Atmospheric polycyclic aromatic hydrocarbons in India: geographical distribution, sources and associated health risk-a review.

Atmospheric distribution of polycyclic aromatic hydrocarbons and associated human health risks have been studied in India. However, a comprehensive overview is not available in India, this review highlights the possible sources, and associated cancer risks in people living in different zones of India. Different databases were searched for the scientific literature on polycyclic aromatic hydrocarbons in ambient air in India. Database searches have revealed a total of 55 studies conducted at 139 locations in India in the last 14 years between 1996 and 2018. Based on varying climatic conditions in India, the available data was analysed and distributed with four zone including north, east, west/central and south zones. Comparatively higher concentrations were reported for locations in north zone, than east, west/central and south zones. The average concentrations of ∑PAHs is lower in east zone, and concentrations in north, west/central and south zones are higher by 1.67, 1.47, and 1.12 folds respectively than those in east zone. Certain molecular diagnostic ratios and correlation receptor models were used for identification of possible sources, which aided to the conclusion that both pyrogenic and petrogenic activities are the mixed sources of PAH emissions to the Indian environment. Benzo(a)pyrene toxicity equivalency for different zones is estimated and presented. Estimated Chronic daily intake (CDI) due to inhalation of PAHs and subsequently, cancer risk (CR) is found to be ranging from extremely low to low in various geographical zones of India.

Comprehensive analysis of metal(loid)s and associated metal(loid) resistance genes in atmospheric particulate matter.

Despite global concerns about metal(loid)s in atmospheric particulate matter (PM), the presence of metal(loid) resistance genes (MRGs) in PM remains unknown. Therefore, we conducted a comprehensive investigation of the metal(loid)s and associated MRGs in PMs in two seasons (summer and winter) in Xiamen, China. According to the geoaccumulation index (Igeo), most metal(loid)s, except for V and Mn, exhibited enrichment in PM, suggesting potential anthropogenic sources. By employing Positive Matrix Factorization (PMF) model, utilizing a dataset encompassing both total and bioaccessible metal(loid)s, along with backward trajectory simulations, traffic emissions were determined to be the primary potential contributor of metal(loid)s in summer, whereas coal combustion was observed to have a dominant contribution in winter. The major contributor to the carcinogenic risk of metal(loid)s in both summer and winter was predominantly attributed to coal combustion, which serves as the main source of bioaccessible Cr. Bacterial communities within PMs showed lower diversity and network complexity in summer than in winter, with Pseudomonadales being the dominant order. Abundant MRGs, including the As(III) S-adenosylmethionine methyltransferase gene (arsM), Cu(I)-translocating P-type ATPase gene (copA), Zn(II)/Cd(II)/Pb(II)-translocating P-type ATPase gene (zntA), and Zn(II)-translocating P-type ATPase gene (ziaA), were detected within the PMs. Seasonal variations were observed for the metal(loid) concentration, bacterial community structure, and MRG abundance. The bacterial community composition and MRG abundance within PMs were primarily influenced by temperature, rather than metal(loid)s. This research offers novel perspectives on the occurrence of metal(loid)s and MRGs in PMs, thereby contributing to the control of air pollution.

Atmospheric gaseous mercury and associated health risk assessment in the economic capital of India.

