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1.
Proc Natl Acad Sci U S A ; 120(15): e2220228120, 2023 Apr 11.
Artigo em Inglês | MEDLINE | ID: mdl-37011187

RESUMO

Hydroxyl radical (OH) is a key oxidant that triggers atmospheric oxidation chemistry in both gas and aqueous phases. The current understanding of its aqueous sources is mainly based on known bulk (photo)chemical processes, uptake from gaseous OH, or related to interfacial O3 and NO3 radical-driven chemistry. Here, we present experimental evidence that OH radicals are spontaneously produced at the air-water interface of aqueous droplets in the dark and the absence of known precursors, possibly due to the strong electric field that forms at such interfaces. The measured OH production rates in atmospherically relevant droplets are comparable to or significantly higher than those from known aqueous bulk sources, especially in the dark. As aqueous droplets are ubiquitous in the troposphere, this interfacial source of OH radicals should significantly impact atmospheric multiphase oxidation chemistry, with substantial implications on air quality, climate, and health.

2.
Environ Sci Technol ; 58(3): 1563-1576, 2024 Jan 23.
Artigo em Inglês | MEDLINE | ID: mdl-38183415

RESUMO

Uncertain chemical mechanisms leading to brown carbon (BrC) formation affect the drivers of the radiative effects of aerosols in current climate predictions. Herein, the aqueous-phase reactions of methylglyoxal (MG) and typical reduced nitrogen species (RNSs) are systematically investigated by using combined quantum chemical calculations and laboratory experiments. Imines and diimines are identified from the mixtures of methylamine (MA) and ammonia (AM) with MG, but not from dimethylamine (DA) with the MG mixture under acidic conditions, because deprotonation of DA cationic intermediates is hindered by the amino groups occupied by two methyl groups. It leads to N-heterocycle (NHC) formation in the MG + MA (MGM) and MG + AM (MGA) reaction systems but to N-containing chain oligomer formation in the MG + DA (MGD) reaction system. Distinct product formation is attributed to electrostatic attraction and steric hindrance, which are regulated by the methyl groups of RNSs. The light absorption and adverse effects of NHCs are also strongly related to the methyl groups of RNSs. Our finding reveals that BrC formation is mainly contributed from MG reaction with RNSs with less methyl groups, which have more abundant and broad sources in the urban environments.


Assuntos
Poluentes Atmosféricos , Dimetilaminas , Aldeído Pirúvico , Carbono , Nitrogênio , Metilaminas , Aerossóis/análise
3.
J Environ Sci (China) ; 141: 225-234, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38408823

RESUMO

Acetylacetone (AcAc) is a typical class of ß-diketones with broad industrial applications due to the property of the keto-enol isomers, but its isomerization and chemical reactions at the air-droplet interface are still unclear. Hence, using combined molecular dynamics and quantum chemistry methods, the heterogeneous chemistry of AcAc at the air-droplet interface was investigated, including the attraction of AcAc isomers by the droplets, the distribution of isomers at the air-droplet interface, and the hydration reactions of isomers at the air-droplet interface. The results reveal that the preferential orientation of two AcAc isomers (keto- and enol-AcAc) to accumulate and accommodate at the acidic air-droplet interface. The isomerization of two AcAc isomers at the acidic air-droplet interface is more favorable than that at the neutral air-droplet interface because the "water bridge" structure is destroyed by H3O+, especially for the isomerization from keto-AcAc to enol-AcAc. At the acidic air-droplet interface, the carbonyl or hydroxyl O-atoms of two AcAc isomers display an energetical preference to hydration. Keto-diol is the dominant products to accumulate at the air-droplet interface, and excessive keto-diol can enter the droplet interior to engage in the oligomerization. The photooxidation reaction of AcAc will increase the acidity of the air-droplet interface, which indirectly facilitate the uptake and formation of more keto-diol. Our results provide an insight into the heterogeneous chemistry of ß-diketones and their influence on the environment.


