Nitrogen-containing Organic Compounds Research Articles

Effects of different low-temperature pyrolysis treatments on the biotoxicity of biochar derived from tobacco stalks

The pyrolytic treatment of tobacco stalk (TS) waste results in the production of a large amount of biochar, which is usually used for environmental remediation. However, little attention has been given to the effects of different pyrolysis methods on the biotoxicity of TS biochar. This study examined the effects of three different pyrolysis methods at 350 °C (fast pyrolysis, slow pyrolysis, and low-temperature carbonization) on the biotoxicity of TS biochar (Escherichia coli (E. coli) growth and wheat germination). The results revealed that the dissolved organic matter (DOM) of the three types of biochar promoted the growth of E. coli, and the maximum growth of E. coli was ranked as DOM-F350 > DOM-S350 > DOM-350. However, the DOM inhibited the growth of the wheat seeds, with the growth index (below 0.8) of the wheat seeds ranked as DOM-350 > DOM-F350 > DOM-S350. The alkali metal content, pH and humus-like substance content of biochar may be responsible for the biotoxicity of biochar through various mechanisms. In addition, TS-S350 exhibited greater biotoxicity than did TS-F350 because of the greater content of toxic nitrogen-containing organic compounds. These findings can provide reliable theoretical guidance for the effective management and safe utilization of TS waste.

Comparison of genotoxic impurities in extracted nicotine vs. synthetic nicotine.

Nicotine is a chiral alkaloid; nitrogen-containing organic compound that occurs naturally. (S)-nicotine is extracted from Tobacco plants and used as the key addictive ingredient in many smoking products. Synthetic nicotine has gained the interest of many smoking product manufacturers over the last few decades due to the ease and low cost of manufacturing. Another claimed advantage of synthetic nicotine is the absence of genotoxic impurities that form during the extraction process of nicotine. These impurities are other plant alkaloids, phenolic compounds, and heavy metals. Additionally, the U. S. FDA has implemented new regulations on the quality control of synthetic nicotine. However, only a very few research articles have been published on assessing the complete impurity profile of synthetic nicotine. Therefore, the need to know the composition difference between tobacco-extracted nicotine vs. synthetic nicotine is highly necessary. In this research study, the impurity profile of thirteen different lots of synthetic nicotine was compared with fourteen lots of nicotine extracted from plants using in-house analytical methods. First, the samples were tested for other alkaloids and phenols by reversed-phase High-Performance Liquid Chromatography (HPLC). Second, the chiral purity was analyzed by normal phase HPLC. Third, lead and arsenic content were tested by atomic absorption and fluorescence spectrometry. Fourth, nicotine-specific nitrosamines were tested by LC-MS. The reversed phase HPLC data suggested similar quantities of total impurities in both synthetic and tobacco-extracted nicotine (0.1%). However, synthetic nicotine lacks some impurities such as cotinine, nornicotine, and nicotine-N-oxide. Additionally, the synthetic nicotine lots used in this study have high enantiomeric purity similar to the tobacco-extracted nicotine.

Dominant influence of biomass combustion and cross-border transport on nitrogen-containing organic compound levels in the southeastern Tibetan Plateau

Abstract. The Tibetan Plateau (TP) is highly susceptible to climate change, and nitrogen-containing organic compounds (NOCs) in fine particulate matter (PM2.5) represent one of the largest uncertainties with respect to their impact on the climate in high-altitude areas. Previous studies have shown that NOCs play a vital role in the nitrogen budget of PM2.5. However, our understanding of the composition and sources of NOCs in PM2.5, particularly in the TP, is limited. Here, we aim to enhance our understanding of NOCs in the TP region by examining their identification, concentration levels, sources, and origins. We conducted field sampling at a regional background sampling site in Gaomeigu, in the southeastern margin of the TP from 11 March to 13 May 2017, followed by laboratory analysis of the NOCs collected on the filters. The daily mass concentrations of NOCs ranged from 714.4 to 3887.1 ng m−3, with an average of 2119.4 ± 875.0 ng m−3 during the campaign. This average concentration was approximately 40 % higher than that reported at a typical regional site in the North China Plain (NCP), highlighting a more significant presence of NOCs in the Tibetan area. Biomass burning and secondary sources were identified as the major contributors to total NOCs. This was further substantiated by a regional air quality model, which indicated that over 80 % of the aerosol in the southeast of the TP originated from neighboring countries. This study improves our understanding of NOCs' contribution to PM2.5 in the TP and their potential impacts on climate stability in high-altitude areas.

