-world fleet is 639 ± 156 mg kg fuel-1, higher than the reconstructed result (188 mg kg fuel-1) based on dynamometer tests coupled with fleet composition inside the tunnel. Considering the minimal variation of SOA/CO in emission standards, we also reconstruct CO and find the critical role of high-emitting events in the real-world SOA burden. Different profiles of organic gases are detected inside the tunnel than tailpipe exhaust, such as more abundant C6-C9 aromatics, C11-C16 species, and benzothiazoles, denoting contributions from non-tailpipe emissions to SOA formation. Using these surrogate chemical compounds, we roughly estimate that high-emitting, evaporative emission, and asphalt-related and tire sublimation share 14, 20, and 10% of the SOA budget, respectively, partially explaining the gap between field and laboratory research. These experimental results highlight the importance of non-tailpipe emissions to atmospheric SOA.

Transforming waste brake pads from automobiles into Nano-Catalyst: Synergistic Fe-C-Cu triple sites for efficient fenton-like oxidation of organic pollutants.

The arbitrary disposal of used brake pads from motor vehicles has resulted in severe heavy metal pollution and resource wastage, highlighting the urgent need to explore the significant untapped potential of these discarded materials. In this study, The in-situ growth of highly dispersed Fe2O3 nanocrystals was achieved by simple oxidation annealing of brake pad debris(BPD). Interestingly, Cu remained unoxidized and acted as a "valence state transformation bridge of Fe2O3" to construct the "triple Fe-C-Cu sites". The Fenton degradation experiment of pollutants was conducted under constant temperature conditions at 40 °C, a stirring rate of 1300 rpm, a pH value of 3, a catalyst dosage of 0.5 g/L, pollutant dosage ranging from 50 to 400 mg/L, and H2O2 dosage of 0.25 g/L. Experimental results showed that BPD treated at 300 °C for 2 h exhibited optimal Fenton-like oxidation activity, achieving rapid degradation of over 90 % of refractory antibiotics, such as tetracycline and ciprofloxacin, in organic wastewater within 10 min. This remarkable performance was mainly attributed to the synergistic effect of "Fe-C-Cu triple sites", where the electron-donating role of C in the Fe-C and Cu-C interfaces facilitated the conversion of the Fe(III) to Fe(II) and Cu(II) to Cu(I). In addition, the ability of Cu2+ to accept electrons at the Fe-Cu interface promoted the transition from Fe (II) to Fe (III). This "balance of electron gain and loss" accelerated the interfacial electron transfer and the recycle of dual Fenton sites, Fe(II)/Fe(III) and Cu(I)/Cu(II), to generate more ·OH from H2O2. Therefore, this strategy of functionalizing BPD as Fenton-like catalysts without the addition of external Fe provides intriguing prospects for understanding the construction of Fe-based Fenton catalysts and resource utilization of Fe-containing solid waste materials.

Brake wear-derived particles: Single-particle mass spectral signatures and real-world emissions.

Brake wear is an important but unregulated vehicle-related source of atmospheric particulate matter (PM). The single-particle spectral fingerprints of brake wear particles (BWPs) provide essential information for understanding their formation mechanism and atmospheric contributions. Herein, we obtained the single-particle mass spectra of BWPs by combining a brake dynamometer with an online single particle aerosol mass spectrometer and quantified real-world BWP emissions through a tunnel observation in Tianjin, China. The pure BWPs mainly include three distinct types of particles, namely, Ba-containing particles, mineral particles, and carbon-containing particles, accounting for 44.2%, 43.4%, and 10.3% of the total BWP number concentration, respectively. The diversified mass spectra indicate complex BWP formation pathways, such as mechanical, phase transition, and chemical processes. Notably, the mass spectra of Ba-containing particles are unique, which allows them to serve as an excellent indicator for estimating ambient BWP concentrations. By evaluating this indicator, we find that approximately 4.0% of the PM in the tunnel could be attributable to brake wear; the real-world fleet-average emission factor of 0.28 mg km-1 veh-1 is consistent with the estimation obtained using the receptor model. The results presented herein can be used to inform assessments of the environmental and health impacts of BWPs to formulate effective emissions control policies.

Optical properties of vehicular brown carbon emissions: Road tunnel and chassis dynamometer tests.

