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1.
RSC Adv ; 14(18): 12303-12312, 2024 Apr 16.
Artigo em Inglês | MEDLINE | ID: mdl-38633496

RESUMO

As dienes contain two C[double bond, length as m-dash]C bonds, theoretically, they are much more chemically reactive with hydroxyl radical (˙OH) than alkenes and alkanes, and the reaction with ˙OH is one of the main atmospheric degradation routes of dienes during the daytime. In our work, rate coefficients of three types of acyclic dienes: conjugated as 3-methyl-1,3-pentadiene (3M13PD), isolated as 1,4-hexadiene (14HD), and cumulated as 1,2-pentadiene (12PD) reaction with ˙OH were measured in the temperature range of 273-318 K and 1 atm using the relative rate method. At 298 ± 3 K, the rate coefficients for those reactions were determined to be k3M13PD+OH = (15.09 ± 0.72) × 10-11, k14HD+OH = (9.13 ± 0.62) × 10-11, k12PD+OH = (3.34 ± 0.40) × 10-11 (as units of cm3 per molecule per s), in the excellent agreement with values of previously reported. The first measured temperature dependence for 3M13PD, 14HD and 12PD reaction with ˙OH can be expressed by the following Arrhenius expressions in units of cm3 per molecule per s: k3M13PD+OH = (8.10 ± 2.23) × 10-11 exp[(173 ± 71)/T]; k14HD+OH = (9.82 ± 5.10) × 10-12 exp[(666 ± 123)/T]; k12PD+OH = (1.13 ± 0.87) × 10-12 exp[(1038 ± 167)/T] (as units of cm3 per molecule per s). The kinetic discussion revealed that the relative position between these two C[double bond, length as m-dash]C could significantly affect the reactivity of acyclic dienes toward ˙OH. A simple structure-activity relationship (SAR) method was proposed to estimate the reaction rate coefficients of acyclic dienes with ˙OH.

2.
Environ Sci Technol ; 58(13): 5911-5920, 2024 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-38437592

RESUMO

HONO acts as a major OH source, playing a vital role in secondary pollutant formation to deteriorate regional air quality. Strong unknown sources of daytime HONO have been widely reported, which significantly limit our understanding of radical cycling and atmospheric oxidation capacity. Here, we identify a potential daytime HONO and OH source originating from photoexcited phenyl organic nitrates formed during the photoreaction of aromatics and NOx. Significant HONO (1.56-4.52 ppb) and OH production is observed during the photoreaction of different kinds of aromatics with NOx (18.1-242.3 ppb). We propose an additional mechanism involving photoexcited phenyl organic nitrates (RONO2) reacting with water vapor to account for the higher levels of measured HONO and OH than the model prediction. The proposed HONO formation mechanism was evidenced directly by photolysis experiments using typical RONO2 under UV irradiation conditions, during which HONO formation was enhanced by relative humidity. The 0-D box model incorporated in this mechanism accurately reproduced the evolution of HONO and aromatic. The proposed mechanism contributes 5.9-36.6% of HONO formation as the NOx concentration increased in the photoreaction of aromatics and NOx. Our study implies that photoexcited phenyl organic nitrates are an important source of atmospheric HONO and OH that contributes significantly to atmospheric oxidation capacity.


Assuntos
Poluentes Ambientais , Ácido Nitroso , Ácido Nitroso/análise , Radical Hidroxila , Oxirredução , Raios Ultravioleta , Nitratos
3.
Sci Total Environ ; 919: 170802, 2024 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-38342469