Mercury cycling in coastal metropolitan areas on the west coast of India becomes complex due to the combined effects of both intensive domestic anthropogenic emissions and marine air masses. The present study is based on yearlong data of continuous measurements of gaseous elemental mercury (GEM) concentration concurrent with meteorological parameters and some air pollutants at a coastal urban site in Mumbai, on the west coast of India, for the first time. The concentration of GEM was found in a range between 2.2 and 12.3 ng/m3, with a mean of 3.1 ± 1.1 ng/m3, which was significantly higher than the continental background values in the Northern Hemisphere (~ 1.5 ng/m3). Unlike particulates, GEM starts increasing post-winter to peak during the monsoon and decrease towards winter. July had the highest concentration of GEM followed by October, and a minimum in January. GEM exhibited a distinct diurnal cycle, mainly with a broad peak in the early morning, a narrow one by nightfall, and a minimum in the afternoon. The peaks and their timing suggest the origin of urban mobility and the start of local activities. A positive correlation between SO2, PM2.5, temperature, relative humidity, and GEM indicates that emissions from local industrial plants in the Mumbai coastal area. Principal component analysis (PCA) and cluster analysis (CA) confirm this fact. Monthly back trajectory analysis showed that air mass flows are predominantly from the Arabian Sea and local human activities. Assessment of human health risks by USEPA model reveals that the hazardous quotient, HQ < 1, implies negligible carcinogenic risk. GEM observations in Mumbai during the study period are below the World Health Organization's (WHO) safe limit (200 ng/m3) for long-term inhalation.

Occurrence and Fate of Per- and Polyfluoroalkyl Substances (PFAS) in Atmosphere: Size-Dependent Gas-Particle Partitioning, Precipitation Scavenging, and Amplification.

The concerns about the fate of per- and polyfluoroalkyl substances (PFAS) in the atmosphere are continuously growing. In this study, size-fractionated particles, gas, and rainwater samples were simultaneously collected in Shijiazhuang, China, to investigate the multiphase distribution of PFAS in the atmosphere. Perfluoroalkyl carboxylic acids (PFCAs) dominated the total concentration of PFAS in atmospheric media. A strong positive relationship (0.79 < R2 < 0.99) was observed between the concentration of PFCAs and organic matter fraction (fOM) in different particle size fractions, while no such relationship for perfluoroalkyl sulfonic acids (PFSAs) and fOM, suggesting fOM may be an important factor influencing the size-dependent distribution of PFCAs. Temperature played a key role in the gas-particle partitioning of PFAS, while it did not significantly affect their particle-size-dependent distribution. The associative concentration fluctuation of particle and particle-bound PFAS during precipitation suggested that precipitation scavenging was an important mechanism for the removal of PFAS from the atmosphere. Furthermore, temporary increases in atmospheric PFAS concentrations were observed during the precipitation. Fugacity ratios of PFAS in rainwater and gas phase (log fR/fG ranged between 2.0 and 6.6) indicated a strong trend for PFAS to diffuse from the rainwater to the gas phase during the precipitation, which may explain that the concentration of PFAS in the gas phase continued to increase even at the end of the precipitation.

Assessing pesticides in the atmosphere: A global study on pollution, human health effects, monitoring network and regulatory performance.

Pesticides are widely used in agriculture, but their impact on the environment and human health is a major concern. While much attention has been given to their presence in soil, water, and food, there have been few studies on airborne pesticide pollution on a global scale. This study aimed to assess the extent of atmospheric pesticide pollution in countries worldwide and identify regional differences using a scoring approach. In addition to analyzing the health risks associated with pesticide pollution, we also examined agricultural practices and current air quality standards for pesticides in these countries. The pollution scores varied significantly among the countries, particularly in Europe. Asian and Oceanic countries generally had higher scores compared to those in the Americas, suggesting a relatively higher level of air pollution caused by pesticides in these regions. It is worth noting that the current pollution levels, as assessed theoretically, pose minimal health risks to humans. However, studies in the literature have shown that excessive exposure to pesticides present in the atmosphere has been associated with various health problems, such as cancer, neuropsychiatric disorders, and other chronic diseases. Interestingly, European countries had the highest overall pesticide application intensities, but this did not necessarily correspond to higher atmospheric pesticide pollution scores. Only a few countries have established air quality standards specifically for pesticides. Furthermore, pollution scores across states in the USA were investigated and the global sampling sites were mapped. The findings revealed that the scores varied widely in the USA and the current sampling sites were limited or unevenly distributed in some countries, particularly the Nordic countries. These findings can help global relevant environmental agencies to set up comprehensive monitoring networks. Overall, the present research highlights the need to create a pesticide monitoring system and increase efforts to enhance pesticide regulation, ensure consistency in standards, and promote international cooperation.