Assuntos
Pentanonas , Água , Isomerismo , Pentanonas/química , Água/química
4.
J Environ Sci (China) ; 138: 660-670, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38135429

RESUMO

Industrial coking facilities are an important emission source for volatile organic compounds (VOCs). This study analyzed the atmospheric VOC characteristics within an industrial coking facility and its surrounding environment. Average concentrations of total VOCs (TVOCs) in the surrounding residential activity areas (R1 and R2), the coking facility (CF) and the control area (CA) were determined to be 138.5, 47.8, 550.0, and 15.0 µg/m3, respectively. The cold drum process and coking and quenching areas within the coking facility were identified as the main polluting processes. The spatial variation in VOCs composition was analyzed, showing that VOCs in the coking facility and surrounding areas were mainly dominated by aromatic compounds such as BTX (benzene, toluene, and xylenes) and naphthalene, with concentrations being negatively correlated with the distance from the coking facility (p < 0.01). The sources of VOCs in different functional areas across the monitoring area were analyzed, finding that coking emissions accounted for 73.5%, 33.3% and 27.7% of TVOCs in CF, R1 and R2, respectively. These results demonstrated that coking emissions had a significant impact on VOC concentrations in the areas surrounding coking facility. This study evaluates the spatial variation in exposure to VOCs, providing important information for the influence of VOCs concentration posed by coking facility to surrounding residents and the development of strategies for VOC abatement.


Assuntos
Poluentes Atmosféricos , Coque , Ozônio , Compostos Orgânicos Voláteis , Compostos Orgânicos Voláteis/análise , Poluentes Atmosféricos/análise , Monitoramento Ambiental/métodos , Benzeno , China , Ozônio/análise
5.
J Am Chem Soc ; 145(41): 22649-22658, 2023 Oct 18.
Artigo em Inglês | MEDLINE | ID: mdl-37811579

RESUMO

The heterogeneous reaction of nitryl chloride (ClNO2) on the air-water surface plays a significant role in the chloride lifecycle. The air-water surface is ubiquitous on ice surfaces under supercooled conditions, affecting the uptake and heterogeneous reaction processes of trace gases. Previous studies suggest that ClNO2 is formed on Cl-doped ice surfaces following the N2O5 uptake. Herein, a distinctive heterogeneous reaction mechanism of ClNO2 is suggested on an air-water surface containing Cl under supercooled conditions using combined classic molecular dynamics (MD) and Born-Oppenheimer MD simulations. It is found that N2O5 dissociates into a NO2+ and NO3- ionic pair on the top air-water surface. In the top layer of the surface containing barely any Cl-, NO2+ proceeds through hydrolysis and produces H3O+ and HNO3. Thus, surface acidification appears because of H3O+ yields. With NO2+ diffusion to the deep layer of the surface, NO2+ reacts with Cl- and forms ClNO2. Note that ClNO2 formation competes with NO2+ hydrolysis, and the rate of ClNO2 formation is 27.7[Cl-] larger than that of NO2+ hydrolysis. Afterward, the reaction of ClNO2 with Cl- becomes barrierless with the catalysis by H3O+, which is not feasible on a neutral surface. Cl2 is thus generated and escapes into the atmosphere (low solubility of Cl2), contributing to the Cl radical. The proposed mechanism bolsters the current understanding of ClNO2's fate and its role in Cl chemistry in extremely cold environments like the Arctic and other high-latitude regions in wintertime.

6.
Environ Sci Technol ; 57(41): 15580-15587, 2023 10 17.
Artigo em Inglês | MEDLINE | ID: mdl-37804225

RESUMO

We present experimental evidence that atomic and molecular iodine, I and I2, are produced spontaneously in the dark at the air-water interface of iodide-containing droplets without any added catalysts, oxidants, or irradiation. Specifically, we observe I3- formation within droplets, and I2 emission into the gas phase from NaI-containing droplets over a range of droplet sizes. The formation of both products is enhanced in the presence of electron scavengers, either in the gas phase or in solution, and it clearly follows a Langmuir-Hinshelwood mechanism, suggesting an interfacial process. These observations are consistent with iodide oxidation at the interface, possibly initiated by the strong intrinsic electric field present there, followed by well-known solution-phase reactions of the iodine atom. This interfacial chemistry could be important in many contexts, including atmospheric aerosols.