The role elucidating of EPS in thermal hydrolysis and nitrogen conversion of sewage sludge during hydrothermal carbonization process, and its effect on hydrochar's properties

Hydrothermal carbonization (HTC) was conducted to observe the effect of extracellular polymeric substances (EPS) structure on the nitrogen migration mechanism during the HTC process. The denitrification efficiency of activated sewage sludge (ASS) decreases with an increase in EPS stripping intensity. Loosely and tightly bound extracellular polymers diminish the denitrification effectiveness by inhibiting the hydrolysis of nitrogen-containing organic compounds and protecting the cell structure, respectively. Intracellular nucleic acids and proteins generate stable N-containing species, such as heterocyclic-N and quaternary-N, which are unfavorable for deep denitrification. In general, nitrogen removal is more effective outside the cell than inside. Deep destruction of EPS eliminated a considerable number of N-containing components, and the N/C value of hydrochar at 180 °C without cell membrane protection was 0.06, which dropped to half that of ASS (0.11). This study revealed the influence of EPS structure on nitrogen migration in hydrothermal environment and provided significant insights for the preparation of clean solid fuels.

Insight into wet scavenging effects on sulfur and nitrogen containing organic compounds in urban Beijing

Sulfur-containing organic compounds (SOCs) and nitrogen-containing organic compounds (NOCs) play critical roles in regulating the physical and chemical properties of organic aerosols (OA), while the understanding of them remains limited. Here, the high-resolution real-time measurements of submicron aerosols were conducted in urban Beijing, mainly to investigate wet scavenging effects on the potential formation and evolution mechanism of OA, especially SOCs and NOCs. OA composition transitioned from being primarily SOCs before wet processes to NOCs after wet processes. Further molecular fragments identification suggested SOCs mainly comprised glycolic acid sulfate formed by aqueous-phase processing during the entire observation, and aromatic- and monoterpene-derived SOCs formed by photochemical processing before snowfall. NOCs species were diverse and dominated by highly oxidized amides and amino acids mainly produced by photochemical processing. This study provided an in-depth insight into the potential formation and evolution pathways of SOCs and NOCs in OA in the urban atmosphere.

Rapid aqueous-phase dark reaction of phenols with nitrosonium ions: Novel mechanism for atmospheric nitrosation and nitration at low pH.

Dark aqueous-phase reactions involving the nitrosation and nitration of aromatic organic compounds play a significant role in the production of light-absorbing organic carbon in the atmosphere. This process constitutes a crucial aspect of tropospheric chemistry and has attracted growing research interest, particularly in understanding the mechanisms governing nighttime reactions between phenols and nitrogen oxides. In this study, we present new findings concerning the rapid dark reactions between phenols containing electron-donating groups and inorganic nitrite in acidic aqueous solutions with pH levels <3.5. This reaction generates a substantial amount of nitroso- and nitro-substituted phenolic compounds, known for their light-absorbing properties and toxicity. In experiments utilizing various substituted phenols, we demonstrate that their reaction rates with nitrite depend on the electron cloud density of the benzene ring, indicative of an electrophilic substitution reaction mechanism. Control experiments and theoretical calculations indicate that the nitrosonium ion (NO+) is the reactive nitrogen species responsible for undergoing electrophilic reactions with phenolate anions, leading to the formation of nitroso-substituted phenolic compounds. These compounds then undergo partial oxidation to form nitro-substituted phenols through reactions with nitrous acid (HONO) or other oxidants like oxygen. Our findings unveil a novel mechanism for swift atmospheric nitrosation and nitration reactions that occur within acidic cloud droplets or aerosol water, providing valuable insights into the rapid nocturnal formation of nitrogen-containing organic compounds with significant implications for climate dynamics and human health.