Occurrence of N-nitrosamines in the atmosphere and human health risk: A case study in an urban area of Chuncheon, Gangwon State, South Korea.

This study aimed to investigate the occurrence of eight nitrosamines (NAs) in particulate (PM2.5) and gaseous phases and assess the human health risk associated with these compounds in an urban area of Chuncheon, Gangwon State, South Korea, across four sampling seasons. The findings revealed that the total concentrations of eight NAs measured during the sampling period exceeded the public health recommendation of 0.3 ng/m3 provided by the Norwegian Institute of Public Health, indicating a potential human health risk from NA exposures. In particular, the average total NA concentration observed in the gaseous samples during the winter of 2021 was 18.1 ± 6.46 ng/m3. The primary emission sources could potentially impact the concentrations of NAs in the atmosphere due to their significant positive correlation with primary emission species such as NO2, CO, and SO2. Moreover, the levels of particulate NAs during the summer were negatively correlated with O3, suggesting that their formation might be influenced by ozonation in the aqueous aerosol phase. In addition, the total NA concentrations measured in the gaseous phase were four to six times higher than those measured in the PM2.5 phase throughout the sampling period. Thus, domestic sources have the potential to impact the pollution levels of the research area more significantly than long-range atmospheric transport. In particular, the highest concentrations of NAs in the gas phase were observed during the winter, while the lowest concentrations were recorded in the summer, possibly influenced by photolysis. Nevertheless, the study suggested that tertiary amines might contribute to the presence of gaseous NAs in sunlight. Consequently, further studies focusing on the occurrence of tertiary amines in the gas phase should be considered. The cumulative lifetime cancer risks estimated from inhalation exposure exceeded the acceptable risk level of 10⁻6 for all age groups across all four seasons. Therefore, it is crucial to implement effective control measures to mitigate potential health risks associated with exposure to NAs.

Atmospheric Degradation of Ecologically Important Biogenic Volatiles: Investigating the Ozonolysis of (E)-ß-Ocimene, Isomers of α and ß-Farnesene, α-Terpinene and 6-Methyl-5-Hepten-2-One, and Their Gas-Phase Products.

Biogenic volatile organic compounds (bVOCs), synthesised by plants, are important mediators of ecological interactions that can also undergo a series of reactions in the atmosphere. Ground-level ozone is a secondary pollutant generated through sunlight-driven reactions between nitrogen oxides (NOx) and VOCs. Its levels have increased since the industrial revolution and reactions involving ozone drive many chemical processes in the troposphere. While ozone precursors often originate in urban areas, winds may carry these hundreds of kilometres, causing ozone formation to also occur in less populated rural regions. Under elevated ozone conditions, ozonolysis of bVOCs can result in quantitative and qualitative changes in the gas phase, reducing the concentrations of certain bVOCs and resulting in the formation of other compounds. Such changes can result in disruption of bVOC-mediated behavioural or ecological interactions. Through a series of gas-phase experiments using Gas Chromatography Mass Spectrometry (GC-MS) and Proton Transfer Reaction Mass Spectrometry (PTR-MS), we investigated the products and their yields from the ozonolysis of a range of ubiquitous bVOCs, which were selected because of their importance in mediating ecological interactions such as pollinator and natural enemy attraction and plant-to-plant communication, namely: (E)-ß-ocimene, isomers of α and ß-farnesene, α-terpinene and 6-methyl-5-hepten-2-one. New products from the ozonolysis of these compounds were identified, and the formation of these compounds is consistent with terpene-ozone oxidation mechanisms. We present the degradation mechanism of our model bVOCs and identify their reaction products. We discuss the potential ecological implications of the degradation of each bVOC and of the formation of reaction products.

Theoretical investigation on the mechanism and kinetics of the OH•‒initiated atmospheric degradation of p-chloroaniline: Addition of ∑g-3O2 and isomerization of peroxy radicals.