Assuntos
Iodo , Água , Água/química , Iodetos/química , Iodo/química
7.
Environ Sci Technol ; 57(43): 16414-16423, 2023 10 31.
Artigo em Inglês | MEDLINE | ID: mdl-37844141

RESUMO

Urban ambient air contains a cocktail of antibiotic resistance genes (ARGs) emitted from various anthropogenic sites. However, what is largely unknown is whether the airborne ARGs exhibit site-specificity or their pathogenic hosts persistently exist in the air. Here, by retrieving 1.2 Tb metagenomic sequences (n = 136), we examined the airborne ARGs from hospitals, municipal wastewater treatment plants (WWTPs) and landfills, public transit centers, and urban sites located in seven of China's megacities. As validated by the multiple machine learning-based classification and optimization, ARGs' site-specificity was found to be the most apparent in hospital air, with featured resistances to clinical-used rifamycin and (glyco)peptides, whereas the more environmentally prevalent ARGs (e.g., resistance to sulfonamide and tetracycline) were identified being more specific to the nonclinical ambient air settings. Nearly all metagenome-assembled genomes (MAGs) that possessed the site-featured resistances were identified as pathogenic taxa, which occupied the upper-representative niches in all the neutrally distributed airborne microbial community (P < 0.01, m = 0.22-0.50, R2 = 0.41-0.86). These niche-favored putative resistant pathogens highlighted the enduring antibiotic resistance hazards in the studied urban air. These findings are critical, albeit the least appreciated until our study, to gauge the airborne dimension of resistomes' features and fates in urban atmospheric environments.


Assuntos
Genes Bacterianos , Metagenoma , Cidades , Antibacterianos/farmacologia , China
8.
Environ Sci Technol ; 57(35): 13004-13014, 2023 09 05.
Artigo em Inglês | MEDLINE | ID: mdl-37526013

RESUMO

High-resolution mass spectrometry is an advanced technique for comprehensive screening of toxic chemicals. In this study, urine samples were collected from both an occupationally exposed population at a coking site and normal inhabitants to identify novel urinary biomarkers for occupational exposure to coking contaminants. A coking-site-appropriate analytical method was developed for unknown chemical screening. Through nontarget screening, 515 differential features were identified, and finally, 32 differential compounds were confirmed as candidates for the current study, including 13 polycyclic aromatic hydrocarbon (PAH) metabolites. Besides monohydroxy-PAHs (such as 1-&2-naphthol, 2-&9-hydroxyfluorene, 2-&4-phenanthrol, and 1-&2-hydroxypyrene), many other PAH metabolites including dihydroxy metabolites, PAH oxide, and sulfate conjugate were detected, suggesting that the quantification based solely on monohydroxy-PAHs significantly underestimated the human exposure to PAHs. Furthermore, several novel compounds were recognized that could be considered as biomarkers for the exposure to coking contaminants, including quinolin-2-ol (1.10 ± 0.44 ng/mL), naphthylmethanols (11.4 ± 5.47 ng/mL), N-hydroxy-1-aminonaphthalene (0.78 ± 0.43 ng/mL), hydroxydibenzofurans (17.4 ± 7.85 ng/mL), hydroxyanthraquinone (0.13 ± 0.053 ng/mL), and hydroxybiphenyl (2.70 ± 1.03 ng/mL). Despite their lower levels compared with hydroxy-PAHs (95.1 ± 30.8 ng/mL), their severe toxicities should not be overlooked. The study provides a nontarget screening approach to identify chemicals in human urine, which is crucial for accurately assessing the health risks of toxic chemicals in the coking industry.