Regulating active oxygen species and acidity of Ca doped LaMnO3 perovskite catalysts toward efficient n-butylamine oxidation

It is of great significance to design catalysts with high activity, N2 selectivity and stability for nitrogen-containing volatile organic compound (NVOC) catalytic purification. Meanwhile, the role of oxygen species in NVOC catalytic oxidation is still ambiguous. Herein, the oxygen species of La-Mn perovskite catalysts were engineered by doping Ca in La site to elucidate their role in catalytic n-butylamine oxidation. Results demonstrate that La0.9Ca0.1MnO3 exhibits the highest activity owing to its abundant adsorbed oxygen species and high surface area, achieving 100 % n-butylamine conversion (500 ppm; GHSV=60,000 mL g−1h−1) at 200 °C with N2 selectivity of ca. 95 %. More adsorbed oxygen species generated due to Ca doping accelerates the oxidation rate and C-C cleavage of alcohol and acetate intermediates, resulting in higher CO2 yield. Meanwhile, Ca-doping also modifies the acidity of catalysts, which affects the adsorption/desorption process of alkaline substances and yield of nitrogen-containing products. In addition, La0.9Ca0.1MnO3 shows superior stability, high water and SO2 resistance, and acceptable activity for other common NVOCs, demonstrating a promising catalyst for NVOC oxidation even under harsh operation conditions. Furthermore, the toxic effect of pollutant or products during n-butylamine catalytic oxidation on the growth of Chlorella Vulgaris was investigated and results suggest that catalytic oxidation is an environmentally friendly method for NVOC purification. This work sheds light on the relationships among oxygen species, catalyst acidity, and n-butylamine catalytic oxidation, which expand the understanding of rational design of efficient catalyst for NVOC oxidation.

Fate of organic nitrogen in amino acids during alternating denitrification and nitrification

Nitrogen-containing organic compounds, such as amino acids in soybean-processing wastewater, can be used as electron donors to drive denitrification, but their biodegradation releases ammonium nitrogen that must be nitrified and denitrified to maintain total-nitrogen removal. We evaluated glutamate, isoleucine, and methionine as example amino acids to explore the fate of nitrogen when they are used as electron donor to drive denitrification during two stages of alternating denitrification and nitrification. The experimental results documented that each amino acid enabled complete removal of exogenous NO3− in the first stage of denitrification and complete NO3− removal in the second stage. After two alternations of denitrification and nitrification, the TN concentration in effluent was less than 5 mgN/L for all amino acids, and COD in the effluent was less than 25 mg/L. Based on stoichiometry and the ratio of chemical oxygen demand (COD) to organic N in each amino acid, 57%–66% of the COD from the amino acids had to be oxidized to reduce the endogenous NO3−–N in the first stage. N from the amino acids was nitrified and denitrified in the subsequent nitrification and denitrification stages, and the percentages of COD used for denitrification from both stages were 72%–85%. The residual NH4+-N concentrations were slightly higher with methionine, possibly due to inhibition from sulfide released from methionine.

Different formation pathways of nitrogen-containing organic compounds in aerosols and fog water in northern China

Abstract. While aqueous-phase processing is known to contribute to the formation of nitrogen-containing organic compounds (NOCs), the specific pathways involved remain poorly understood. In this study, we aimed to characterize the NOCs present in both pre-fog aerosols and fog water collected at a suburban site in northern China. Fourier-transform ion cyclotron resonance mass spectrometry was utilized to analyze the molecular composition of NOCs in both negative and positive modes of electrospray ionization (ESI− and ESI+). In both pre-fog aerosols and fog water samples, NOCs constituted a significant portion, accounting for over 60 % of all assigned formulas in ESI− and more than 80 % in ESI+. By comparing the molecular composition of NOCs originating from biomass burning, coal combustion, and vehicle emissions, we identified that 72.3 % of NOCs in pre-fog aerosols were attributed to primary anthropogenic sources (pNOCs), while the remaining NOCs were categorized as secondary NOCs formed within the aerosols (saNOCs). Unique NOCs found in fog water were classified as secondary NOCs formed within the fog water (sfNOCs). Through a comprehensive “precursor–product pair” screening involving 39 reaction pathways, we observed that the nitration reaction, the amine pathway, and the intramolecular N-heterocycle pathway of NH3 addition reactions contributed 43.6 %, 22.1 %, and 11.6 % of saNOCs, respectively. In contrast, these pathways contributed 26.8 %, 28.4 %, and 29.7 % of sfNOCs, respectively. This disparity in formation pathways is likely influenced by the diverse precursors, the aqueous acidity, and the gas-phase species partitioning. Correspondingly, saNOCs were found to contain a higher abundance of carbohydrate-like and highly oxygenated compounds with two nitrogen atoms compared to pNOCs. Conversely, sfNOCs exhibited a higher content of lipid-like compounds with fewer oxygen atoms. These results underscore the distinct secondary processes contributing to the diversity of NOCs in aerosols and fog water, which may lead to their different climate effects.