Brown carbon (BrC), as an important light-absorbing aerosol, significantly impacts regional and global climate. Vehicle emission is a nonnegligible source of BrC, but the optical properties of BrC emitted from vehicles remain poorly understood. This study evaluates the absorption Ångström exponent (AAE) of traffic-related light-absorbing aerosols (i.e., AAETr) and the absorption emission factor (EFabs) of vehicular BrC via chassis dynamometer tests and a road tunnel measurement in Tianjin, China. AAETr are estimated as 0.98-1.33 and 1.11 ± 0.001 for tested vehicles and on-road vehicle fleet, respectively. The AAE of vehicular BrC (AAEBrC) is 3.83 ± 0.092 for on-road vehicle fleet. The vehicle technology updates effectively reduce the EFabs of vehicular BrC. Among the four tested China 5 and China 6 gasoline vehicles in the chassis dynamometer tests, BrC EFabs of China 5 gasoline direct injection vehicle is the highest, while China 6 mixing fuel injection vehicle exhibits the lowest EFabs. The BrC EFabs of on-road vehicle fleet at 370 nm wavelength are 0.081 ± 0.0058 m2 kg-1 for mixed fleet, 0.074 ± 0.018 m2 kg-1 for gasoline vehicles (GVs), and 1.66 ± 0.71 m2 kg-1 for diesel vehicles (DVs) in the tunnel measurement. EFabs of GV fleet in the road tunnel is higher than China 5 and China 6 vehicles, as China 1-4 vehicles accounted for 26.8% of the total vehicle fleet in the tunnel. EFabs of vehicular BrC are lower than those from biomass burning and coal combustion emissions. The light absorption of BrC from GVs and DVs accounts for 7.2 ± 2.1% and 1.5 ± 0.77% of total traffic-related absorption at 370 nm, respectively. Our study provides optical features of BrC from vehicle source and could contribute to estimating the impacts of vehicular aerosol emissions on global and regional climate change.

Tunnel measurements reveal significant reduction in traffic-related light-absorbing aerosol emissions in China.

Light-absorbing aerosols (LAA), including black carbon (BC) and brown carbon (BrC), profoundly impact regional and global climate. Vehicle emission is an important source of LAA in urban areas, but real-world emission features of LAA from the urban vehicle fleet are not fully understood. This study evaluates traffic-related BC and BrC emission factors (EFs) and their vehicular emission inventories via road tunnel measurements in Tianjin, China, in 2017 and 2021. The distance-based and fuel-based EFs of BC for the mixed fleet were 1.05 ± 1.28 mg km-1 veh-1 and 0.057 ± 0.057 g (kg-fuel)-1, respectively, in 2021, with a dramatic decrease of 80.6 % compared to those in 2017. The BC EFs for gasoline vehicles (GVs, including traditional gasoline and hybrid vehicles) and diesel vehicles (DVs) were 0.55 ± 0.065 mg km-1 veh-1 and 10.5 ± 2.52 mg km-1 veh-1, respectively, in 2021. Compared to 2017, the BrC EFs also decreased significantly in 2021, by 10.8-53.6 %, with 0.32 ± 0.45 mg km-1 veh-1 and 0.018 ± 0.020 g (kg-fuel)-1 of distance-based and fuel-based EFs for mixed fleet. The BrC EFs for GVs and DVs were 0.091 ± 0.024 mg km-1 veh-1 and 3.06 ± 0.91 mg km-1 veh-1, respectively, in 2021. Based on the BC and BrC EFs for GVs and DVs and annual mileage for each vehicle category, the annual vehicular LAA emission inventories were estimated. From 2017 to 2021, the annual vehicular LAA emissions in Tianjin have been significantly reduced, by 69 % for BC and 10 % for BrC. DVs account for a small amount of the vehicle population (8.4 %), but contribute to most of the BC (83 %) and BrC (86 %). Our study demonstrates the significant reduction of vehicular light-absorbing aerosols emission due to vehicle pollution prevention and control in China.

Applying machine learning to construct braking emission model for real-world road driving.