Assuntos
Cocaína , Coque , Exposição Ocupacional , Hidrocarbonetos Policíclicos Aromáticos , Humanos , Coque/análise , Cromatografia Líquida de Alta Pressão , Exposição Ocupacional/análise , Cocaína/análise , Biomarcadores , Monitoramento Ambiental/métodos
9.
Environ Sci Technol ; 57(25): 9252-9265, 2023 06 27.
Artigo em Inglês | MEDLINE | ID: mdl-37311058

RESUMO

The deterioration of air quality via anthropogenic activities during the night period has been deemed a serious concern among the scientific community. Thereby, we explored the outdoor particulate matter (PM) concentration and the contributions from various sources during the day and night in winter and spring 2021 in a megacity, northwestern China. The results revealed that the changes in chemical compositions of PM and sources (motor vehicles, industrial emissions, coal combustion) at night lead to substantial PM toxicity, oxidative potential (OP), and OP/PM per unit mass, indicating high oxidative toxicity and exposure risk at nighttime. Furthermore, higher environmentally persistent free radical (EPFR) concentration and its significant correlation with OP were observed, suggesting that EPFRs cause reactive oxygen species (ROS) formation. Moreover, the noncarcinogenic and carcinogenic risks were systematically explained and spatialized to children and adults, highlighting intensified hotspots to epidemiological researchers. This better understanding of day-night-based PM formation pathways and their hazardous impact will assist to guide measures to diminish the toxicity of PM and reduce the disease led by air pollution.


Assuntos
Poluentes Atmosféricos , Material Particulado , Criança , Humanos , Material Particulado/análise , Poluentes Atmosféricos/análise , Radicais Livres/análise , Espécies Reativas de Oxigênio , China , Monitoramento Ambiental
10.
Environ Sci Technol ; 57(41): 15379-15391, 2023 Oct 17.
Artigo em Inglês | MEDLINE | ID: mdl-37775339

RESUMO

Coking contamination in China is complex and poses potential health risks to humans. In this study, we collected urine samples from coking plant workers, nearby residents, and control individuals to analyze 25 coking-produced aromatic compounds (ACs), including metabolites of polycyclic aromatic hydrocarbons (PAHs) and their derivatives, chlorophenols, and nitrophenols. The median concentration of total ACs in urine of workers was 102 µg·g-1 creatinine, significantly higher than that in the other two groups. Hydroxy-PAHs and hydroxy hetero-PAHs were the dominant ACs. Workers directly exposed from coking industrial processes, i.e., coking, coal preparation, and chemical production processes, showed higher concentrations of hydroxy-PAHs and hydroxy hetero-PAHs (excluding 5-hydroxyisoquinoline), while those from indirect exposure workshops had higher levels of other ACs, indicating different sources in the coking plant. The AC mixture in workers demonstrated positive effects on DNA damage and lipid peroxidation with 5-hydroxyisoquinoline and 3-hydroxycarbazole playing a significant role using a quantile g-computation model. Monte Carlo simulation revealed that coking contamination elevated the carcinogenic risk for exposed workers by 5-fold compared to controls with pyrene, pentachlorophenol, and carbazole contributing the most, and workers from coking process are at the highest risk. This study enhances understanding of coking-produced AC levels and provides valuable insights into coking contamination control.

11.
Environ Res ; 219: 115158, 2023 02 15.
Artigo em Inglês | MEDLINE | ID: mdl-36580988

RESUMO

Occupational workers and residents near petrochemical industry facilities are exposed to multiple contaminants on a daily basis. However, little is known about the co-exposure effects of different pollutants based on biotransformation. The study examined benzo[a]pyrene (BaP), a representative polycyclic aromatic hydrocarbon related to the petrochemical industry, to investigate changes in toxicity and co-exposure mechanism associated with different monoaromatic hydrocarbons (MAHs). A central composite design method was used to simulate site co-exposure scenarios to reveal biotransformation of BaP when co-exposed with benzene, toluene, chlorobenzene, or nitrobenzene in microsome systems. BaP metabolism depended on MAH concentration, and association of MAH with microsome concentration/incubation time. Particularly, MAH co-exposure negatively affected BaP glucuronidation, an important phase Ⅱ detoxification process. BaP metabolite intensities decreased to 43%-80% for OH-BaP-G, and 32%-71% for diOH-BaP-G in co-exposure system with MAHs, compared with control group. Furthermore, glucuronidation was affected by competitive and time-dependent inhibition. Co-exposure significantly decreased gene expression of UGT 1A10 and BCRP/ABCG2 in HepG2 cells, which are involved in BaP detoxification through metabolism and transmembrane transportation. Therefore, human co-exposure to multiple contaminants may deteriorate toxic effects of these chemicals by disturbing metabolic pathways. This study provides a reference for assessing toxic effects and co-exposure risks of pollutants.


