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The sensitivity of tropospheric ozone (O3) to its precursors volatile organic compounds (VOCs) and nitrogen oxides (NOX) determines the emission reduction strategy for O3 mitigation. Due to the lack of comprehensive vertical measurements of VOCs, the vertical distribution of O3 sensitivity regimes has not been well understood. O3 precursor sensitivity determined by ground-level measurements has been generally used to guide O3 control strategy. Here, to precisely diagnose O3 sensitivity regimes at different heights in the planetary boundary layer (PBL), we developed a vertical measurement system based on an unmanned aerial vehicle platform to conduct comprehensive vertical measurements of VOCs, NOX and other relevant parameters. Our results suggest that the O3 precursor sensitivity shifts from a VOC-limited regime at the ground to a NOX-limited regime at upper layers, indicating that the ground-level O3 sensitivity cannot represent the situation of the whole PBL. We also found that the state-of-the-art photochemical model tends to underestimate oxygenated VOCs at upper layers, resulting in overestimation of the degree of VOCs-limited regime. Therefore, thorough vertical measurements of VOCs to accurately diagnose O3 precursor sensitivity is in urgent need for the development of effective O3 control strategies.
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Controlling volatile organic compounds (VOCs) emitted from the automobile manufacturing industry requires establishing VOCs emission factors (EFs) and source profiles refinedly. In this study, 41 samples involved 32 VOCs discharge links were collected from three factories. The EFs and VOCs source profiles were estimated by the material balance method and weighted average method, respectively. The ozone formation potential (OFP) of the 110 VOCs species were calculated by the maximum incremental reactivity (MIR). According to estimations, the ranges of EFs were 0.23-1.66 kg VOCs/SUV car and 2.14-14.86 g VOCs/m2 painted area. EFs of six materials were firstly estimated, which are electrophoretic primer (152.31 ± 97.39 g VOCs/SUV car, 0.97 ± 0.38 g VOCs/m2 painted area), sealant (48.39 ± 26.20 g VOCs/SUV car, 0.46 ± 0.25 g VOCs/m2 painted area), floating coat (87.40 ± 75.63 g VOCs/SUV car, 0.86 ± 0.74 g VOCs/m2 painted area), colored paint (127.24 ± 168.24 g VOCs/SUV car, 1.25 ± 1.66 g VOCs/m2 painted area), varnish (205.46 ± 218.14 g VOCs/SUV car, 2.01 ± 2.15 g VOCs/m2 painted area), and cleaning solvent (328.54 ± 404.94 g VOCs/SUV car, 3.23 ± 3.98 g VOCs/m2 painted area). OVOCs (37.40-51.60 %) and aromatics (36.40-37.00 %) were the dominant components. n-Butyl acetate, 1,2,4-trimethylbenzene, undecane, n-hexanal, acetone, 1,2,3-trimethylbenzene, 1,3,5 -trimethylbenzene, m/p/o-xylene, 3-ethylbenzene, and 4-ethylbenzene were the major VOCs species, accounting for 68 % of total VOCs in the automobile manufacturing industry. Considering the OFP values of species, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, 1,2,3-trimethylbenzene, m/p-xylene, acetaldehyde, methyl ethyl ketone are the key active species that should be prioritized for control.
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Evaporative emissions release organic compounds comparable to gasoline exhaust in China. However, the measurement of intermediate volatility organic compounds (IVOCs) is lacking in studies focusing on gasoline evaporation. This study sampled organics from a real-world refueling procedure and analyzed the organic compounds using comprehensive two-dimensional gas chromatography coupled with a mass spectrometer (GC×GC-MS). The non-target analysis detected and quantified 279 organics containing 93 volatile organic compounds (VOCs, 64.9 ± 7.4 % in mass concentration), 182 IVOCs (34.9 ± 7.4 %), and 4 semivolatile organic compounds (SVOCs, 0.2 %). The refueling emission profile was distinct from that of gasoline exhaust. The b-alkanes in the B12 volatility bin are the most abundant IVOC species (1.9 ± 1.4 µg m-3) in refueling. A non-negligible contribution of 17.5 % to the ozone formation potential (OFP) from IVOCs was found. Although IVOCs are less in concentration, secondary organic aerosol potential (SOAP) from IVOCs (58.1 %) even exceeds SOAP from VOCs (41.6 %), mainly from b-alkane in the IVOC range. At the molecular level, the proportion of cyclic compounds in SOAP (12.1 %) indeed goes above its mass concentration (3.1 %), mainly contributed by cyclohexanes and cycloheptanes. As a result, the concentrations and SOAP of cyclic compounds (>50 %) could be overestimated in previous studies. Our study found an unexpected contribution of IVOCs from refueling procedures to both ozone and SOA formation, providing new insights into secondary pollution control policy.