RESUMO

Nitrous oxide (N2O) and nitrogen oxides (NOx) (i.e., nitric oxide (NO) and nitrogen dioxide (NO2)), which could be produced in wastewater treatment process and result in greenhouse effect and atmospheric pollution, respectively, have been studied limitedly in their emission characteristics and transformation mechanisms. In this study, intelligent oxygen regulation was applied in anoxic/oxic wastewater treatment process (I-A/O), and its effects on regulating NOx and N2O transformations were extensively explored by comparing it with conventional A/O process (C-A/O). Results showed that the average emission amounts of N2O and NOx in I-A/O were 7.45 ± 0.66 mg and 1.88 ± 0.10 mg, respectively. Satisfactory reduction of N2O by 29.28 %-45.08 % was achieved in I-A/O compared to that of C-A/O, but together with increased NOx emission by 83.19 %-120.57 %. Pearson correlation and transcriptional analysis suggested that NO2--N reduction in the anoxic phase dominated N2O production, while no significant N2O production in the oxic phase was found. Hence, the reduced N2O production in I-A/O was mainly attributed to its efficient denitrification process. On the other hand, both the anoxic and oxic phases played important roles in NO production. More importantly, sufficient oxygen in I-A/O promoted the ammonia oxidation process, resulting in higher NO emission in I-A/O in the oxic phase. The imbalance in NO and N2O emissions was then amplified by the NOR enzyme, which mediates the conversion of NO to N2O in both the anoxic and oxic phases. Besides, carbon emission reduction by 31.32 %-36.50 % was obtained in I-A/O due to aeration consumption savings and greenhouse gas emissions reduction compared to C-A/O. Overall, intelligent oxygen regulation optimized the nitrogen transformation and achieved carbon emission reduction in A/O process, but special attention should be paid to the associated risk caused by increased NO emissions.

4.
Proc Natl Acad Sci U S A ; 120(35): e2302048120, 2023 Aug 29.
Artigo em Inglês | MEDLINE | ID: mdl-37603738

RESUMO

Gaseous nitrous acid (HONO) is a critical source of hydroxyl radicals (OH) in the troposphere. While both direct and secondary sources contribute to atmospheric HONO, direct emissions have traditionally been considered minor contributors. In this study, we developed δ15N and δ18O isotopic fingerprints to identify six direct HONO emission sources and conducted a 1-y case study on the isotopic composition of atmospheric HONO at rural and urban sites. Interestingly, we identified that livestock farming is a previously overlooked direct source of HONO and determined its HONO to ammonia (NH3) emission ratio. Additionally, our results revealed that spatial and temporal variations in atmospheric HONO isotopic composition can be partially attributed to direct emissions. Through a detailed HONO budget analysis incorporating agricultural sources, we found that direct HONO emissions accounted for 39~45% of HONO production in rural areas across different seasons. The findings were further confirmed by chemistry transport model simulations, highlighting the significance of direct HONO emissions and their impact on air quality in the North China Plain. These findings provide compelling evidence that direct HONO emissions play a more substantial role in contributing to atmospheric HONO than previously believed. Moreover, the δ15N and δ18O isotopic fingerprints developed in this study may serve as a valuable tool for further research on the atmospheric chemistry of reactive nitrogen gases.

5.
Sci Total Environ ; 885: 163807, 2023 Aug 10.
Artigo em Inglês | MEDLINE | ID: mdl-37146814

RESUMO

Nearly 10-year (2013-2022) data on atmospheric particulate matters (PMs) were collected to investigate the air quality in a suburban site of Orléans city (France). The PM10 concentration decreased slightly between 2013 and 2022. PMs concentrations showed a monthly variation with higher concentration in cold periods. PM10 presented a clear bimodal diurnal variation peaking at morning rush hour and midnight, whereas the fine PMs such as PM2.5 and PM1.0 only had significant peaks during nighttime. Further, PM10 had more pronounced week-end effect than other fine PMs. COVID-19 lockdown impact on PMs levels was further investigated, showing that the lockdown during cold season could result in an increase of PMs concentrations because of the enhanced household heating. We concluded that PM10 could originate from biomass burning and fossil fuel related activities, air parcels from the western Europe through Paris were also important source of PM10 in the investigated area. Fine PMs, such as PM2.5 and PM1.0, originated mainly from biomass burning in addition to secondary formation at the local scale. This study provides a long-term PMs measurement database to explore the sources and characterization of PMs in central France, which could support future regulation and formulation of air quality standards.