Atmospheric oxidation of the p-chloroaniline-OH• adduct [C6H4ClNH2-OH]• (AD-C2) by ∑g-3O2 and internal isomerization processes of peroxy radical [C6H4ClNH2-OH]•-O2 are theoretically investigated at the M06-2X/aug-cc-pVTZ and CBS-QB3//M06-2X/aug-cc-pVTZ level of theories. Potential energy surfaces (PESs) for the most efficient pathways indicated that the oxidation process begins via the complexation of individual reactants in syn mode forming PRCy-iOO-syn (y = 2,5) in an exothermic and endogenic step. The syn mode addition is favored over the anti one due to the formation of internal hydrogen bond between the hydroxyl and peroxy groups. Formation of new C5-OO bond in PRCy-iOO-syn complex is an unimolecular process which is exothermic and exoergic. This pathway is predominated over other internal conversions due to the presence of stronger intramolecular hydrogen bond. Cyclization of the produced [C6H4ClNH2-OH]•-O2 peroxy radical AD-C2-5OO-syn into the bicyclic peroxy radical AD-C2-5,6OO-syn is the last step which is strongly endothermic and endogenic. The rate coefficients are calculated by means of the RRKM theory over the temperature range 250-350 K and at a pressure range of 0.1 bar to the high-pressure limit. The RRKM rate coefficients at the M06-2X/aug-cc-pVTZ level for the first bimolecular and last unimolecular steps are in order of 10-16 cm3 molecule-1 s-1 and 10-7 s-1, respectively, while the obtained rate coefficients at the CBS-QB3//M06-2X/aug-cc-pVTZ are overestimated about two order of magnitude.

Impact of M Dwarfs Ultraviolet Radiation on Prebiotic Chemistry: The Case of Adenine.

To date, several exoplanets have been found to orbit within the habitable zone of main sequence M stars (M dwarfs). These stars exhibit different levels of chromospheric activity that produces ultraviolet (UV) radiation. UV may be harmful to life, but it can also trigger reactions of prebiotic importance on the surface of a potentially habitable planet (PHP). We created a code to obtain the adenine yield for a known adenine synthesis route from diaminomaleonitrile (DAMN). We used computational methods to calculate the reaction coefficient rates (photolysis rate J and rate constant K) for the intermediate molecules DAMN, diaminofumaronitrile (DAFN), and 4-aminoimidazole-5-carbonitrile (AICN) of the adenine synthesis route. We used stellar UV sources and a mercury lamp to compare the theoretical results with experiments performed with lamps. The surface UV flux of planets in the habitable zone of two active M dwarfs (Proxima Centauri and AD Leonis) and the prebiotic Earth was calculated using the photochemical model ATMOS, considering a CO2-N2-H2O atmosphere. We obtained UV absorption coefficients for DAMN and DAFN and thermodynamic parameters that are useful for prebiotic chemistry studies. According to our results, experiments using UV lamps may underestimate the photolysis production of molecules of prebiotic importance. Our results indicate that photolysis reactions are fast with a yield of 50% of AICN in 10 s for the young Sun and ∼1 h for Proxima Centauri b. Planets around active M dwarfs may provide the most favorable environment for UV-mediated production of compounds relevant to the origins of life. The kinetic reaction AICN + HCN  adenine is the bottleneck of the pathway with reaction rates <10-22 L/(mol·s).

Characterization of Polycyclic Aromatic Hydrocarbons (PAHs) associated with fine aerosols in ambient atmosphere of high-altitude urban environment in Sikkim Himalaya.

