Search Results (126)

Biogenic volatile organic compounds (BVOCs) are low-boiling-point compounds commonly synthesized by secondary metabolic pathways in plants. As key precursors of ozone (O₃) and secondary organic aerosols (SOA), BVOCs play a critical role in ecosystem-atmosphere interactions. However, their emission from both marine and terrestrial ecosystems, as well as their association with climate and the environment, remain poorly characterized. In light of recent advances in BVOC research, including the establishment of emission inventories, identification of driving factors, and evaluation of ecological and environmental impacts, this study reviews the latest advancements in the field. The findings underscore that the carbon losses via BVOC emission should not be overlooked when estimating the terrestrial carbon balance. Additionally, more work needs to be conducted to quantify the emission factors of specific tree species and to establish links between BVOC emission and climate or environment change. This study contributes to a deeper understanding of vegetation ecology and its environmental functions. Full article

This perspective explores the use of biochar, a carbon-rich material derived from biomass, as a sustainable solution for mitigating volatile organic compounds (VOCs) emitted during asphalt production and use. VOCs from asphalt contribute to ozone formation and harmful secondary organic aerosols (SOAs), which negatively impact air quality and public health. Biochar, with its high surface area and capacity to adsorb VOCs, provides an effective means of addressing these challenges. By tailoring biochar’s surface chemistry, it can efficiently capture VOCs, while also offering long-term carbon sequestration benefits. Additionally, biochar enhances the durability of asphalt, extending road lifespan and reducing maintenance needs, making it a promising material for sustainable infrastructure. Despite these promising benefits, several challenges remain. Variations in biochar properties, driven by differences in feedstock and production methods, can affect its performance in asphalt. Moreover, the integration of biochar into existing plant operations requires the further development of methods to streamline the process and ensure consistency in biochar’s quality and cost-effectiveness. Standardizing production methods and addressing logistical hurdles will be crucial for biochar’s widespread adoption. Research into improving its long-term stability in asphalt is also needed to ensure sustained efficacy over time. Overcoming these challenges will be essential for fully realizing biochar’s potential in sustainable infrastructure development Full article

In this study, the chemical compositions of PM_2.5 (particulate matter < 2.5 μm) and the molecular compositions of methanol-soluble organic carbon (MSOC) in suburban Shanghai during summer were measured to investigate the molecular characteristics of organic aerosol (OA) under high humidity. Diurnal variation analysis reveals the influence of relative humidity (RH) on secondary organic aerosol (SOA) components. Organosulfates (OSs), particularly nitrooxy-OSs, exhibit a positive correlation with increasing humidity rather than atmospheric oxidants in this high-humidity site. This suggests that high RH can promote the formation of OSs, possibly through enhancing particle surface area and volume, and creating a favorable environment for aqueous-phase or heterogeneous reactions in the particle phase. A considerable proportion of CHOS compounds may be derived from anthropogenic aliphatic hydrocarbon derivatives. These compounds exhibit slightly elevated daytime concentrations due to increased emissions of long-chain aliphatics from sources such as diesel combustion, as well as photochemically enhanced oxidation to OSs. In contrast, CHONS compounds increased at night, driven by high-humidity liquid-phase oxidation. Terpenoid derivatives accounted for 13.4% of MSOC and contributed over 40% to nighttime CHONS. These findings highlight humidity’s important role in driving daytime and nighttime processing of anthropogenic and biogenic precursors to form SOA, even under low SO₂ and NO_x conditions. Full article

Nitro-functionalized heterocycles, such as nitroimidazoles, are significant environmental contaminants and have been identified as components of secondary organic aerosols (SOA) and biomass-burning organic aerosols (BBOA). Their strong absorption in the near-UV (300–400 nm) makes photochemistry a critical aspect of their atmospheric processing. This study investigates both the direct near-UV photochemistry and hydroxyl radical (OH) oxidation of 4-nitroimidazole (4-NI). The atmospheric photolysis rate of 4-NI in the near-UV (300–400 nm) was found to be J_4-NI = 4.3 × 10⁻⁵ (±0.8) s⁻¹, corresponding to an atmospheric lifetime of 391 (±77) min under bulk aqueous conditions simulating aqueous aerosols and cloud water. Electrospray ionization mass spectrometry (ESI-MS) analysis following irradiation indicated loss of the nitro group, while NO elimination was observed as a more minor channel in direct photolysis. In addition, the rate constant for the reaction of 4-NI with OH radicals, k_NI+OH, was determined to be 2.9 × 10⁹ (±0.6) M⁻¹s⁻¹. Following OH oxidation, ESI-MS results show the emergence of a dominant peak at m/z = 130 amu, consistent with hydroxylation of 4-NI. Computational results indicate that OH radical addition occurs with the lowest barrier at the C2 and C5 positions of 4-NI. The combined results from direct photolysis and OH oxidation experiments suggest that OH-mediated degradation is likely to dominate under aerosol-phase conditions, where OH radical concentrations are elevated, while direct photolysis is expected to be the primary loss mechanism in high-humidity environments and bulk cloud water. Full article