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The container manufacturing industry is the key contributor of industrial volatile organic compounds (VOCs). Emission factors (EFs) and source profiles of container manufacturing industry were comprehensively investigated basing on multiple VOCs discharge links. 17 samples were collected from a typical container manufacturing enterprise based on field measurements. The material balance method and weighted average method were applied to estimate EFs and establish VOCs source profiles. It is found that diluent use (DU) was the largest contributor (39.96 %), followed by intermediate painting spaying (IMPS), primer painting (PP), chassis painting (CP), exterior paint spaying (EPS), and interior paint spaying (IPS). EF of the container manufacturing industry (2.90 kg VOCs/ Twenty-foot Equivalent Units, TEU) was firstly estimated. EFs of six processes were further estimated. The EFs of DU, IMPS, PP, CP, EPS, and IPS were 1.22, 0.74, 0.42, 0.33, 0.20, and 0.00045 kg VOCs/TEU, respectively. EFs of six materials were further estimated. The EF of the diluent was largest (382.74 kg VOCs/t material), followed by water-based epoxy intermediate paint (132.09 kg VOCs/t material), organic-based epoxy zinc-rich priming paint (91.31 kg VOCs/t material). EFs of other paints ranged from 0.0047 to 43.01 kg VOCs/t material. These results suggest that the replacement of lower- VOCs- contained diluent and effective control from diluent consumption are dramatically conducive to VOCs reduction. Source profiles were established at the industry and individual process levels. Aromatics (77.05-98.38 %) were dominant components in all processes, followed by alkane and OVOCs. m/p-Xylene, o-xylene, and ethylbenzene were the key active species that should be prioritized for control. Overall, EFs and source profiles of the container manufacturing industry were firstly proposed, conducing to the systematic formulation of VOCs control strategies.
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The coordinated control of PM2.5 and ozone has become the strategic goal of national air pollution control. Considering the gradual decline in PM2.5 concentration and the aggravation of ozone pollution, a better understanding of the coordinated control of PM2.5 and ozone is urgently needed. Here, we collected and sorted air pollutant data for 337 cities from 2015 to 2020 to explore the characteristics of PM2.5 and ozone pollution based on China's five major air pollution regions. The results show that it is necessary to continue to strengthen the emission reduction in PM2.5 and ozone precursors, and control NOx and VOCs while promoting a dramatic emission reduction in PM2.5. The primary method of curbing ozone pollution is to strengthen the emission control of VOCs, with a long-term strategy of achieving substantial emission reductions in NOx, because VOCs and NOx are also precursors to PM2.5; hence, their reductions also contribute to the reduction in PM2.5. Therefore, the implementation of a multipollutant emission reduction control strategy aimed at the prevention and control of PM2.5 and ozone pollution is the only means to realize the coordinated control of PM2.5 and ozone.
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Contaminantes Atmosféricos , Contaminación del Aire , Ozono , Ozono/análisis , Material Particulado/análisis , Monitoreo del Ambiente/métodos , Contaminantes Atmosféricos/análisis , Contaminación del Aire/prevención & control , Contaminación del Aire/análisis , ChinaRESUMEN
Aromatic hydrocarbons are important contributors to the formation of ozone and secondary organic aerosols in urban environments. The different parallel pathways in aromatic oxidation, however, remain inadequately understood. Here, we investigated the production yields and chemical distributions of gas-phase tracer products during the photooxidation of alkylbenzenes at atmospheric OH levels with NOx present using high-resolution mass spectrometers. The peroxide-bicyclic intermediate pathway emerged as the major pathway in aromatic oxidation, accounting for 52.1 ± 12.6%, 66.1 ± 16.6%, and 81.4 ± 24.3% of the total OH oxidation of toluene, m-xylene, and 1,3,5-trimethylbenzene, respectively. Notably, the yields of bicyclic nitrates produced from the reactions of bicyclic peroxy radicals (BPRs) with NO were considerably lower (3-5 times) than what the current mechanism predicted. Alongside traditional ring-opening products formed through the bicyclic pathway (dicarbonyls and furanones), we identified a significant proportion of carbonyl olefinic acids generated via the 1,5-aldehydic H-shift occurring in subsequent reactions of BPRs + NO, contributing 4-7% of the carbon flow in aromatic oxidation. Moreover, the observed NOx-dependencies of ring-opening and ring-retaining product yields provide insights into the competitive nature of reactions involving BPRs with NO, HO2, and RO2, which determine the refined product distributions and offer an explanation for the discrepancies between the experimental and model-based results.