6.
Sci Total Environ ; 881: 163438, 2023 Jul 10.
Artigo em Inglês | MEDLINE | ID: mdl-37054793

RESUMO

Atmospheric HONO acts as a major source for OH radicals in polluted areas, playing an important role in formation of secondary pollutants. However, the atmospheric HONO sources remain unclear. Here we propose that the heterogeneous reaction of NO2 on aerosols during aging processes acts as the dominant source for nocturnal HONO. Based on the nocturnal variations of HONO and related species in Tai'an city of China, we firstly developed new method to estimate the localized HONO dry deposition velocity (v(HONO)). The estimated v(HONO) of 0-0.077 m/s was in a good agreement with the reported ranges. Additionally, we set up a parametrization to reflect the HONO formation from the aged air parcels based on the variation of HONO/NO2 ratio. The detailed variation of nocturnal HONO could be well reproduced by a complete budget calculation coupled with above parameterizations, with the difference between the observed and calculated HONO levels being <5 %. The results also revealed the average contribution of HONO formation from aged air parcels to atmospheric HONO could achieve to be ~63 % in average.

7.
IEEE Trans Cybern ; 53(2): 859-873, 2023 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-35439160

RESUMO

Decision and control are core functionalities of high-level automated vehicles. Current mainstream methods, such as functional decomposition and end-to-end reinforcement learning (RL), suffer high time complexity or poor interpretability and adaptability on real-world autonomous driving tasks. In this article, we present an interpretable and computationally efficient framework called integrated decision and control (IDC) for automated vehicles, which decomposes the driving task into static path planning and dynamic optimal tracking that are structured hierarchically. First, the static path planning generates several candidate paths only considering static traffic elements. Then, the dynamic optimal tracking is designed to track the optimal path while considering the dynamic obstacles. To that end, we formulate a constrained optimal control problem (OCP) for each candidate path, optimize them separately, and follow the one with the best tracking performance. To unload the heavy online computation, we propose a model-based RL algorithm that can be served as an approximate-constrained OCP solver. Specifically, the OCPs for all paths are considered together to construct a single complete RL problem and then solved offline in the form of value and policy networks for real-time online path selecting and tracking, respectively. We verify our framework in both simulations and the real world. Results show that compared with baseline methods, IDC has an order of magnitude higher online computing efficiency, as well as better driving performance, including traffic efficiency and safety. In addition, it yields great interpretability and adaptability among different driving scenarios and tasks.

8.
Sci Total Environ ; 854: 158675, 2023 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-36089050

RESUMO

Activators affect the physical and chemical properties of carbon products. However, the effects of different activation mechanisms and pyrolysis conditions on the properties of carbon products still need to be explored. In this study, we obtained a new biochar by impregnation of reed powder with an alkali metal salt (CaCl2) under a specific pyrolysis procedure and pyrolysis conditions. Impregnation by CaCl2 can reduce the activation energy of the biomass while capturing and immobilizing oxygenated organic matter during pyrolysis. The new biochar has a high adsorption capacity of organic matters, for example Bisphenol A (BPA). The adsorption results showed that the modified biochar demonstrated a 364.5 % improvement in the adsorption capacity compared to the original biochar. The final performance enhancement was correlated with the confinement conditions of the environment and the procedure of pyrolysis. These procedures ultimately changed the pore distribution, functional group type, aromaticity, and degree of defects of the modified biochar. This study is important to screen synthetic pathways for identifying compounds with excellent adsorption effects.


Assuntos
Poluentes Ambientais , Poluentes Químicos da Água , Cloreto de Cálcio , Adsorção , Carvão Vegetal/química , Carbono , Poluentes Químicos da Água/análise
9.
Sci Total Environ ; 858(Pt 2): 159905, 2023 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-36343810