Atmospheric aqueous-phase reactions have been recognized as an important source of secondary organic aerosols (SOAs). However, the unclear reaction kinetics and mechanics hinder the in-depth understanding of the SOA sources and formation processes. This study selected ten different substituted phenolic compounds (termed as PhCs) emitted from biomass burning as precursors, to investigate the kinetics using OH oxidation reactions under simulated sunlight. The factors influencing reaction rates were examined, and the contribution of reactive oxygen species (ROS) was evaluated through quenching and kinetic analysis experiments. The results showed that the pseudo-first-order rate constants (k_obs) for the OH oxidation of phenolic compounds ranged from 1.03 × 10⁻⁴ to 7.85 × 10⁻⁴ s⁻¹ under simulated sunlight irradiation with an initial H₂O₂ concentration of 3 mM. Precursors with electron-donating groups (-OH, -OCH₃, -CH₃, etc.) exhibited higher electrophilic radical reactivity due to the enhanced electron density of the benzene ring, leading to higher reaction rates than those with electron-withdrawing groups (-NO₂, -CHO, -COOH). At pH 2, the second-order reaction rate (k_{PhCs, OH}) was lower than at pH 5. However, the k_obs did not show dependence on pH. The presence of O₂ facilitated substituted phenols’ photodecay. Inorganic salts and transition metal ions exhibited varying effects on reaction rates. Specifically, NO₃⁻ and Cu²⁺ promoted k_{PhCs, OH}, Cl⁻ significantly enhanced the reaction at pH 2, while SO₄²⁻ inhibited the reaction. The k_{PhCs, OH} were determined to be in the range of 10⁹~10¹⁰ L mol⁻¹ s⁻¹ via the bimolecular rate method, and a modest relationship with their oxidation potential was found. Additionally, multiple substituents can suppress the reactivity of phenolic compounds toward •OH based on Hammett plots. Quenching experiments revealed that •OH played a dominant role in phenolic compound degradation (exceeding 65%). Electron paramagnetic resonance confirmed the generation of singlet oxygen (¹O₂) in the system, and probe-based quantification further explored the concentrations of •OH and ¹O₂ in the system. Based on reaction rates and concentrations, the atmospheric aqueous-phase lifetimes of phenolic compounds were estimated, providing valuable insights for expanding atmospheric kinetic databases and understanding the chemical transformation and persistence of phenolic substances in the atmosphere. Full article

Biogenic volatile organic compounds (BVOCs) emitted by plants contribute to secondary air pollution through photochemical reactions in sunlight. Due to the influence of multiple factors, accurately characterizing and quantifying the emission of BVOCs from plant sources is challenging, which poses significant obstacles to the effective management and control of BVOCs. Therefore, this paper summarizes the emission mechanisms of BVOCs from plants, explores the primary factors influencing variations in the emission rates of these compounds, and evaluates the advantages and limitations of contemporary “measurement-modeling” methods for characterizing BVOC emissions. It is concluded that current measurement techniques still need to be further developed to meet the criteria of simplicity, affordability, and high precision simultaneously, and in terms of modeling and prediction studies, there is a lack of in-depth research on the atmospheric chemistry of BVOCs and the synergistic effects of multiple factors. Finally, it is suggested to leverage interdisciplinary strengths to develop advanced measurement technologies and high-resolution models for monitoring volatile compounds. Additionally, strategically selecting low-BVOC tree species in pollution-vulnerable urban areas—contingent on rigorous ecological assessments—combined with stringent controls on anthropogenic precursors (e.g., anthropogenic volatile organic compounds (AVOCs)) could serve as a complementary measure to mitigate secondary pollution. Full article