Exploring the molecular characteristics of organic matter in low-rank coals using GC×GC/TOF-MS plus data mining

In-depth understanding the form of organic matter in low-rank coals contributes to the clean and efficient utilization of coals. Two low-rank coals were successively dissolved with cyclohexane, acetone and methanol at 300 °C, respectively. Six thermal dissolution (TD) extracts were comparatively analyzed using comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (GC×GC/TOF-MS). Cyclohexane tends to extract low-polar compounds inherent in coal, such as aliphatic hydrocarbons, arenes and phenols. Acetone can extract monocyclic aromatic hydrocarbons containing alkyl side chains. Meanwhile, acetone can form N-H⋯O hydrogen bonds with nitrogen-containing organic compounds (NCOCs), facilitating the extraction of a greater quantity of NCOCs. Methanol breaks the ArCH2OArR structural unit within coal molecules and forms the dominant alkyl-substituted phenol. It was revealed that sequentially TD at 300 °C using different solvents only breaks intermolecular forces and weak covalent bonds. Additionally, a series of isomers of tricyclic aromatic hydrocarbons and alkylphenols were authenticated by GC×GC/TOF-MS. Principal component analysis and hierarchical clustering analysis were applied to mine effective molecular information from the extensive MS data. The statistical results indicate that solvent had a significant impact on the structure and composition of the TD extracts, more so than the variations in coal species. Thus, the conjunction of GC×GC/TOF-MS and chemometrics provided methodological guidance for an enhanced comprehension of the molecular structure of coals.

Hydroamination of alkenes with dinitrogen and titanium polyhydrides.

An ideal synthesis of alkyl amines would involve the direct use of abundant and easily accessible molecules such as dinitrogen (N2) and feedstock alkenes1-4. However, this ambition remains a great challenge as it is usually difficult to simultaneously activate both N2 and a simple alkene and combine them together through carbon-nitrogen (C-N) bond formation. Currently, the synthesis of alkyl amines relies on the use of ammonia produced through the Haber-Bosch process and prefunctionalized electrophilic carbon sources. Here we report the hydroamination of simple alkenes with N2 in a trititanium hydride framework, which activates both alkenes and N2, leading to selective C-N bond formation and providing the corresponding alkyl amines on further hydrogenation and protonation. Computational studies reveal key mechanistic details of N2 activation and selective C-N bond formation. This work demonstrates a strategy for the transformation of N2 and simple hydrocarbons into nitrogen-containing organic compounds mediated by a multinuclear hydride framework.

Synergistic Catalytic Removal of NOx and n-Butylamine via Spatially Separated Cooperative Sites.

Synergistic control of nitrogen oxides (NOx) and nitrogen-containing volatile organic compounds (NVOCs) from industrial furnaces is necessary. Generally, the elimination of n-butylamine (n-B), a typical pollutant of NVOCs, requires a catalyst with sufficient redox ability. This process induces the production of nitrogen-containing byproducts (NO, NO2, N2O), leading to lower N2 selectivity of NH3 selective catalytic reduction of NOx (NH3-SCR). Here, synergistic catalytic removal of NOx and n-B via spatially separated cooperative sites was originally demonstrated. Specifically, titania nanotubes supported CuOx-CeO2 (CuCe-TiO2 NTs) catalysts with spatially separated cooperative sites were creatively developed, which showed a broader active temperature window from 180 to 340 °C, with over 90% NOx conversion, 85% n-B conversion, and 90% N2 selectivity. A synergistic effect of the Cu and Ce sites was found. The catalytic oxidation of n-B mainly occurred at the Cu sites inside the tube, which ensured the regular occurrence of the NH3-SCR reaction on the outer Ce sites under the matching temperature window. In addition, the n-B oxidation would produce abundant intermediate NH2*, which could act as an extra reductant to promote NH3-SCR. Meanwhile, NH3-SCR could simultaneously remove the possible NOx byproducts of n-B decomposition. This novel strategy of constructing cooperative sites provides a distinct pathway for promoting the synergistic removal of n-B and NOx.