RESUMO

Atmospheric black carbon (BC) concentration over a nearly 5 year period (mid-2017-2021) was continuously monitored over a suburban area of Orléans city (France). Annual mean atmospheric BC concentration were 0.75 ± 0.65, 0.58 ± 0.44, 0.54 ± 0.64, 0.48 ± 0.46 and 0.50 ± 0.72 µg m-3, respectively, for the year of 2017, 2018, 2019, 2020 and 2021. Seasonal pattern was also observed with maximum concentration (0.70 ± 0.18 µg m-3) in winter and minimum concentration (0.38 ± 0.04 µg m-3) in summer. We found a different diurnal pattern between cold (winter and fall) and warm (spring and summer) seasons. Further, fossil fuel burning contributed >90 % of atmospheric BC in the summer and biomass burning had a contribution equivalent to that of the fossil fuel in the winter. Significant week days effect on BC concentrations was observed, indicating the important role of local emissions such as car exhaust in BC level at this site. The behavior of atmospheric BC level with COVID-19 lockdown was also analyzed. We found that during the lockdown in warm season (first lockdown: 27 March-10 May 2020 and third lockdown 17 March-3 May 2021) BC concentration were lower than in cold season (second lockdown: 29 October-15 December 2020), which could be mainly related to the BC emission from biomass burning for heating. This study provides a long-term BC measurement database input for air quality and climate models. The analysis of especially weekend and lockdown effect showed implications on future policymaking toward improving local and regional air quality as well.


Assuntos
Poluentes Atmosféricos , COVID-19 , Humanos , Poluentes Atmosféricos/análise , Monitoramento Ambiental , Carbono/análise , Controle de Doenças Transmissíveis , Aerossóis e Gotículas Respiratórios , Fuligem/análise , Combustíveis Fósseis , Estações do Ano
10.
IEEE Trans Neural Netw Learn Syst ; 33(11): 6584-6598, 2022 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-34101599

RESUMO

In reinforcement learning (RL), function approximation errors are known to easily lead to the Q -value overestimations, thus greatly reducing policy performance. This article presents a distributional soft actor-critic (DSAC) algorithm, which is an off-policy RL method for continuous control setting, to improve the policy performance by mitigating Q -value overestimations. We first discover in theory that learning a distribution function of state-action returns can effectively mitigate Q -value overestimations because it is capable of adaptively adjusting the update step size of the Q -value function. Then, a distributional soft policy iteration (DSPI) framework is developed by embedding the return distribution function into maximum entropy RL. Finally, we present a deep off-policy actor-critic variant of DSPI, called DSAC, which directly learns a continuous return distribution by keeping the variance of the state-action returns within a reasonable range to address exploding and vanishing gradient problems. We evaluate DSAC on the suite of MuJoCo continuous control tasks, achieving the state-of-the-art performance.

11.
Sci Total Environ ; 780: 146249, 2021 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-34030329

RESUMO

This work reports new kinetic and mechanistic information on the atmospheric chemistry of ketones. Both absolute and relative rate methods were used to determine the rate constants for OH reactions with 2-methyl-3-pentanone (2M3P), 3-methyl-2-pentanone (3M2P) and 4-methyl-2-pentanone (4M2P), three widely used compounds in the industry. This work constitutes the first temperature dependence study of the reactions of OH with 2M3P and 3M2P. The following rate constants values are recommended at 298 K (in 10-12 cm3 molecule-1 s-1): kOH+2M3P = 3.49 ± 0.5; kOH+3M2P = 6.02 ± 0.14 and kOH+4M2P = 11.02 ± 0.42. The following Arrhenius expressions (in units of cm3 molecule-1 s-1) adequately describe the measured rate constants for OH reactions with 2M3P and 3M2P in the temperature range 263-373 K: k2M3P = (2.33 ± 0.06) × 10-12 exp((127.4 ± 18.6)/T) and k3M2P = (1.05 ± 0.14) × 10-12 exp((537 ± 41)/T). Products studies from the reactions of OH with the investigated ketones were conducted in a 7.3 m3 simulation chamber using PTR-ToF-MS, UHPLC-MS and GC-MS. A series of short chain carbonyl compounds including formaldehyde, acetone, acetaldehyde, 2-butanone and 2-methypropanal were observed as products. Combining the yields of carbonyls measured with those estimated from the SAR method, we propose various mechanistic degradation schemes of the investigated ketones initiated by reaction with OH radicals.