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Ozono , Peróxidos , Oxidación-Reducción , Nitratos , Espectrometría de Masas , AerosolesRESUMEN
Indoor pollutants change over time and place. Exposure to hazardous organics is associated with adverse health effects. This work sampled gaseous organics by Tenax TA tubes in two indoor rooms, i.e., an office set as samples, and the room of chassis dynamometer (RCD) set as backgrounds. Compounds are analyzed by a thermal desorption comprehensive two-dimensional gas chromatography-quadrupole mass spectrometer (TD-GC × GC-qMS). Four new chemicals of emerging concern (CECs) are screened in 469 organics quantified. We proposed a three-step pipeline for CECs screening utilizing GC × GC including 1) non-target scanning of organics with convincing molecular structures and quantification results, 2) statistical analysis between samples and backgrounds to extract useful information, and 3) pixel-based property estimation to evaluate the contamination potential of addressed chemicals. New CECs spotted in this work are all intermediate volatility organic compounds (IVOCs), containing mintketone, isolongifolene, ß-funebrene, and (5α)-androstane. Mintketone and sesquiterpenes may be derived from the use of volatile chemical products (VCPs), while (5α)-androstane is probably human-emitted. The occurrence and contamination potential of the addressed new CECs are reported for the first time. Non-target scanning and the measurement of IVOCs are of vital importance to get a full glimpse of indoor organics.
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Androstanos , Gases , Humanos , Cromatografía de Gases y Espectrometría de Masas/métodos , Espectrometría de MasasRESUMEN
Incense burning is a common practice in Asian cultures, releasing hazardous particulate organics. Inhaling incense smoke can result in adverse health effects, yet the molecular compositions of incense-burning organics have not been well investigated due to the lack of measurement of intermediate-volatility and semi-volatile organic compounds (I/SVOCs). To elucidate the detailed emission profile of incense-burning particles, we conducted a non-target measurement of organics emitted from incense combustion. Quartz filters were utilized to trap particles, and organics were analyzed by a comprehensive two-dimensional gas chromatography-mass spectrometer (GC × GC-MS) coupled with a thermal desorption system (TDS). To deal with the complex data obtained by GC × GC-MS, homologs are identified mainly by the combination of selected ion chromatograms (SICs) and retention indexes. SICs of 58, 60, 74, 91, and 97 were utilized to identify 2-ketones, acids, fatty acid methyl esters, fatty acid phenylmethyl esters, and alcohols, respectively. Phenolic compounds contribute the most to emission factors (EFs) among all chemical classes, taking up 24.5 % ± 6.5 % of the total EF (96.1 ± 43.1 µg g-1). These compounds are largely derived from the thermal degradation of lignin. Biomarkers like sugars (mainly levoglucosan), hopanes, and sterols are extensively detected in incense combustion fumes. Incense materials play a more important role in shaping emission profiles than incense forms. Our study provides a detailed emission profile of particulate organics emitted from incense burning across the full-volatility range, which can be used in the health risk assessments. The data processing procedure in this work could also benefit those with less experience in non-target analysis, especially GC × GC-MS data processing.