Atmospheric intermediate volatile organic compounds (IVOCs) are important precursors of secondary organic aerosols (SOAs), and in-depth research on them is crucial for atmospheric pollution control. This review systematically synthesizes global advancements in understanding IVOC sources, emissions characterization, compositional characteristics, ambient concentrations, SOA contributions, and health risk assessments. IVOCs include long-chain alkanes (C₁₂~C₂₂), sesquiterpenes, polycyclic aromatic hydrocarbons, monocyclic aromatic hydrocarbons, phenolic compounds, ketones, esters, organic acids, and heterocyclic compounds, which originate from primary emissions and secondary formation. Primary emissions include direct emissions from anthropogenic and biogenic sources, while secondary formation mainly results from radical reactions or particulate surface reactions. Recently, the total IVOC emissions have decreased in some countries, while emissions from certain sources, such as volatile chemical products, have increased. Ambient IVOC concentrations are generally higher in urban rather than in rural areas, higher indoors than outdoors, and on land rather than over oceans. IVOCs primarily generate SOAs via oxidation reactions with hydroxyl radicals, nitrate radicals, the ozone, and chlorine atoms, which contribute more to SOAs than traditional VOCs, with higher SOA yields. SOA tracers for IVOC species like naphthalene and β-caryophyllene have been identified. Integrating IVOC emissions into regional air quality models could significantly improve SOA simulation accuracy. The carcinogenic risk posed by naphthalene should be prioritized, while benzo[a]pyrene requires a combined risk assessment and hierarchical management. Future research should focus on developing high-resolution online detection technologies for IVOCs, clarifying the multiphase reaction mechanisms involved and SOA tracers, and conducting comprehensive human health risk assessments. Full article

The interaction of nitrate radicals (NO₃) with the air–water interface is a critical aspect of atmospheric chemistry, influencing processes such as secondary organic aerosol (SOA) formation, pollutant transformation, and nighttime oxidation. This study investigates the behavior of NO₃ radicals at the air–water interface and in bulk water environments through ab initio molecular dynamics simulations, directly comparing them with Cl and ClO radicals. Three distinct configurations of NO₃ in water droplets were analyzed: surface-parallel, surface-perpendicular, and bulk-phase. The results reveal environment-dependent dynamics, with surface-localized NO₃ radicals exhibiting fewer but more flexible hydrogen bonds compared to bulk-solvated radicals. Analysis of radial distribution functions, coordination numbers, and population distributions demonstrates that NO₃ radicals maintain distinct interfacial and bulk-phase preferences, with rapid equilibration in both environments. Electronic structure analysis shows significant modulation of spin density and molecular orbital distributions between surface and bulk environments. The comparative analysis with Cl and ClO radicals highlights how the unique planar geometry and delocalized π-system of NO₃ influence its hydration patterns and interfacial activity. These results offer fundamental molecular-level insights into NO₃ radical behavior at the air–water interface and in aqueous environments, enhancing our understanding of their role in heterogeneous atmospheric processes and nocturnal chemistry. Full article

Oligomerization of glyoxal (GL) and methylglyoxal (MG) plays a vital role in secondary organic aerosol (SOA) formation in aqueous aerosols. However, the influence of emerging contaminants on the oligomerization of GL and MG remains unclear. Therefore, using quantum chemical and kinetic calculations, we investigated the oligomerization of GL and MG in the presence of phthalate esters (PAEs), including dimethyl phthalate (DMP), diethyl phthalate (DEP), dipropyl phthalate (DPP), and dibutyl phthalate (DBP), and the role of PAEs in the oligomerization. Our findings indicate that the direct PAE-mediated oligomerization of GL and MG is hindered due to the lack of reactive sites. However, the oligomerization of GL and MG is readily mediated by the hydrolysates of PAEs, which are the preferred forms of PAEs in weakly acidic aerosols, attributable to the additional -OH groups. The mechanisms show that the indirect PAE-mediated oligomerization proceeds via three-step reactions, including nucleophilic attack on carbenium ions, hydration, and deprotonation, which are thermodynamically and kinetically favorable. Our results reveal that the role of PAEs in the GL/MG oligomerization needs to be emphasized, particularly in conditions with a pH value approaching neutrality. Full article