Assuntos
Poluentes Ambientais , Hidrocarbonetos Policíclicos Aromáticos , Humanos , Benzo(a)pireno/toxicidade , Membro 2 da Subfamília G de Transportadores de Cassetes de Ligação de ATP , Proteínas de Neoplasias/metabolismo , Hidrocarbonetos Policíclicos Aromáticos/toxicidade , Poluentes Ambientais/toxicidade , Tolueno
12.
Proc Natl Acad Sci U S A ; 117(24): 13294-13299, 2020 06 16.
Artigo em Inglês | MEDLINE | ID: mdl-32493751

RESUMO

Secondary organic aerosol (SOA) represents a major constituent of tropospheric fine particulate matter, with profound implications for human health and climate. However, the chemical mechanisms leading to SOA formation remain uncertain, and atmospheric models consistently underpredict the global SOA budget. Small α-dicarbonyls, such as methylglyoxal, are ubiquitous in the atmosphere because of their significant production from photooxidation of aromatic hydrocarbons from traffic and industrial sources as well as from biogenic isoprene. Current experimental and theoretical results on the roles of methylglyoxal in SOA formation are conflicting. Using quantum chemical calculations, we show cationic oligomerization of methylglyoxal in aqueous media. Initial protonation and hydration of methylglyoxal lead to formation of diols/tetrol, and subsequent protonation and dehydration of diols/tetrol yield carbenium ions, which represent the key intermediates for formation and propagation of oligomerization. On the other hand, our results reveal that the previously proposed oligomerization via hydration for methylglyoxal is kinetically and thermodynamically implausible. The carbenium ion-mediated mechanism occurs barrierlessly on weakly acidic aerosols and cloud/fog droplets and likely provides a key pathway for SOA formation from biogenic and anthropogenic emissions.

13.
J Environ Sci (China) ; 129: 90-103, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-36804245

RESUMO

Pathogenic microbes with antibiotic resistance can thrive on municipal solid waste as nutrients and be aerosolized and transported to vicinities during waste disposal processes. However, the characterization of pathogenic bioaerosols and assessment of their exposure risks are lacking. Herein, particle size, concentration, activity, antibiotic resistance, and pathogenicity of airborne microorganisms were assessed in different sectors of a typical landfill. Results showed that active sector in downwind direction has the highest bioaerosol level (1234 CFU/m3), while residential area has the highest activity (14.82 mg/L). Botanical deodorizer from mist cannon can effectively remove bioaerosol. Most bioaerosols can be inhaled into respiratory system till bronchi with sizes ranging from 2.1-3.3 and 3.3-4.7 µm. Pathogenic bacteria (Bacilli, Bacillus, and Burkholderia-Paraburkholderia) and allergenic fungi (Aspergillus, Cladosporium, and Curvularia) prevailed in landfill. Although high abundance of microbial volatile organic compounds (mVOCs) producing bioaerosols were detected, these mVOCs contributed little to odor issues in landfill. Notably, surrounding areas have higher levels of antibiotic-resistance genes (ARGs) than inner landfill with tetC, acrB, acrF, mdtF, and bacA as dominant ones. Most ARGs were significantly correlated with bacterial community, while environmental parameters mainly influenced fungal prevalence. These findings can assist in reducing and preventing respiratory allergy or infection risks in occupational environments relating to waste management.