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Ambient gas- and particle-phase intermediate volatility and semi-volatile organic compounds (I/SVOCs) of Beijing were analyzed by a thermal desorption comprehensive two-dimensional gas chromatography quadrupole mass spectrometry (TD-GC × GC-qMS). A pixel-based scheme combing the integration-based approach was applied for partition coefficients estimation and fingerprints identification. Blob-by-blob recognition was firstly utilized to characterize I/SVOCs from the molecular level. 412 blobs in gas-phase and 460 blobs in particle-phase were resolved, covering a total response of 47.5% and 43.5%. A large pool of I/SVOCs was found with a large diversity of chemical classes in both gas- and particle-phase. Acids (8.5%), b-alkanes (5.8%), n-alkanes (C8-C25, 5.3%), and aromatics (4.4%) were dominant in gas-phase while esters (7.0%, including volatile chemical product compounds, VCPs), n-alkanes (C9-C34, 5.7%), acids (4.6%), and siloxanes (3.6%) were abundant in particle-phase. Air pollutants were then evaluated by a two-parameter linear free energy relationship (LFER) model, which could be further implemented in the two-dimensional volatility basis set (2D-VBS) model. Multiway principal component analysis (MPCA) and partial least squares-discriminant analysis (PLS-DA) implied that naphthalenes, phenol, propyl-benzene isomers, and oxygenated volatile organic compounds (OVOCs) were key components in the gas-phase under different pollution levels. This work gives more insight into property estimation and fingerprints identification for complex ambient samples.
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Contaminantes Atmosféricos , Compuestos Orgánicos Volátiles , Contaminantes Atmosféricos/análisis , Alcanos , Ésteres , Cromatografía de Gases y Espectrometría de Masas , Compuestos Orgánicos Volátiles/análisisRESUMEN
Formaldehyde (HCHO) can possibly be taken by atmospheric particles due to its moderate solubility. Although previous model studies have proposed that uptake by particles was a large sink for HCHO, direct observation of HCHO partitioning and estimation of HCHO uptake coefficient (γ) for tropospheric conditions are still limited. In this work, online measurements of gaseous HCHO (HCHOg) and particulate HCHO (HCHOp) were carried out simultaneously at an urban site in Beijing in winter and spring. The results indicated that the average concentrations of HCHOp ranged from 0.15 to 0.4 µg m-3, accounting for 1.2% to 10% of the total HCHO (i.e., HCHOg + HCHOp). The median values of estimated γ based on the measured data were in the range of about 1.09 ∗ 10-5-2.42 ∗ 10-4, with lower values during PM2.5 pollution episodes. Besides, the pH and liquid water content of aerosols that are mainly determined by ambient relative humidity (RH) and inorganic salt composition were identified as the main influencing factors of γ. We propose that the HCHO uptake process was mainly driven by hydrone and hydrogen ions in particles.
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Contaminantes Atmosféricos , Gases , Contaminantes Atmosféricos/análisis , Polvo , Monitoreo del Ambiente , Formaldehído/análisis , Gases/análisis , Material Particulado/análisisRESUMEN
Volatile organic compounds (VOCs) play an important role in air pollution. In this study, we conducted comprehensive field observations to investigate wintertime air pollution in Beijing, Wangdu, and Dezhou in the Beijing-Tianjin-Hebei region during 2017 and 2018. The average VOC concentrations of the three sites were 35.6 ± 26.6, 70.9 ± 56.3, and 50.5 ± 40.0 ppbv, respectively. The species with the highest concentration were similar in all three sites and included ethane, ethylene, acetylene, acetone, and toluene. The VOC mixing ratios of the three sites showed synchronous growth during pollution episodes and were 1.2-2 times higher than those during clean periods. Moreover, the OH loss rates (LOH) during pollution episodes were 1.2-1.7 times that during clean periods. The crucial reactive species in the three sites were ethylene, propylene, and acetaldehyde, contributing approximately 70% to the total LOH during pollution periods. According to the source apportionment analysis, vehicle exhausts were the largest source of VOCs in Beijing, accounting for more than 50% of the total emissions. During the pollution episodes, Beijing's industrial emissions decreased, but the secondary and background sources increased. Coal combustion was significant (approximately 40%) in Wangdu and should therefore be prioritized in emission reduction policies. In Dezhou, industrial emissions had a considerable impact on the VOC mixing ratio during pollution periods and should therefore be prioritized. The backward trajectory analysis showed that VOCs from the southern region likely contribute to Beijing's VOC pollution, highlighting the importance of regional integration for air quality management.