Polycyclic Aromatic Hydrocarbons (PAHs) compounds are ubiquitous in ambient air due to their persistence, carcinogenicity, and mutagenicity. Gangtok being one of the cleanest cities in India located in Eastern Himalayan region, witnesses high developmental activities with enhanced urbanization affecting the ambient air quality. The present study aims to measure PM2.5 and PAHs in the ambient atmosphere of the Sikkim Himalaya to understand the influence of natural and anthropogenic activities on aerosol loading and their chemical characteristics. The PM2.5 samples were collected and analysed for the duration from Jan 2020 to Feb 2021.The seasonal mean concentrations of PM2.5 and PAHs were observed to be high during autumn and low during summer season. Overall, the annual mean concentration of PM2.5 was found higher than the prescribed limit of World Health Organization and National Ambient Air Quality Standards. The concentration of the 16 individual PAHs were found to be highest during autumn season (55.26 ± 37.15 ng/m3). Among the different PAHs, the annual mean concentration of fluorene (3.29 ± 4.07 ng/m3) and naphthalene (1.15 ± 3.76 ng/m3) were found to be the highest and lowest, respectively. The Molecular Diagnostic Ratio (MDR) test reveals higher contribution from heavy traffic activities throughout the winter and autumn seasons. The other possible sources identified over the region are fossil fuel combustion, and biomass burning. The multivariate statistical analysis (Multifactor Principal Component Analysis) also indicates a strong association between PM2.5 /PAHs and meteorological variables across the region in different seasons. The precipitation and wind pattern during the study period suggests that major contribution of the PM2.5 and PAHs were from local sources, with minimal contribution from long-range transport. The findings are important for comprehending the trends of PAH accumulation over a high-altitude urban area, and for developing sustainable air quality control methods in the Himalayan region.

Size-resolved gas-particle partitioning characteristics of typical semi-volatile organic compounds in urban atmosphere.

Understanding particle size distribution and size-resolved gas-particle partitioning of semi-volatile organic compounds (SVOCs) is important for characterizing their fate in atmosphere. However, the size-resolved gas-particle partitioning characteristics of SVOCs has not been adequately considered. To address this issue, the present study collected gaseous and size-fractioned particulate samples both in and outside of schools, offices, and residences in three districts of different urbanization levels in a megacity, Guangzhou, South China during two seasons. Typical SVOCs, including 15 polycyclic aromatic hydrocarbons (PAHs), six organophosphate esters and seven phthalic acid esters were measured. Emission sources, physicochemical properties, and environmental conditions at the sampling sites considerably impacted the spatiotemporal distribution patterns and particle size distribution of target SVOCs. Not all observed gas-particle partition coefficients (Kp) of target SVOCs were negatively correlated with subcooled liquid-vapor pressures (PL0), probably because certain factors, such as the non-exchangeable part of the particle-bound SVOCs, were not considered in traditional gas-particle partition theories. Particle size was an important factor affecting gas-particle partitioning. Adsorption was the dominant mechanism for PAHs with high molecular weight in different particle modes. A new model was established to predict size-resolved Kp of PAHs with high molecular weight based on PL0 and particle size.

Geochemical studies of low molecular weight organic acids in the atmosphere: sources, formation pathways, and gas/particle partitioning.

Low molecular weight monocarboxylic acids (LMW monoacids, C1-C10) are the most abundant gaseous organic compound class in the atmosphere. Formic or acetic acid is the dominant volatile organic compound (VOC) in Earth's atmosphere. They can largely contribute to rainwater acidity, especially in the tropical forest, and react with alkaline metals, ammonia, and amines, contributing to new particle formation and secondary organic aerosol production. Gaseous and particulate LMW monoacids were abundantly reported in China. They can be directly emitted from fossil fuel combustion and biomass burring; however, the secondary formation is more important than primary emissions via the photochemical oxidation of anthropogenic and biogenic VOCs. In this paper, we review the distributions of LMW monoacids from urban, mountain, and marine sites as well as from rainwater and alpine snow samples and discuss their sources and formation mechanisms in the atmosphere. We also discuss their importance as cloud condensation nuclei (CCN) and provide future perspectives of LMW monoacids study in the warming world.

Multiple evaluations of atmospheric behavior between Criegee intermediates and HCHO: Gas-phase and air-water interface reaction.