12.
Sci Total Environ ; 749: 141406, 2020 Dec 20.
Artigo em Inglês | MEDLINE | ID: mdl-32818857

RESUMO

Phytohormones emitted into the atmosphere perform many functions relating to the defence, pollination and competitiveness of plants. To be effective, their atmospheric lifetimes must be sufficient that these signals can be delivered to their numerous recipients. We investigate the atmospheric loss processes for methyl salicylate (MeSA), a widely emitted plant volatile. Simulation chambers were used to determine gas-phase reaction rates with OH, NO3, Cl and O3; photolysis rates; and deposition rates of gas-phase MeSA onto organic aerosols. Room temperature rate coefficients are determined (in units of cm3 molecule-1 s-1) to be (3.20 ± 0.46) × 10-12, (4.19 ± 0.92) × 10-15, (1.65 ± 0.44) × 10-12 and (3.33 ± 2.01) × 10-19 for the reactions with OH, NO3, Cl and O3 respectively. Photolysis is negligible in the actinic range, despite having a large reported near-UV chromophore. Conversely, aerosol uptake can be competitive with oxidation under humid conditions, suggesting that this compound has a high affinity for hydrated surfaces. A total lifetime of gas-phase MeSA of 1-4 days was estimated based on all these loss processes. The competing sinks of MeSA demonstrate the need to assess lifetimes of semiochemicals holistically, and we gain understanding of how atmospheric sinks influence natural communication channels within complex multitrophic interactions. This approach can be extended to other compounds that play vital roles in ecosystems, such as insect pheromones, which may be similarly affected during atmospheric transport.

13.
Environ Sci Technol ; 54(18): 11048-11057, 2020 09 15.
Artigo em Inglês | MEDLINE | ID: mdl-32808764

RESUMO

Nitrous acid (HONO) is a major precursor of tropospheric hydroxyl radical (OH) that accelerates the formation of secondary pollutants. The HONO sources, however, are not well understood, especially in polluted areas. Based on a comprehensive winter field campaign conducted at a rural site of the North China Plain, a box model (MCM v3.3.1) was used to simulate the daytime HONO budget and nitrate formation. We found that HONO photolysis acted as the dominant source for primary OH with a contribution of more than 92%. The observed daytime HONO could be well explained by the known sources in the model. The heterogeneous conversion of NO2 on ground surfaces and the homogeneous reaction of NO with OH were the dominant HONO sources with contributions of more than 36 and 34% to daytime HONO, respectively. The contribution from the photolysis of particle nitrate and the reactions of NO2 on aerosol surfaces was found to be negligible in clean periods (2%) and slightly higher during polluted periods (8%). The relatively high OH levels due to fast HONO photolysis at the rural site remarkably accelerated gas-phase reactions, resulting in the fast formation of nitrate as well as other secondary pollutants in the daytime.


Assuntos
Nitratos , Ácido Nitroso , Aerossóis , China , Radical Hidroxila , Ácido Nitroso/análise
14.
J Environ Sci (China) ; 95: 111-120, 2020 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-32653170

RESUMO

Rate coefficients for the reaction of NO3 radicals with 6 unsaturated volatile organic compounds (VOCs) in a 7300 L simulation chamber at ambient temperature and pressure have been determined by the relative rate method. The resulting rate coefficients were determined for isoprene, 2-carene, 3-carene, methyl vinyl ketone (MVK), methacrolein (MACR) and crotonaldehyde (CA), as (6.6 ± 0.8) × 10-13, (1.8 ± 0.6) × 10-11, (8.7 ± 0.5) × 10-12, (1.24 ± 1.04) × 10-16, (3.3 ± 0.9) × 10-15 and (5.7 ± 1.2) × 10-15 cm3/(molecule•sec), respectively. The experiments indicate that NO3 radical reactions with all the studied unsaturated VOCs proceed through addition to the olefinic bond, however, it indicates that the introduction of a carbonyl group into unsaturated VOCs can deactivate the neighboring olefinic bond towards reaction with the NO3 radical, which is to be expected since the presence of these electron-withdrawing substituents will reduce the electron density in the π orbitals of the alkenes, and will therefore reduce the rate coefficient of these electrophilic addition reactions. In addition, we investigated the product formation from the reactions of 2-carene and 3-carene with the NO3 radical. Qualitative identification of an epoxide (C10H16OH+), caronaldehyde (C10H16O2H+) and nitrooxy-ketone (C10H16O4NH+) was achieved using a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) and a reaction mechanism is proposed.