Assuntos
Antibacterianos , Bacillus , Resistência Microbiana a Medicamentos/genética , Bactérias/genética , Genes Bacterianos , Instalações de Eliminação de Resíduos , Microbiologia do Ar , Monitoramento Ambiental
14.
J Environ Sci (China) ; 126: 722-733, 2023 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-36503797

RESUMO

Fugitive emission has been becoming an important source of volatile organic compounds (VOCs) in pharmaceutical industry, but the exact contribution of fugitive emission remains incompletely understood. In present study, pollution characteristics, odorous activity and health risk of stack and fugitive emissions of VOCs from four functional units (e.g., workshop, sewage treatment station, raw material storage and hazardous waste storage) of three representative pharmaceutical factories were investigated. Workshop was the dominant contributor to VOCs of fugitive emission in comparison with other functional units. Extreme high concentration of VOCs from fugitive emission in unsealed workshop (94.87 mg/m3) was observed relative to sealed one (1.18 mg/m3), accounting for 31% and 5% of total VOCs, respectively. Fugitive emission of VOCs in the unsealed workshop mainly consisted of n-hexane, 1-hexene and dichloromethane. Odorous activity indexes and non-cancer hazard ratios of these VOCs from fugitive emission in the unsealed workshop were as high as that from stack exhaust. Furthermore, cancer risk of dichloromethane from fugitive emission and stack exhaust was up to (1.6-1.8) × 10-5. Odorous activity or health risk index of the VOCs from fugitive emission was up to 13 or 11 times of the corresponding threshold value, posing remarkable health threat on pharmaceutical workers. Our findings highlighted the possibly underestimated contribution of fugitive emission on VOCs in the pharmaceutical industry.


Assuntos
Compostos Orgânicos Voláteis , Humanos , Poluição Ambiental , Indústria Farmacêutica , Medição de Risco , Cloreto de Metileno , Emissões de Veículos , Preparações Farmacêuticas
15.
J Environ Sci (China) ; 126: 103-112, 2023 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-36503740

RESUMO

Organosulfate (OSA) nanoparticles, as secondary organic aerosol (SOA) compositions, are ubiquitous in urban and rural environments. Hence, we systemically investigated the mechanisms and kinetics of aqueous-phase reactions of 1-butanol/1-decanol (BOL/DOL) and their roles in the formation of OSA nanoparticles by using quantum chemical and kinetic calculations. The mechanism results show that the aqueous-phase reactions of BOL/DOL start from initial protonation at alcoholic OH-groups to form carbenium ions (CBs), which engage in the subsequent esterification or oligomerization reactions to form OSAs/organosulfites (OSIs) or dimers. The kinetic results reveal that dehydration to form CBs for BOL and DOL reaction systems is the rate-limiting step. Subsequently, about 18% of CBs occur via oligomerization to dimers, which are difficult to further oligomerize because all reactive sites are occupied. The rate constant of BOL reaction system is one order of magnitude larger than that of DOL reaction system, implying that relative short-chain alcohols are more prone to contribute OSAs/OSIs than long-chain alcohols. Our results reveal that typical long-chain alcohols contribute SOA formation via esterification rather than oligomerization because OSA/OSI produced by esterification engages in nanoparticle growth through enhancing hygroscopicity.


Assuntos
Álcoois , Álcoois Graxos , Aerossóis , Butanóis , Polímeros , 1-Butanol
16.
J Environ Sci (China) ; 131: 123-140, 2023 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-37225374

RESUMO

Rational design and synthesis of highly efficient and robust photocatalysts with positive exciton splitting and interfacial charge transfer for environmental applications is critical. Herein, aiming at overcoming the common shortcomings of traditional photocatalysts such as weak photoresponsivity, rapid combination of photo-generated carriers and unstable structure, a novel Ag-bridged dual Z-scheme g-C3N4/BiOI/AgI plasmonic heterojunction was successfully synthesized using a facile method. Results showed that Ag-AgI nanoparticles and three-dimensional (3D) BiOI microspheres were decorated highly uniformly on the 3D porous g-C3N4 nanosheet, resulting in a higher specific surface area and abundant active sites. The optimized 3D porous dual Z-scheme g-C3N4/BiOI/Ag-AgI manifested exceptional photocatalytic degradation efficiency of tetracycline (TC) in water with approximately 91.8% degradation efficiency within 165 min, outperforming majority of the reported g-C3N4-based photocatalysts. Moreover, g-C3N4/BiOI/Ag-AgI exhibited good stability in terms of activity and structure. In-depth radical scavenging and electron paramagnetic resonance (EPR) analyses confirmed the relative contributions of various scavengers. Mechanism analysis indicated that the improved photocatalytic performance and stability were ascribed to the highly ordered 3D porous framework, fast electron transfer of dual Z-scheme heterojunction, desirable photocatalytic performance of BiOI/AgI and synergistic effect of Ag plasmas. Therefore, the 3D porous Z-scheme g-C3N4/BiOI/Ag-AgI heterojunction had a good prospect for applications in water remediation. The current work provides new insight and useful guidance for designing novel structural photocatalysts for environment-related applications.