Given the high abundance of water in the atmosphere, the reaction of Criegee intermediates (CIs) with (H2O)2 is considered to be the predominant removal pathway for CIs. However, recent experimental findings reported that the reactions of CIs with organic acids and carbonyls are faster than expected. At the same time, the interface behavior between CIs and carbonyls has not been reported so far. Here, the gas-phase and air-water interface behavior between Criegee intermediates and HCHO were explored by adopting high-level quantum chemical calculations and Born-Oppenheimer molecular dynamics (BOMD) simulations. Quantum chemical calculations evidence that the gas-phase reactions of CIs + HCHO are submerged energy or low energy barriers processes. The rate ratios speculate that the HCHO could be not only a significant tropospheric scavenger of CIs, but also an inhibitor in the oxidizing ability of CIs on SOx in dry and highly polluted areas with abundant HCHO concentration. The reactions of CH2OO with HCHO at the droplet's surface follow a loop structure mechanism to produce i) SOZ (), ii) BHMP (HOCH2OOCH2OH), and iii) HMHP (HOCH2OOH). Considering the harsh reaction conditions between CIs and HCHO at the interface (i.e., the two molecules must be sufficiently close to each other), the hydration of CIs is still their main atmospheric loss pathway. These results could help us get a better interpretation of the underlying CIs-aldehydes chemical processes in the global polluted urban atmospheres.

Selection and Analytical Performances of the Dragonfly Mass Spectrometer Gas Chromatographic Columns to Support the Search for Organic Molecules of Astrobiological Interest on Titan.

Titan is a key planetary body for astrobiology, with the presence of a subsurface ocean and a dense atmosphere, in which complex chemistry is known to occur. Approximately 1-Titan-year after the Cassini-Huygens mission arrived in the saturnian system, Dragonfly rotorcraft will land on Titan's surface by 2034 for an exhaustive geophysical and chemical investigation of the Shangri-La organic sand sea region. Among the four instruments onboard Dragonfly, the Dragonfly Mass Spectrometer (DraMS) is dedicated to analyze the chemical composition of surface samples and noble gases in the atmosphere. One of the DraMS analysis modes, the Gas Chromatograph-Mass Spectrometer (GC-MS), is devoted to the detection and identification of organic molecules that could be involved in the development of a prebiotic chemistry or even representative of traces of past or present life. Therefore, DraMS-GC subsystem should be optimized to detect and identify relevant organic compounds to meet this objective. This work is focused on the experimental methods employed to select the chromatographic column to be integrated in DraMS-GC, to assess the analytical performances of the column selected, and also to assess the performances of the second DraMS-GC column, which is devoted to the separation of organic enantiomers. Four different stationary phases have been tested to select the most relevant one for the separation of the targeted chemical species. The results show that the stationary phase composed of polymethyl (95%) diphenyl (5%) siloxane is the best compromise in terms of efficiency, robustness, and retention times of the molecules. The combination of the general and the chiral columns in DraMS is perfectly suited to in situ chemical analysis on Titan and for the detection of expected diverse and complex organic compounds.

A perspective on iron (Fe) in the atmosphere: air quality, climate, and the ocean.

As scientists engage in research motivated by climate change and the impacts of pollution on air, water, and human health, we increasingly recognize the need for the scientific community to improve communication and knowledge exchange across disciplines to address pressing and outstanding research questions holistically. Our professional paths have crossed because our research activities focus on the chemical reactivity of Fe-containing minerals in air and water, and at the air-sea interface. (Photo)chemical reactions driven by Fe can take place at the surface of the particles/droplets or within the condensed phase. The extent and rates of these reactions are influenced by water content and biogeochemical activity ubiquitous in these systems. One of these reactions is the production of reactive oxygen species (ROS) that cause damage to respiratory organs. Another is that the reactivity of Fe and organics in aerosol particles alter surficial physicochemical properties that impact aerosol-radiation and aerosol-cloud interactions. Also, upon deposition, aerosol particles influence ocean biogeochemical processes because micronutrients such as Fe or toxic elements such as copper become bioavailable. We provide a perspective on these topics and future research directions on the reactivity of Fe in atmospheric aerosol systems, from sources to short- and long-term impacts at the sinks with emphasis on needs to enhance the predictive power of atmospheric and ocean models.