Brake emissions from vehicles are increasing as the number of vehicles increases. However, current research on brake emissions, particularly the intensity and characteristics of emissions under real road conditions, is significantly inadequate compared to exhaust emissions. To this end, a dataset of 600 (200 unique real-world braking events simulated using three types of brake pads) real-world braking events (called brake pad segments) was constructed and a mapping function between the average brake emission intensity of PM2.5 from the segments and the segment features was established by five algorithms (multiple linear regression (MLR) and four machine learning algorithms). Based on the five algorithms, the importance of the different features of the fragments was discussed and brake energy intensity (BEI) and metal content (MC) of the brake pad emissions were identified as the most significant factors affecting brake emissions and used as the final modeling features. Among the five algorithms, categorical boosting (CatBoost) had the best prediction performance, with a mean R2 and RMSE of 0.83 and 0.039 respectively for the tenfold cross-validation. In addition, the CatBoost-based model was further compared with the MOVES model to demonstrate its applicability. The CatBoost-based model has better prediction performance than the MOVES model. The MOVES model overpredicts brake fragment emissions for urban roads and underpredicts brake fragment emissions for motorways. Furthermore, the CatBoost-based model was interpreted and visualized by an individual conditional expectation (ICE) plot to break the machine learning "black box", with BEI and MC showing nonlinear monotonic increasing relationships with braking emissions. ICE plot also provides viable technical solutions for controlling brake emissions in the future. Both avoiding aggressive braking driving behavior (e.g., the application of smart transportation technologies) and using brake pads with less metal content (e.g., using ceramic brake pads) can effectively reduce brake emissions. The construction of a machine learning-based brake emission model and the white-boxing of its model provide excellent insights for the future detailed assessment and control of brake emissions.

Parameterization of the ambient aerosol refractive index with source appointed chemical compositions.

The refractive index of ambient aerosols is widely used in the climate model and remote sensing. Traditionally, the real part of the refractive index (RRI) of the ambient aerosol is calculated from the measured mass fraction of the main inorganic components with known refractive index, without full resolving the effects of variation in the RRI of organic components, which always contribute more than 50 % of the total aerosol mass. For the first time, the ambient aerosol RRI and the aerosol chemical components were measured concurrently at a suburban site Changping, in Beijing, China. Measurements results show that the ambient aerosol ranges between 1.57 and 1.71 with a mean value of 1.66. The mean mass fractions of organic aerosol (OA), nitrate, sulfate, ammonium, and chloride to total non-refractory aerosol loading are 43.1 %, 21.9 %, 21.6 %, 13.1 %, and 0.3 % respectively. Source appointment analysis of the organic aerosol show that the fossil fuel-related OA, cooking OA, biomass burning OA, less oxidized oxygenated OA and more oxidized OOA contributes 18.0 %, 11.2 %, 4.1 %, 39.9 %, 26.7 % to the total aerosol. A new parameterization scheme of the ambient aerosol RRI, which considers the source appointed OA, is proposed based on the concurrent measurements of RRI and chemical composition. The measured and parameterized RRI shows good consistency with a correlation coefficient of 0.79 and slope of 0.98. Our measurement results reveal that a significant deviation of the calculated RRI exists without considering the variation of the RRI of the aerosol organic component. The parametrization scheme is adopted and applicable in aerosol model for bettering estimating the corresponding optical and radiative effects.

Larger than expected variation range in the real part of the refractive index for ambient aerosols in China.

The real part of the refractive index (RRI) of ambient aerosol, which is widely used in remote sensing and atmospheric models, is one of the key factors determining its particles' optical properties. The characteristics of ambient aerosol RRI in China have not yet been well studied owing to a lack of observations. For the first time, the properties of aerosol RRI were studied based on field measurements in China at four sites with different atmospheres. The results revealed that the measured ambient aerosol RRI varied significantly between 1.36 and 1.78, increasing with the mass ratio of organic components. The scattering coefficient and direct radiative effects of the aerosols were estimated to increase by factors of 2 and 3, respectively, when RRI increased from 1.36 to 1.78. Our results indicate that variation in ambient aerosol RRI should be considered in aerosol and climate models to achieve an accurate estimation of aerosol's radiative impacts.

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.

Remarkable nucleation and growth of ultrafine particles from vehicular exhaust.

High levels of ultrafine particles (UFPs; diameter of less than 50 nm) are frequently produced from new particle formation under urban conditions, with profound implications on human health, weather, and climate. However, the fundamental mechanisms of new particle formation remain elusive, and few experimental studies have realistically replicated the relevant atmospheric conditions. Previous experimental studies simulated oxidation of one compound or a mixture of a few compounds, and extrapolation of the laboratory results to chemically complex air was uncertain. Here, we show striking formation of UFPs in urban air from combining ambient and chamber measurements. By capturing the ambient conditions (i.e., temperature, relative humidity, sunlight, and the types and abundances of chemical species), we elucidate the roles of existing particles, photochemistry, and synergy of multipollutants in new particle formation. Aerosol nucleation in urban air is limited by existing particles but negligibly by nitrogen oxides. Photooxidation of vehicular exhaust yields abundant precursors, and organics, rather than sulfuric acid or base species, dominate formation of UFPs under urban conditions. Recognition of this source of UFPs is essential to assessing their impacts and developing mitigation policies. Our results imply that reduction of primary particles or removal of existing particles without simultaneously limiting organics from automobile emissions is ineffective and can even exacerbate this problem.