Assuntos
Compostos Heterocíclicos , Tetraciclina , Antibacterianos , Microesferas , Água
17.
Environ Sci Technol ; 56(3): 1791-1800, 2022 02 01.
Artigo em Inglês | MEDLINE | ID: mdl-35061374

RESUMO

Iodinated aromatic disinfection byproducts (I-DBPs) are a group of nonregulated but highly toxic DBPs. The formation of I-DBPs is attributed mainly to HOI because it is the most abundant reactive iodine species in chloraminated water. In this study, we used computational modeling of thermodynamics to examine the mechanism of iodination of aromatic contaminants, e.g., dipeptides and phenols. Computational prediction of the energy barriers of the formation of iodinated tyrosylglycine (I-Tyr-Gly) (66.9 kcal mol-1) and hydroxylated Tyr-Gly (OH-Tyr-Gly) (46.0 kcal mol-1) via iodination with HOI favors the formation of OH-Tyr-Gly over I-Tyr-Gly. Unexpectedly, mass spectrometry experiments detected I-Tyr-Gly but not OH-Tyr-Gly, suggesting that I-Tyr-Gly formation cannot be attributed to HOI alone. To clarify this result, we examined the thermodynamic role of the most reactive iodine species H2OI+ in the formation of aromatic I-DBPs under chloramination. Computational modeling of thermodynamic results shows that the formation of a loosely bonded complex of aromatic compounds with H2OI+ is the key step to initiate the iodination process. When H2OI+ serves as an acid catalyst and an iodinating agent, with HOI or H2O acting as a proton acceptor, the energy barrier of I-DBP formation was significantly lower (10.8-13.1 kcal mol-1). Therefore, even with its low concentration, H2OI+ can be involved in the formation of I-DBPs. These results provide insight into the mechanisms of aromatic I-DBP formation and important information for guiding research toward controlling I-DBPs in drinking water.


Assuntos
Desinfetantes , Água Potável , Iodo , Poluentes Químicos da Água , Purificação da Água , Catálise , Desinfecção , Iodetos , Iodo/análise , Poluentes Químicos da Água/análise
18.
Ecotoxicol Environ Saf ; 236: 113486, 2022 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-35397445

RESUMO

Methanethiol is a widely existing malodorous pollutant with health effects on the human population. However, the cytotoxicity mechanism of methanethiol in vitro and its metabolic transformation (bioactivation or detoxification) have not been fully elucidated. Herein, the metabolites of methanethiol during cell culture and the cytotoxicity of methanethiol in human bronchial epithelial (16HBE) cells were investigated. Results indicate that methanethiol (10-50 µM) was partially converted into dimethyl sulfide, mainly catalyzed by thiol S-methyltransferase in the 16HBE cells, and then it induced potent cytotoxicity and cell membrane permeability. Moreover, methanethiol induced intracellular reactive oxygen species (ROS) up to 50 µM and further activated the tumor necrosis factor (TNF) signaling pathway, which eventually led to the decline in the mitochondrial membrane potential (MMP) and cell necrosis. However, all these effects were significantly alleviated with gene silencing of the methyltransferase-like protein 7B (METTL7B). These results indicate that methanethiol may induce cell necrosis in human respiratory tract cells mainly mediated by S-methyltransferase with interfering TNF and ROS induction. Non-target metabolomics results suggest that methanethiol potently affects expression of endogenous small molecule metabolites in 16HBE cells. To some extent, this work shows the possible conversion path and potential injury mechanism of human respiratory tract cells exposed to methanethiol.