Predictive Models of Gas/Particulate Partition Coefficients (KP) for Polycyclic Aromatic Hydrocarbons and Their Oxygen/Nitrogen Derivatives.

Polycyclic aromatic hydrocarbons (PAHs) and their oxygen/nitrogen derivatives released into the atmosphere can alternate between a gas phase and a particulate phase, further affecting their environmental behavior and fate. The gas/particulate partition coefficient (KP) is generally used to characterize such partitioning equilibrium. In this study, the correlation between log KP of fifty PAH derivatives and their n-octanol/air partition coefficient (log KOA) was first analyzed, yielding a strong linear correlation (R2 = 0.801). Then, Gaussian 09 software was used to calculate quantum chemical descriptors of all chemicals at M062X/6-311+G (d,p) level. Both stepwise multiple linear regression (MLR) and support vector machine (SVM) methods were used to develop the quantitative structure-property relationship (QSPR) prediction models of log KP. They yield better statistical performance (R2 > 0.847, RMSE < 0.584) than the log KOA model. Simulation external validation and cross validation were further used to characterize the fitting performance, predictive ability, and robustness of the models. The mechanism analysis shows intermolecular dispersion interaction and hydrogen bonding as the main factors to dominate the distribution of PAH derivatives between the gas phase and particulate phase. The developed models can be used to predict log KP values of other PAH derivatives in the application domain, providing basic data for their ecological risk assessment.

Assessment of organochlorine pesticides in the atmosphere of South Korea: spatial distribution, seasonal variation, and sources.

Organochlorine pesticides (OCPs) are widely used in certain countries. We determined atmospheric concentrations, distribution patterns, and seasonal variations of OCPs at four sites in South Korea for 1 year. Samples of 22 OCPs were collected using a high-volume air sampler, and measured via the isotope dilution method with HRGC/HRMS. In South Korea, pentachlorobenzene (PeCB), hexachlorocyclohexane (HCB), and endosulfan (EnSF) were dominant, accounting for > 87% of total OCPs. Spatial distributions showed significant differences and the highest levels were observed in Seosan (295.2 pg·m-3), indicating the compounding potential of diverse sources as Seosan has concentrated large-scale industrial complexes and agricultural activity (Seoul: 243.6 pg·m-3 > Jeju: 193.5 pg·m-3 > Baengnyeong: 178.2 pg·m-3). The isomeric ratios of OCPs in the South Korean atmosphere indicated that the dominant sources of HCB and dichlorodiphenyltrichloroethane were primarily used in the past; meanwhile, chlordane (CHL) and EnSFs were derived from recent material inputs. Seasonally, OCP concentrations largely peaked in summer with minimum values in winter. This apparent temperature dependence suggests the re-volatilization of accumulated chemicals into the atmosphere. Additionally, an air mass back trajectory indicated the influence of pollutants released from a reservoir through long-range atmospheric transport in the summer. In particular, restricted OCPs are primarily released into the atmosphere by inadvertent sources, such as industrial activities and volatilization from contaminated areas. Thus, severe OCP pollution in Korea is due to the mobile nature of the particles. These data can be useful for the continuous monitoring of long-range transported air pollutants that are transferred between countries.

Rapid Gas-Phase Autoxidation of Nicotine in the Atmosphere.