Peatland Wildfires Enhance Nitrogen-Containing Organic Compounds in Marine Aerosols over the Western Pacific.

Peatland wildfires contribute significantly to the atmospheric release of light-absorbing organic carbon, often referred to as brown carbon. In this study, we examine the presence of nitrogen-containing organic compounds (NOCs) within marine aerosols across the Western Pacific Ocean, which are influenced by peatland fires from Southeast Asia. Employing ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) in electrospray ionization (ESI) positive mode, we discovered that NOCs are predominantly composed of reduced nitrogenous bases, including CHN+ and CHON+ groups. Notably, the count of NOC formulas experiences a marked increase within plumes from peatland wildfires compared to those found in typical marine air masses. These NOCs, often identified as N-heterocyclic alkaloids, serve as potential light-absorbing chromophores. Furthermore, many NOCs demonstrate pyrolytic stability, engage in a variety of substitution reactions, and display enhanced hydrophilic properties, attributed to chemical processes such as methoxylation, hydroxylation, methylation, and hydrogenation that occur during emission and subsequent atmospheric aging. During the daytime atmospheric transport, aging of aromatic N-heterocyclic compounds, particularly in aliphatic amines prone to oxidation and reactions with amine, was observed. The findings underscore the critical role of peatland wildfires in augmenting nitrogen-containing organics in marine aerosols, underscoring the need for in-depth research into their effects on marine ecosystems and regional climatic conditions.

Automated Method for the Sensitive Analysis of Volatile Amines in Seawater.

Methylamines are polar, volatile, and organic nitrogen-containing compounds. They are challenging to analyze, limiting our understanding of their occurrence and role within the marine nitrogen cycle. We describe an automated headspace solid-phase microextraction method, coupled with gas chromatography and nitrogen phosphorus detection (HS-SPME-GC-NPD), for analyzing methylamines in seawater. Three SPME conditions were investigated: temperature, equilibration, and extraction. The method was 6-24 times more sensitive to trimethylamine (TMA) than to dimethylamine (DMA) and monomethylamine (MMA). DMA and TMA were detected in small seawater volumes (2.5-10 mL), at volumes 100-400 times that previously reported. Detection limits of 19.1, 6.6, and 4.1 nM (nMol L-1) for MMA, DMA, and TMA, respectively, were measured in 10 mL sample volumes. Sample throughput was 4-6 times greater than previously reported similar methods. According to the Blue Applicability Grade Index (BAGI) metric, the method was considered "practical" and scored 62.5. The method was used to measure methylamines in seawater samples collected from the Southern Ocean. DMA and TMA were detected at concentrations from < LoD-35 nM and < LoD-48 nM, respectively. This study offers a systematic and standardized method for MA analysis in seawater and can significantly advance understanding of their role in marine systems.

The effect of non-Saccharomyces yeasts on biogenic amines in Sauvignon Blanc wine and Gewürztraminer wine

Biogenic amine (BA) is a class of nitrogen-containing small molecular organic compounds with biological activity. Excessive BAs in wine affect flavor and quality of wine and are hazardous to human health. However, little attention has been paid to the effect of non-Saccharomyces yeasts and Saccharomyces cerevisiae mixed fermentation on BAs in white wine. The effect of mixed fermentation on BAs and amino acids in wine was investigated using two white grapes of Sauvignon Blanc and Gewürztraminer. Higher levels of total amino acids and BAs in Gewürztraminer wine compared to Sauvignon Blanc wine may be due to different grape varieties. Mixed fermentation did not influence BA profiles in Sauvignon Blanc wine, while it increased total BAs content. VL3 (VL) fermented wine has 33.7% less BAs content than EC1118 (EC) single-strain fermented wine. Similar phenomenon was found in Gewürztraminer wine produced by different fermentation combinations except that cadaverine was only detected in wine produced by Hanseniaspora uvarum participated in mixed fermentations. Principal coordinate analysis (PCoA) and permutational multivariate analysis of variance (PERMANOVA) revealed that the effects on BAs were related to grape varieties and yeast species in white wine. Ethanolamine, tryptamine, isoamylamine and histamine content in wine were related to grape varieties. Collectively, mixed fermentation increased BAs content in Sauvignon Blanc and Gewürztraminer wine. The content of BAs in wine fermented by VL single-strain fermentation was lower than that fermented by EC single-strain fermentation, which is more suitable for the winemaking of white wine.