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Contaminantes Atmosféricos , Compuestos Orgánicos Volátiles , Contaminantes Atmosféricos/análisis , Beijing , China , Monitoreo del Ambiente , Emisiones de Vehículos/análisis , Compuestos Orgánicos Volátiles/análisisRESUMEN
A volatile organic compound (VOC) emissions inventory of the petroleum refinery in Hebei was established. This refinery emits 1859.2 tons of VOCs per year, with wastewater collection and treatment system being the largest emissions source, accounting for 59.6% individually, followed by the recirculating cooling water system (13.4%), storage tanks (11.1%), and equipment leaks (9.4%). Organized and fugitive samples were collected simultaneously for different processes of each emissions source. A total of 100 VOC species were characterized and quantified using a gas chromatography-mass spectrometry/flame ionization detection system. The VOC emissions concentrations and chemical composition of each process were quite different. Most of the processes used alkanes as the main chemome. We concluded from the composite source profile weighted by the amount of VOC emissions that the characteristic species of this petroleum refinery were ethane (15.4%), propylene (11.7%), propane (8.5%), iso-pentane (8.3%), and toluene (4.7%). The ozone (O3) formation potential (OFP) and secondary organic aerosol formation potential (SOAP) were evaluated, and the results indicated that alkenes (mainly propylene) and aromatics (mainly toluene) were the priority control compounds. This study clarifies the current status of VOC emissions in the refinery in terms of emissions intensity, emissions components, and O3 and SOA reactivity. The key emissions sources and species screened provide scientific support for reducing refined emissions from the petrochemical industry.
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Contaminantes Atmosféricos , Ozono , Petróleo , Compuestos Orgánicos Volátiles , Contaminantes Atmosféricos/análisis , China , Monitoreo del Ambiente , Ozono/análisis , Petróleo/análisis , Compuestos Orgánicos Volátiles/análisisRESUMEN
Nitrated phenols (NPs) are important atmospheric pollutants that affect air quality, radiation, and health. The recent development of the time-of-flight chemical ionization mass spectrometer (ToF-CIMS) allows quantitative online measurements of NPs for a better understanding of their sources and environmental impacts. Herein, we deployed nitrate ions as reagent ions in the ToF-CIMS and quantified six classes of gaseous NPs in Beijing. The concentrations of NPs are in the range of 1 to 520 ng m-3. Nitrophenol (NPh) has the greatest mean concentration. Dinitrophenol (DNP) shows the greatest haze-to-clean concentration ratio, which may be associated with aqueous production. The high concentrations and distinct diurnal profiles of NPs indicate a strong secondary formation to overweigh losses, driven by high emissions of precursors, strong oxidative capacity, and high NOx levels. The budget analysis on the basis of our measurements and box-model calculations suggest a minor role of the photolysis of NPs (<1 ppb h-1) in producing OH radicals. NPs therefore cannot explain the underestimated OH production in urban environments. Discrepancies between these results and the laboratory measurements of the NP photolysis rates indicate the need for further studies aimed at understanding the production and losses of NPs in polluted urban environments.
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Contaminantes Atmosféricos , Nitratos , Contaminantes Atmosféricos/análisis , Beijing , Monitoreo del Ambiente , Gases/análisis , Fenoles/análisisRESUMEN
An in-depth study was conducted to quantify and characterize VOC emissions from a petroleum refinery located in Shandong, China. The VOC emission inventory established in this study showed that storage tanks were the largest emission source, accounting for 56.4% of total emissions, followed by loading operations, wastewater collection and treatment system, process vents, and equipment leaks. Meanwhile, the localization factors for refining, storage tanks and loading operations were calculated, which were 1.33, 0.75 and 0.31g VOCs/kg crude oil refined. Furthermore, the characteristics of fugitive and organized emissions were determined for various processes and emission sources using a gas chromatography-mass spectrometry/flame ionization detection (GC-MS/FID) system. Most samples contained mainly alkanes, but the total VOC concentrations and key species varied greatly among processes. The source profile of the refinery, synthesized using the weighted average method, indicated that cis-2-butene (14.5%), n-pentane (10.2%), n-butane (7.4%), isopentane (6.5%) and MTBE (5.9%) were the major species released by this refinery. Assessment of O3 and secondary organic aerosol formation potentials were completed, and the results indicated that cis-2-butene, m/p-xylene, toluene, n-pentane, isopentane, benzene, o-xylene and ethylbenzene were the active species for which treatment should be prioritized.