Nicotine is the most abundant alkaloid chemical in smoke emission. In this work, we investigated the gas-phase oxidation mechanism of nicotine initiated by its reactions with the OH radical and ozone. Both initiation reactions start dominantly by hydrogen atom abstractions from the C1, C3, and -CH3 groups of the methylpyrrolidinyl group and form radicals nicotinyl-1, nicotinyl-3, and nicotinyl-6, respectively. The nicotinyl radicals would recombine rapidly with O2, forming RO2 with rapid intramolecular hydrogen-atom transfers (HATs) with rate coefficients from 4 s-1 to greater than 104 s-1. The rapid HATs in peroxy radicals suggest rapid autoxidation of nicotine in the gas phase. Formation of HCNO and HC(O)NH2, being observed in previous studies, arises likely from secondary reactions or photolysis of intermediate products.

Gas-Phase Ozone Reaction Kinetics of C5-C8 Unsaturated Alcohols of Biogenic Interest.

Unsaturated alcohols are volatile organic compounds (VOCs) that characterize the emissions of plants. Changes in climate together with related increases of biotic and abiotic stresses are expected to increase these emissions in the future. Ozonolysis is one of the oxidation pathways that control the fate of unsaturated alcohols in the atmosphere. The rate coefficients of the gas-phase O3 reaction with seven C5-C8 unsaturated alcohols were determined at 296 K using both absolute and relative kinetic methods. The following rate coefficients (cm3 molecule-1 s-1) were obtained using the absolute method: (1.1 ± 0.2) × 10-16 for cis-2-penten-1-ol, (1.2 ± 0.2) × 10-16 for trans-2-hexen-1-ol, (6.4 ± 1.0) × 10-17 for trans-3-hexen-1-ol, (5.8 ± 0.9) × 10-17 for cis-3-hexen-1-ol, (2.0 ± 0.3) × 10-17 for 1-octen-3-ol, and (8.4 ± 1.3) × 10-17 for trans-2-octen-1-ol. The following rate coefficients (cm3 molecule-1 s-1) were obtained using the relative method: (1.27 ± 0.11) × 10-16 for trans-2-hexen-1-ol, (5.01 ± 0.30) × 10-17 for trans-3-hexen-1-ol, (4.13 ± 0.34) × 10-17 for cis-3-hexen-1-ol, and (1.40 ± 0.12) × 10-16 for trans-4-hexen-1-ol. Alkenols display high reactivities with ozone with lifetimes in the hour range. Rate coefficients show a strong and complex dependence on the structure of the alkenol, particularly the relative position of the OH group toward the C═C double bond. The results are discussed and compared to both the available literature data and four structure-activity relationship (SAR) methods.

Solvation and Hydrolysis Reaction of Isocyanic Acid at the Air-Water Interface: A Computational Study.

Isocyanic acid (HNCO) is known to be inert to strong oxidants and photolysis in the atmosphere but often appears in different forms of smoke; therefore, it is linked to various smoke-related illnesses due to tobacco usage or wildfire events. To date, the major loss pathway of HNCO is believed to be through its uptake on aerosol droplets. However, the molecular mechanisms underlying such an uptake process are still incompletely understood. Herein, we use the Born-Oppenheimer molecular dynamics (BOMD) simulations to study solvation and hydrolysis reactions of HNCO on water droplets at ambient temperature. The BOMD simulations indicate that the scavenging of HNCO by water droplets is largely attributed to the preferential adsorption of HNCO at the air-water interface, rather than inside bulk water. Specifically, the H atom of HNCO interacts with the O atom of interfacial water, leading to the formation of a hydrogen bond (H-bond) of (HNCO)H···O(H2O), which prevents HNCO from evaporating. Moreover, the interfacial water can act as H-bond acceptors/donors to promote the proton transfer during the HNCO hydrolysis reaction. Compared to the gas phase, the activation barrier is lowered from 45 to 14 kcal·mol-1 on the water surface, which facilitates the formation of the key intermediate of NH2COOH. This intermediate eventually decomposes into NH3 and CO2, consistent with the previous study [ Atmos. Chem. Phys. 2016, 16, 703-714]. The new molecular insight into HNCO solvation and reaction on the water surface improves our understanding of the uptake of HNCO on aerosols.