Measurement report: Characteristics of nitrogen-containing organics in PM2.5 in Ürümqi, northwestern China – differential impacts of combustion of fresh and aged biomass materials

Abstract. Nitrogen-containing organic compounds (NOCs) are abundant and important aerosol components deeply involved in the global nitrogen cycle. However, the sources and formation processes of NOCs remain largely unknown, particularly in the city (Ürümqi, China) farthest from the ocean worldwide. Here, NOCs in PM2.5 collected in Ürümqi over a 1-year period were characterized by ultra-high-resolution mass spectrometry. The abundance of CHON compounds (mainly oxygen-poor unsaturated aliphatic-like species) in the positive ion mode was higher in the warm period than in the cold period, which was largely attributed to the contribution of fresh biomass material combustion (e.g., forest fires) associated with amidation of unsaturated fatty acids in the warm period, rather than the oxidation processes. However, CHON compounds (mainly nitro-aromatic species) in the negative ion mode increased significantly in the cold period, which was tightly related to aged biomass combustion (e.g., dry straws) in wintertime Ürümqi. For CHN compounds, alkyl nitriles and aromatic species showed higher abundance in the warm and cold periods, respectively. Alkyl nitriles can be derived from fresh biomass material combustion associated with the dehydration of amides (the main CHON compounds in the warm period). In contrast, aromatic species were tightly related to aged biomass burning. These findings further suggested different impacts of the combustion of fresh and aged biomass materials on NOC compositions in different seasons. The overall results shed light on the mechanisms by which fresh and aged biomass materials release different NOCs during combustion.

The synergistic effect of NOx and SO2 on the formation and light absorption of secondary organic aerosols from ο-xylene photooxidation

Both NOx and SO2 are important anthropogenic air pollutants that significantly affect secondary organic aerosols (SOA) formation. However, our understanding of the combined effects of NOx and SO2 on SOA formation is still insufficient. The concentrations, optical properties, and chemical compositions of SOA formed through ο-xylene photooxidation under various NOx concentrations were investigated with or without SO2 in the chamber. It was found that SOA mass concentration increased from 60 to 129 μg m−3 when the initial NOx concentration was increased from 0 to 900 ppb. The presence of 50 ppb SO2 not only enhanced ο-xylene SOA formation by 1.6–2.9 times, but also changed the evolution of SOA with NOx. The enhancement of ο-xylene SOA formation was primarily attributed to acid-catalyzed heterogeneous reactions initiated by nitric acid and sulfuric acid. However, SOA concentration decreased under 900 ppb NOx when SO2 was present, likely due to the decrease in sulfate production because of the competition between NOx and SO2 for ·OH. In addition, nitrogen-containing organic compounds (NOCs) concentrations and mass absorption coefficients (MACλ=365 nm) were promoted by both NOx and SO2. Our research indicates that the promotion of both NOCs formation by NOx, and oligomer formation by SO2 were the main reasons for the enhanced SOA light absorption. The present research provides a scientific basis for understanding the combined effects of both NOx and SO2 on ο-xylene SOA formation, and illustrates that the imbalanced reduction of anthropogenic air pollutants would lead to new characteristics in SOA pollution.

Unveiling the Molecular Characteristics, Origins, and Formation Mechanism of Reduced Nitrogen Organic Compounds in the Urban Atmosphere of Shanghai Using a Versatile Aerosol Concentration Enrichment System.