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Contaminantes Atmosféricos , Petróleo , Compuestos Orgánicos Volátiles , Contaminantes Atmosféricos/análisis , China , Monitoreo del Ambiente , Petróleo/análisis , Compuestos Orgánicos Volátiles/análisisRESUMEN
Solvent use and paint consumption are significant source sectors of volatile organic compounds (VOCs) emissions in China. The occupational painters have high risk of health effect due to exposure to high VOCs concentration. However, the toxic components in coating environment have not been carefully identified, and the health risks of VOCs exposure have not been sufficiently assessed. This study collected air samples from nine workshops of three major coating sectors in the Yangtze River Delta of China, namely cargo container coating, ship equipment coating, and furniture coating, to evaluate the non-cancer and cancer risk of toxic VOCs exposure to occupational painters under a normal working condition. The results show that the container coating had highest cancer risk (2.29 × 10-6-5.53 × 10-6) exceeding the safe limit of 1.0 × 10-6, while non-cancer risk of all workshops was lower than acceptable level of 1. Ethylbenzene and 1,2-dichloropropane should be targeted for priority removal during the container coating process in attempt to reduce adverse health effect on the occupational painters. This study helps better understand the health risk of VOCs exposure in coating workshops in China and provides information for policy-makers to formulate possible control of specific toxic compounds during coating process.
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Contaminantes Atmosféricos , Compuestos Orgánicos Volátiles , Contaminantes Atmosféricos/análisis , China , Monitoreo del Ambiente , Pintura , Medición de Riesgo , Ríos , Compuestos Orgánicos Volátiles/análisisRESUMEN
A lot of restrictive measures were implemented in China during January-February 2020 to control rapid spread of COVID-19. Many studies reported impact of COVID-19 lockdown on air quality, but little research focused on ambient volatile organic compounds (VOCs) till now, which play important roles in production of ozone and secondary organic aerosol. In this study, impact of COVID-19 lockdown on VOCs mixing ratios and sources were assessed based on online measurements of VOCs in Nanjing during December 20, 2019-Feburary 15, 2020 (P1-P2) and April 15-May 13, 2020 (P3). Average VOCs levels during COVID-19 lockdown period (P2) was 26.9 ppb, about half of value for pre-lockdown period (P1). Chemical composition of VOCs also showed significant changes. Aromatics contribution during decreased from 13% during P1 to 9% during P2, whereas alkanes contribution increased from 64% to 68%. Positive matrix factorization (PMF) was then applied for non-methane hydrocarbons (NMHCs) sources apportionment. Five sources were identified, including a source related to transport and background air masses, three sources related to petrochemical industry or chemical industry (petrochemical industry#1-propene/ethene, petrochemical industry#2-C7-C9 aromatics, and chemical industry-benzene), and a source attributed to gasoline evaporation and vehicular emission. During P2, NMHCs levels from petrochemical industry#2-C7-C9 aromatics showed the largest relative decline of 94%, followed by petrochemical industry#1-propene/ethene (67%), and gasoline evaporation and vehicular emission (67%). Furthermore, ratios of OH reactivity of NMHCs versus NO2 level (ROH,NMHCs/NO2) and total oxidant production rate (P (OX)) were calculated to assess potential influences of COVID-19 lockdown on O3 formation.
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Contaminantes Atmosféricos , COVID-19 , Ozono , Compuestos Orgánicos Volátiles , Contaminantes Atmosféricos/análisis , China , Control de Enfermedades Transmisibles , Monitoreo del Ambiente , Humanos , Ozono/análisis , SARS-CoV-2 , Compuestos Orgánicos Volátiles/análisisRESUMEN
Photolysis of nitrous acid (HONO) is one of the major sources for atmospheric hydroxyl radicals (OH), playing significant role in initiating tropospheric photochemical reactions for ozone (O3) production. However, scarce field investigations were conducted to elucidate this effect. In this study, a field campaign was conducted at a suburban site in southwest China. The whole observation was classified into three periods based on O3 levels and data coverage: the serious O3 pollution period (Aug 13-18 as P1), the O3 pollution period (Aug 22-28 as P2) and the clean period (Sep 3-12 as P3), with average O3 peak values of 96 ppb, 82 ppb and 44 ppb, respectively. There was no significant difference of the levels of O3 precursors (VOCs and NOx) between P1 and P2, and thus the evident elevation of OH peak values in P1 was suspected to be the most possible explanation for the higher O3 peak values. Considering the larger contribution of HONO photolysis to HOX primary production than photolysis of HCHO, O3 and ozonolysis of Alkenes, sensitivity tests of HONO reduction on O3 production rate in P1 are conducted by a 0-dimension model. Reduced HONO concentration effectively slows the O3 production in the morning, and such effect correlates with the calculated production rate of OH radicals from HONO photolysis. Higher HONO level supplying for OH radical initiation in the early morning might be the main reason for the higher O3 peak values in P1, which explained the correlation (R2 = 0.51) between average O3 value during daytime (10:00-19:00 LT) and average HONO value during early morning (00:00-05:00 LT). For nighttime accumulation, a suitable range of relative humidity that favored NO2 conversion within P1 was assumed to be the reason for the higher HONO concentration in the following early morning which promoted O3 peak values.