Air quality simulations were performed for Athens (Greece) in ~1 km resolution applying the models WRF-CAMx for July and December 2019 with the secondary organic aerosol processor (SOAP) and volatility basis set (VBS) organic aerosol (OA) schemes. CAMx results were evaluated against particulate matter (PM) and OA concentrations from the regulatory monitoring network and research monitoring sites (including PM_2.5 low-cost sensors). The repartition of primary OA (POA) and secondary OA (SOA) by CAMx was compared with positive matrix factorization (PMF)-resolved OA components based on aerosol chemical speciation monitor (ACSM) measurements. In July, OA concentrations underestimation was decreased by up to 24% with VBS. In December, VBS introduced small negative biases or resulted in more pronounced (but moderate) underestimations of OA with respect to SOAP. CAMx performance for POA was much better than for SOA, while VBS decreased the overestimation of POA and the underestimation of SOA in both study periods. Despite the SOA concentrations increases by VBS, CAMx still considerably underestimated SOA (e.g., by 65% in July). Better representation of simulated OA concentrations in Athens could benefit by accounting for the missing cooking emissions, by improvements in the biomass burning emissions, or by detailed integration of processes related to OA chemical aging. Full article

Isoprene emissions can affect the oxidizing capacity of the atmosphere and are likely to increase with an increase in the world’s biomass. The emission of isoprene is strongest in tropical forested regions, suggesting a major portion of tropospheric chemistry occurs in the tropics. As well as deforestation and reforestation having a direct impact on the world’s climate through land cover, there is also an indirect environmental impact (e.g., global warming, air pollution) through the resulting change in isoprene emissions. Previously, incomplete understanding of isoprene oxidation chemistry caused a model-measurement breakdown for concentrations of HO_x radicals observed over certain low-NO_x regions, such as the pristine Amazon rainforest. Over the last decade, however, understanding of isoprene oxidation chemistry has been vastly improved. Numerous research studies have provided evidence for the involvement of 1,6-H and 1,5-H shift reactions in the isoprene oxidation mechanism, which increases the level of HO_x recycling that occurs. As well as helping to reduce the model-measurement breakdown observed, the updated isoprene oxidation mechanism affects the tropospheric burdens of other species, including carbon monoxide (CO), methane (CH₄), ozone (O₃), organic peroxides (ROOH), secondary organic aerosol (SOA), and organic nitrates (RONO₂). There are still gaps in the understanding of the impacts and oxidation chemistry of isoprene emissions, which this literature review identifies and discusses. In the future, there is still much scope for further research, including modeling future reforestation scenarios with isoprene emissions and their impacts on both global and regional scales. Full article

Diesel vehicles are recognized as significant mobile sources of particulate matter emissions. As a renewable and environmentally friendly alternative to conventional fossil diesel, biodiesel offers the benefit of reducing greenhouse gas emissions. However, existing research on biodiesel emissions primarily focuses on primary emissions, with a limited understanding of their impact on secondary organic aerosol (SOA) formation. In this study, a diesel engine test bench was employed under idle conditions using three commonly used biodiesel blends. Exhaust emissions were directly introduced into the HAP-SWFU chamber, a quartz glass smog chamber designed to characterize both primary emissions and SOA formation during the photochemical oxidation process. The black carbon and primary organic aerosol (POA) emission factors for the three biodiesel blends under idle conditions ranged from 0.31 to 0.58 g kg⁻¹ fuel and 0.99 to 1.06 g kg⁻¹ fuel, respectively. The particle size of exhaust particulates peaked between 20 and 30 nm, and nucleation-idle conditions were found to be the dominating mode. The SOA production factor was between 0.92 and 1.15 g kg⁻¹ fuel, and the SOA/POA ratio ranged from 1.35 to 2.37, with an average of 1.86. This study concludes that the POA emission factor for biodiesel under idle conditions is comparable to values reported in previous studies on pure diesel exhaust, with the maximum SOA production factor reduced by 38%. Full article