Enhancement in Particulate Organic Nitrogen and Light Absorption of Humic-Like Substances over Tibetan Plateau Due to Long-Range Transported Biomass Burning Emissions.

To elucidate the influence of long-range transported biomass burning organic aerosols (BBOA) on the Tibetan Plateau, the molecular compositions and light absorption of HUmic-Like Substances (HULIS), major fractions of brown carbon, were characterized during the premonsoon season. Under the significant influence of biomass burning, HULIS concentrations increased to as high as 26 times of the background levels, accounting for 54% of water-soluble organic carbon (WSOC) and 50% of organic carbon (OC). The light absorption of HULIS also enhanced up to 42 times of the background levels, contributing 61% of the WSOC absorption and 50% of OC absorption. Meanwhile, elevated nitrogen-containing compounds (NOCs) among HULIS were observed. The NOCs from fresh and aged BBOA were unambiguously identified on the molecular level, through comparing with the molecular compositions of NOCs from lab-controlled and field burning experiments. N-Heterocyclic bases represent major fractions in the reduced nitrogen compounds from fresh BBOA, and nitroaromatic compounds are important groups among the oxidized nitrogen compounds from aged BBOA. The nitrogen-containing compounds, including nitroaromatics and N-heterocyclic compounds, were also important chromophores, which contributed to the enhanced light absorption of extracted HULIS during biomass burning-influenced periods.

Formation and Optical Properties of Brown Carbon from Small α-Dicarbonyls and Amines.

Brown Carbon (BrC) aerosols scatter and absorb solar radiation, directly affecting the Earth's radiative budget. However, considerable uncertainty exists concerning the chemical mechanism leading to BrC formation and their optical properties. In this work, BrC particles were prepared from mixtures of small α-dicarbonyls (glyoxal and methylglyoxal) and amines (methylamine, dimethylamine, and trimethylamine). The absorption and scattering of BrC particles were measured using a photoacoustic extinctometer (405 and 532 nm), and the chemical composition of the α-dicarbonyl-amine mixtures was analyzed using orbitrap-mass spectrometry and thermal desorption-ion drift-chemical ionization mass spectrometry. The single scattering albedo for methylglyoxal-amine mixtures is smaller than that of glyoxal-amine mixtures and increases with the methyl substitution of amines. The mass absorption cross-section for methylglyoxal-amine mixtures is two times higher at 405 nm wavelength than that at 532 nm wavelength. The derived refractive indexes at the 405 nm wavelength are 1.40-1.64 for the real part and 0.002-0.195 for the imaginary part. Composition analysis in the α-dicarbonyl-amine mixtures reveals N-heterocycles as the dominant products, which are formed via multiple steps involving nucleophilic attack, steric hindrance, and dipole-dipole interaction between α-dicarbonyls and amines. BrC aerosols, if formed from the particle-phase reaction of methylglyoxal with methylamine, likely contribute to atmospheric warming.

Size-resolved effective density of submicron particles during summertime in the rural atmosphere of Beijing, China.

Particle density is an important physical property of atmospheric particles. The information on high time-resolution size-resolved particle density is essential for understanding the atmospheric physical and chemical aging processes of aerosols particles. In the present study, a centrifugal particle mass analyzer (CPMA) combined with a differential mobility analyzer (DMA) was deployed to determine the size-resolved effective density of 50 to 350nm particles at a rural site of Beijing during summer 2016. The measured particle effective densities decreased with increasing particle sizes and ranged from 1.43 to 1.55g/cm3, on average. The effective particle density distributions were dominated by a mode peaked at around 1.5g/cm3 for 50 to 350nm particles. Extra modes with peaks at 1.0, 0.8, and 0.6g/cm3 for 150, 240, and 350nm particles, which might be freshly emitted soot particles, were observed during intensive primary emissions episodes. The particle effective densities showed a diurnal variation pattern, with higher values during daytime. A case study showed that the effective density of Aitken mode particles during the new particle formation (NPF) event decreased considerably, indicating the significant contribution of organics to new particle growth.

Potential of secondary aerosol formation from Chinese gasoline engine exhaust.