Reduced nitrogen-containing organic compounds (NOCs) in aerosols play a crucial role in altering their light-absorption properties, thereby impacting regional haze and climate. Due to the low concentration levels of individual NOCs in the air, the utilization of accurate detection and quantification technologies becomes essential. For the first time, this study investigated the diurnal variation, chemical characteristics, and potential formation pathways of NOCs in urban ambient aerosols in Shanghai using a versatile aerosol concentration enrichment system (VACES) coupled with HPLC-Q-TOF-MS. The results showed that NOCs accounted over 60% of identified components of urban organic aerosols, with O/N < 3 compounds being the major contributors (>70%). The predominance of the positive ionization mode suggested the prevalence of reduced NOCs. Higher relative intensities and number fractions of NOCs were observed during nighttime, while CHO compounds showed an opposite trend. Notably, a positive correlation between the intensity of NOCs and ammonium during the nighttime was observed, suggesting that the reaction of ammonium to form imines may be a potential pathway for the formation of reduced NOCs during the nighttime. Seven prevalent types of reduced NOCs in autumn and winter were identified and characterized by an enrichment of CH2 long-chain homologues. These NOCs included alkyl, cyclic, and aromatic amides in CHON compounds, as well as heterocyclic or cyclic amines and aniline homologue series in CHN compounds, which were associated with anthropogenic activities and may be capable of forming light-absorbing chromophores or posing harm to human health. The findings highlight the significant contributions of both primary emissions and ammonium chemistry, particularly amination processes, to the pollution of reduced NOCs in Shanghai's atmosphere.

Molecular analysis of secondary organic aerosol and brown carbon from the oxidation of indole

Abstract. Indole (ind) is a nitrogen-containing heterocyclic volatile organic compound commonly emitted from animal husbandry and from different plants like maize with global emissions of 0.1 Tg yr−1. The chemical composition and optical properties of indole secondary organic aerosol (SOA) and brown carbon (BrC) are still not well understood. To address this, environmental chamber experiments were conducted to investigate the oxidation of indole at atmospherically relevant concentrations of selected oxidants (OH radicals and O3) with or without NO2. In the presence of NO2, the SOA yields decreased by more than a factor of 2, but the mass absorption coefficient at 365 nm (MAC365) of ind-SOA was 4.3 ± 0.4 m2 g−1, which was 5 times higher than that in experiments without NO2. In the presence of NO2, C8H6N2O2 (identified as 3-nitroindole) contributed 76 % to all organic compounds detected by a chemical ionization mass spectrometer, contributing ∼ 50 % of the light absorption at 365 nm (Abs365). In the absence of NO2, the dominating chromophore was C8H7O3N, contributing to 20 %–30 % of Abs365. Indole contributes substantially to the formation of secondary BrC and its potential impact on the atmospheric radiative transfer is further enhanced in the presence of NO2, as it significantly increases the specific light absorption of ind-SOA by facilitating the formation of 3-nitroindole. This work provides new insights into an important process of brown carbon formation by interaction of two pollutants, NO2 and indole, mainly emitted by anthropogenic activities.

Characteristics and source apportionment of water-soluble organic nitrogen (WSON) in PM2.5 in Hong Kong: With focus on amines, urea, and nitroaromatic compounds

Water-soluble organic nitrogen (WSON) is ubiquitous in fine particulate matter (PM2.5) and poses health and environmental risks. However, there is limited knowledge regarding its comprehensive speciation and source-specific contributions. Here, we conducted chemical characterization and source apportionment of WSON in 65 PM2.5 samples collected in Hong Kong during a 1-yr period. Using various mass-spectrometry-based techniques, we quantified 22 nitrogen-containing organic compounds (NOCs), including 17 nitroaromatics (NACs), four amines, and urea. The most abundant amine and NACs were dimethylamine and 4-nitrocatechol, respectively. Two secondary (i.e., secondary formation and secondary nitrate) and five primary sources (i.e., sea salt, fugitive dust, marine vessels, vehicle exhaust, and biomass burning) of WSON and these three categories of NOCs were identified. Throughout the year, secondary sources dominated WSON formation (69.0%), while primary emissions had significant contributions to NACs (77.1%), amines (75.9%), and urea (83.7%). Fugitive dust was the leading source of amines and urea, while biomass burning was the main source of NACs. Our multi-linear regression analysis revealed the significant role of sulfate, NO3, nitrate, liquid water content, and particle pH on WSON formation, highlighting the importance of nighttime NO3 processing and heterogeneous and aqueous-phase formation of NOCs in the Hong Kong atmosphere.