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An emission inventory of precursors is a prerequisite for the simulation of secondary organic aerosol (SOA), which could provide valuable information on the evolution of precursors, formation of SOA, and its influence on fine particle (PM2.5) abundance, oxidative capacity, and climate change. However, an emission inventory of semi-volatile and intermediate volatility organic compounds (S/IVOCs), the key precursor of SOA, particularly the gridded inventory that is appropriate for input into regional air quality models, remains limited in China, leading to an incomplete understanding of S/IVOCs sources and roles in SOA formation and the atmospheric environment. Therefore, a gridded emission inventory of S/IVOCs in China for 2016 was developed based on ample source-specific measured data on emission ratios of S/IVOCs to primary organic aerosols (POA) from literatures. The total emission of S/IVOCs was estimated to be 9.6 Tg, and industry and residential sectors were major sources of S/IVOCs, with contributions of 48.0% and 30.2%, respectively. The spatial variations suggested that S/IVOC emissions were mainly distributed in the highly industrialized and urbanized regions in China, such as Beijing-Tianjin-Hebei (BTH), the Yangtze River Delta (YRD), the Pearl River Delta (PRD), and the Sichuan-Chongqing (SC) regions, though the contributions and temporal patterns varied between different regions. Furthermore, uncertainty of the emission inventory was estimated to be within the range of -66%-153%, which was mainly attributed to emission ratios of IVOCs/POA for industry, transportation, and power plants. The gridded emission inventory developed in this study can be used to estimate the emissions of S/IVOCs in different regions, and can be applied to different models for a better understanding of the environmental effects of S/IVOCs.
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We theoretically and experimentally demonstrate a novel, to the best of our knowledge, mode-locked ytterbium-doped fiber laser with a saturable absorber based on the nonlinear Kerr beam cleanup effect. The saturable absorber was formed by a 2-m graded-index multimode fiber, and a single-mode fiber segment served as a diaphragm. With an all-normal-dispersion-fiber configuration, the laser generated dissipative soliton pulses with pulse duration of 26.38 ps and pulse energy more than 0.25 nJ; output pulses could be compressed externally to 615.7 fs. Moreover, the self-starting mode-locking operation of this laser exhibited a high stability with a measured signal-to-noise ratio of 73.4 dB in the RF spectrum.
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In order to evaluate the volatile organic compounds (VOCs) pollution characteristics in Chengdu and to identify their sources, ambient air sample collection and measurement were conducted at 28 sampling sites covering all districts/counties of Chengdu from May 2016 to January 2017. Meanwhile, a county-level anthropogenic speciated VOCs emission inventory was established by "bottom-up" method for 2016. Then, a comparison was made between the VOCs emissions, spatial variations, and source structures derived from the measurement and emission inventory. Ambient measurements showed that the annual average mixing ratios of VOCs in Chengdu were 57.54 ppbv (12.36 to 456.04 ppbv), of which mainly dominated by alkanes (38.8%) and OVOCs (22.0%). The ambient VOCs in Chengdu have distinct spatiotemporal characteristics, with a high concentration in January at the middle-northern part of the city and a low concentration in September at the southwestern part. The spatial distribution of VOCs estimated by the emission inventory was in good agreement with ambient measurements. Comparison of individual VOCs emissions indicated that the emissions of non-methane hydrocarbon species agreed within ±100% between the two methods. Both positive matrix factorization (PMF) model results and emission inventory showed that vehicle emissions were the major contributor of anthropogenic VOCs in Chengdu (31% and 37%), followed by solvent utilization (26% and 27%) and industrial processes (23% and 30%). The large discrepancies were found between the relative contribution of combustion sources, and the PMF resolved more contributions (20%) than the emission inventory (6%). Overall, this study demonstrates that measurement results and emission inventory were in a good agreement. However, to improve the reliability of the emission inventory, we suggest significant revision on source profiles of oxygenated volatile organic compounds (OVOCs) and halocarbons, as well as more detailed investigation should be made in terms of energy consumption in household.