Light-duty gasoline vehicles have drawn public attention in China due to their significant primary emissions of particulate matter and volatile organic compounds (VOCs). However, little information on secondary aerosol formation from exhaust for Chinese vehicles and fuel conditions is available. In this study, chamber experiments were conducted to quantify the potential of secondary aerosol formation from the exhaust of a port fuel injection gasoline engine. The engine and fuel used are common in the Chinese market, and the fuel satisfies the China V gasoline fuel standard. Substantial secondary aerosol formation was observed during a 4-5hr simulation, which was estimated to represent more than 10days of equivalent atmospheric photo-oxidation in Beijing. As a consequence, the extreme case secondary organic aerosol (SOA) production was 426±85mg/kg-fuel, with high levels of precursors and OH exposure. The low hygroscopicity of the aerosols formed inside the chamber suggests that SOA was the dominant chemical composition. Fourteen percent of SOA measured in the chamber experiments could be explained through the oxidation of speciated single-ring aromatics. Unspeciated precursors, such as intermediate-volatility organic compounds and semi-volatile organic compounds, might be significant for SOA formation from gasoline VOCs. We concluded that reductions of emissions of aerosol precursor gases from vehicles are essential to mediate pollution in China.

Persistent sulfate formation from London Fog to Chinese haze.

Sulfate aerosols exert profound impacts on human and ecosystem health, weather, and climate, but their formation mechanism remains uncertain. Atmospheric models consistently underpredict sulfate levels under diverse environmental conditions. From atmospheric measurements in two Chinese megacities and complementary laboratory experiments, we show that the aqueous oxidation of SO2 by NO2 is key to efficient sulfate formation but is only feasible under two atmospheric conditions: on fine aerosols with high relative humidity and NH3 neutralization or under cloud conditions. Under polluted environments, this SO2 oxidation process leads to large sulfate production rates and promotes formation of nitrate and organic matter on aqueous particles, exacerbating severe haze development. Effective haze mitigation is achievable by intervening in the sulfate formation process with enforced NH3 and NO2 control measures. In addition to explaining the polluted episodes currently occurring in China and during the 1952 London Fog, this sulfate production mechanism is widespread, and our results suggest a way to tackle this growing problem in China and much of the developing world.

Markedly enhanced absorption and direct radiative forcing of black carbon under polluted urban environments.

Black carbon (BC) exerts profound impacts on air quality and climate because of its high absorption cross-section over a broad range of electromagnetic spectra, but the current results on absorption enhancement of BC particles during atmospheric aging remain conflicting. Here, we quantified the aging and variation in the optical properties of BC particles under ambient conditions in Beijing, China, and Houston, United States, using a novel environmental chamber approach. BC aging exhibits two distinct stages, i.e., initial transformation from a fractal to spherical morphology with little absorption variation and subsequent growth of fully compact particles with a large absorption enhancement. The timescales to achieve complete morphology modification and an absorption amplification factor of 2.4 for BC particles are estimated to be 2.3 h and 4.6 h, respectively, in Beijing, compared with 9 h and 18 h, respectively, in Houston. Our findings indicate that BC under polluted urban environments could play an essential role in pollution development and contribute importantly to large positive radiative forcing. The variation in direct radiative forcing is dependent on the rate and timescale of BC aging, with a clear distinction between urban cities in developed and developing countries, i.e., a higher climatic impact in more polluted environments. We suggest that mediation in BC emissions achieves a cobenefit in simultaneously controlling air pollution and protecting climate, especially for developing countries.

Elucidating severe urban haze formation in China.

As the world's second largest economy, China has experienced severe haze pollution, with fine particulate matter (PM) recently reaching unprecedentedly high levels across many cities, and an understanding of the PM formation mechanism is critical in the development of efficient mediation policies to minimize its regional to global impacts. We demonstrate a periodic cycle of PM episodes in Beijing that is governed by meteorological conditions and characterized by two distinct aerosol formation processes of nucleation and growth, but with a small contribution from primary emissions and regional transport of particles. Nucleation consistently precedes a polluted period, producing a high number concentration of nano-sized particles under clean conditions. Accumulation of the particle mass concentration exceeding several hundred micrograms per cubic meter is accompanied by a continuous size growth from the nucleation-mode particles over multiple days to yield numerous larger particles, distinctive from the aerosol formation typically observed in other regions worldwide. The particle compositions in Beijing, on the other hand, exhibit a similarity to those commonly measured in many global areas, consistent with the chemical constituents dominated by secondary aerosol formation. Our results highlight that regulatory controls of gaseous emissions for volatile organic compounds and nitrogen oxides from local transportation and sulfur dioxide from regional industrial sources represent the key steps to reduce the urban PM level in China.