Assuntos
Brônquios , Proteínas de Transporte , Metiltransferases , Compostos de Sulfidrila , Brônquios/efeitos dos fármacos , Brônquios/enzimologia , Brônquios/patologia , Proteínas de Transporte/metabolismo , Ativação Enzimática , Células Epiteliais/efeitos dos fármacos , Células Epiteliais/enzimologia , Células Epiteliais/patologia , Humanos , Metiltransferases/genética , Metiltransferases/metabolismo , Necrose , Espécies Reativas de Oxigênio/metabolismo , Compostos de Sulfidrila/farmacologia
19.
Build Environ ; 219: 109224, 2022 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-35645454

RESUMO

The public transport system, containing a large number of passengers in enclosed and confined spaces, provides suitable conditions for the spread of respiratory diseases. Understanding how diseases are transmitted in public transport environment is of vital importance to public health. However, this is a highly multidisciplinary matter and the related physical processes including the emissions of respiratory droplets, the droplet dynamics and transport pathways, and subsequently, the infection risk in public transport, are poorly understood. To better grasp the complex processes involved, a synthesis of current knowledge is required. Therefore, we conducted a review on the behaviors of respiratory droplets in public transport system, covering a wide scope from the emission profiles of expiratory droplets, the droplet dynamics and transport, to the transmission of COVID-19 in public transport. The literature was searched using related keywords in Web of Science and PubMed and screened for suitability. The droplet size is a key parameter in determining the deposition and evaporation, which together with the exhaled air velocity largely determines the horizontal travel distance. The potential transmission route and transmission rate in public transport as well as the factors influencing the virus-laden droplet behaviors and virus viability (such as ventilation system, wearing personal protective equipment, air temperature and relative humidity) were also discussed. The review also suggests that future studies should address the uncertainties in droplet emission profiles associated with the measurement techniques, and preferably build a database based on a unified testing protocol. Further investigations based on field measurements and modeling studies into the influence of different ventilation systems on the transmission rate in public transport are also needed, which would provide scientific basis for controlling the transmission of diseases.

20.
J Environ Sci (China) ; 114: 401-411, 2022 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-35459503

RESUMO

As more attention is being paid to the characteristics of atmospheric amines, there is also an increasing demand for reliable detection technologies. Herein, a method was developed for simultaneous detection of atmospheric amines in both gaseous and particulate phases using gas chromatography-mass spectrometry (GC-MS). The amine samples were collected with and without phosphoric acid filters, followed by derivatization with benzenesulfonyl chloride under alkaline condition prior to GC-MS analysis. Furthermore, the method was optimized and validated for determining 14 standard amines. The detection limits ranged from 0.0408-0.421 µg/mL (for gaseous samples) and 0.163-1.69 µg/mL (for particulate samples), respectively. The obtained recoveries ranged from 68.8%-180% and the relative standard deviation was less than 30%, indicating high precision and good reliability of the method. Seven amines were simultaneously detected in gaseous and particulate samples in an industrial park using the developed method successfully. Methylamine, dimethylamine and diethylamine together accounted for 76.7% and 75.6% of particulate and gaseous samples, respectively. By comparing the measured and predicted values of gas-particle partition fractions, it was found that absorption process of aqueous phase played a more important role in the gas-partition of amines than physical adsorption. Moreover, the reaction between unprotonated amines and acid (aq.) in water phase likely promoted water absorption. Higher measured partition fraction of dibutylamine was likely due to the reaction with gaseous HCl. The developed method would help provide a deeper understanding of gas-particle partitioning as well as atmospheric evolution of amines.


Assuntos
Aminas , Gases , Aminas/química , Poeira , Cromatografia Gasosa-Espectrometria de Massas/métodos , Reprodutibilidade dos Testes , Água/química
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