Formaldehyde (HCHO), a key volatile organic compound (VOC) in the atmosphere, plays a crucial role in driving photochemical processes. Satellite-based observations of column concentrations of HCHO and other gaseous pollutants (e.g., NO₂) have generally been used in previous studies to elucidate the mechanisms behind secondary organic aerosol (SOA) and ozone (O₃) formation. This study aimed to investigate the characteristics of HCHO by retrieving its vertical profile over Nanjing during the warm season (May–June 2022) and analyzing the diurnal variation in vertical distribution and potential source regions on non-polluted (MDA8 O₃ < 160 μg m⁻³, NO₃P) and O₃-polluted (MDA8 O₃ ≥ 160 μg m⁻³, O₃P) days. Under both conditions, HCHO was primarily concentrated below 1.5 km altitude, with average vertical profiles displaying similar Boltzmann-like distributions. However, HCHO concentrations on O₃P days were 1.2–1.6 times higher than those on non-polluted days at the same altitude below 1.5 km. Maximum HCHO concentrations occurred in the afternoon, while the peak value in the 0.1–0.4 km layers was reached around noon (~11:00 a.m.). The variation rates (VR) of HCHO in the 0.3–1.2 km altitudes had a maximum on O₃P days (approximately 0.33 ppbv h⁻¹), and were significantly higher (p < 0.01) than the VR observed on NO₃P days (0.14–0.20 ppbv h⁻¹). The analysis of footprints showed that HCHO concentrations were jointly influenced by the upstream region and the surroundings of the study site. The study results improve the understanding of the vertical distribution and potential source regions of HCHO. Full article

Sixty-four phenols grouped as nitrated, bromo, amino, methyl, chloro-phenols, and cresols, and thirty-eight organic acids grouped as mono-carboxylic and dicarboxylic are analyzed in forty-two fog samples collected in the Alsace region between 2015 and 2021 to check their atmospheric behavior. Fogwater samples are collected using the Caltech Active Strand Cloudwater Collector (CASCC2), extracted using liquid–liquid extraction (LLE) on a solid cartridge (XTR Chromabond), and then analyzed using gas chromatography coupled with mass spectrometry (GC-MS). The results show the high capability of phenols and acids to be scavenged by fogwater due to their high solubility. Nitro-phenols and mono-carboxylic acids have the highest contributions to the total phenolic and acidic concentrations, respectively. 2,5-dinitrophenol, 3-methyl-4-nitrophenol, 4-nitrophenol, and 3,4-dinitrophenol have the highest concentration, originating mainly from vehicular emissions and some photochemical reactions. The top three mono-carboxylic acids are hexadecenoic acid (C16), eicosanoic acid (C18), and dodecanoic acid (C12), whereas succinic acid, suberic acid, sebacic acid, and oxalic acid are the most concentrated dicarboxylic acids, originated either from atmospheric oxidation (mainly secondary organic aerosols (SOAs)) or vehicular transport. Pearson’s correlations show positive correlations between organic acids and previously analyzed metals (p < 0.05), between mono- and dicarboxylic acids (p < 0.001), and between the analyzed acidic compounds (p < 0.001), whereas no correlations are observed with previously analyzed inorganic ions. Total phenolic and acidic fractions are found to be much higher than those observed for pesticides, polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyls (PCBs) measured at the same region due to their higher scavenging by fogwater. Full article

Intermediate-volatility organic compounds (IVOCs) serve as pivotal precursors to secondary organic aerosol (SOA). They are highly susceptible to substantial wall losses both in indoor environments and within smog chambers even with Teflon walls. Accurately characterizing the wall loss effects of IVOCs is thus essential for simulation studies aiming to replicate their atmospheric behaviors in smog chambers to ensure precise modeling of their physical and chemical processes, including SOA formation, yet a comprehensive understanding of the wall loss behavior of IVOCs remains elusive. In this study, we conducted a thorough characterization of wall losses for typical intermediate-volatility hydrocarbon compounds, including eight normal alkanes (n-alkanes) and eight polycyclic aromatic hydrocarbons (PAHs), using the smog chamber with a 30 m³ Teflon reactor. Changes in the concentrations of gaseous IVOCs with the chamber were observed under dark conditions, and the experimental data were fitted to the reversible gas–wall mass transfer theory to determine the key parameters such as the wall accommodation coefficient (α_w) and the equivalent organic aerosol concentration (C_w) for different species. Our results reveal that C_w values for these hydrocarbon IVOCs range from 0.02 to 5.41 mg/m³, which increase with volatility for the PAHs but are relative stable for alkanes with an average of 3.82 ± 0.92 mg/m³. α_w span from 1.24 × 10⁻⁷ to 1.01 × 10⁻⁶, with the values for n-alkanes initially showing an increase followed by a decrease as carbon numbers rise and volatility decreases. The average α_w for n-alkanes and PAHs are 3.34 × 10⁻⁷ and 6.53 × 10⁻⁷, respectively. Our study shows that IVOCs exhibit different loss rates onto clean chamber walls under dry and dark conditions, with increasing rate as the volatility decreases. This study demonstrates how parameters can be acquired to address wall losses when conducting smog chamber simulation on atmospheric processes of IVOCs. Full article