Assuntos
Poluentes Atmosféricos , Compostos Orgânicos Voláteis , Cinética
15.
J Environ Sci (China) ; 95: 155-164, 2020 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-32653175

RESUMO

The heterogeneous degradation of nitrogen dioxide (NO2) on five samples of natural Icelandic volcanic particles has been investigated. Laboratory experiments were carried out under simulated atmospheric conditions using a coated wall flow tube (CWFT). The CWFT reactor was coupled to a blue light nitrogen oxides analyzer (NOx analyzer), and a long path absorption photometer (LOPAP) to monitor in real time the concentrations of NO2, NO and HONO, respectively. Under dark and ambient relative humidity conditions, the steady state uptake coefficients of NO2 varied significantly between the volcanic samples probably due to differences in magma composition and morphological variation related with the density of surface OH groups. The irradiation of the surface with simulated sunlight enhanced the uptake coefficients by a factor of three indicating that photo-induced processes on the surface of the dust occur. Furthermore, the product yields of NO and HONO were determined under both dark and simulated sunlight conditions. The relative humidity was found to influence the distribution of gaseous products, promoting the formation of gaseous HONO. A detailed reaction mechanism is proposed that supports our experimental observations. Regarding the atmospheric implications, our results suggest that the NO2 degradation on volcanic particles and the corresponding formation of HONO is expected to be significant during volcanic dust storms or after a volcanic eruption.


Assuntos
Atmosfera , Ácido Nitroso , Poeira , Dióxido de Nitrogênio , Luz Solar
16.
Phys Chem Chem Phys ; 21(44): 24592-24600, 2019 Nov 28.
Artigo em Inglês | MEDLINE | ID: mdl-31665197

RESUMO

The rate coefficient for the possible reaction of OH radical with N2O was determined to be k1 < 1 × 10-17 cm3 molecule-1 s-1 between 253 and 372 K using pulsed laser photolysis to generate OH radicals and pulsed laser induced fluorescence to detect them. The rate coefficient for the reaction of NO3 radical with N2O was measured to be k2 < 5 × 10-20 cm3 molecule-1 s-1 at 298 K using a direct method that involves a large reaction chamber equipped with cavity ring down spectroscopic detection of NO3 and N2O5. Various tests were carried out ensure the accuracy of our measurements. Based on our measured upper limits, we suggest that these two reactions alter the atmospheric lifetime of N2O of ∼120 years by less than 4%.

17.
Environ Sci Technol ; 53(15): 8862-8871, 2019 Aug 06.
Artigo em Inglês | MEDLINE | ID: mdl-31291100

RESUMO

Perfluoroketones, used as replacement to halons and CFCs, are excluded from the Montreal Protocol because they are considered as nonozone depleting substances. However, their chemical structure makes them possible greenhouse gases if their atmospheric lifetimes are long enough. To assess that possibility, we investigated the photolysis of perfluoro-2-methyl-3-pentanone (PF-2M3P), and perfluoro-3-methyl-2-butanone (PF-3M2B) using outdoor atmospheric simulation chambers. In addition, the photolysis of a non fluorinated pentanone (2-methyl-3-pentanone, 2M3P) was studied. The results showed that photolysis is the dominant loss pathway of PF-2M3P and PF-3M2B in the troposphere whereas 2M3P is lost by both photolysis and gas phase reaction with atmospheric oxidants. The photolysis effective quantum yields of PF-2M3P, PF-3M2B, and 2M3P were estimated and some of the main products identified. The photolysis of PF-2M3P and PF-3M2B was found to have a minor impact on the atmospheric burden of fluorinated acids. The atmospheric lifetimes of PF-2M3P, PF-3M2B, and 2M3P were estimated to 3-11 days, ∼13 days, and 1-2 days, respectively. Combining the obtained data, it has been concluded that with 100-year time horizon global warming potentials (GWP100) equivalent to <0.21, ∼0.29, and ≤1.3 × 10-7 for PF-2M3P, PF-3M2B, and 2M3P, respectively, these compounds will have a negligible impact on global warming.


Assuntos
Butanonas , Pentanonas , Atmosfera , Aquecimento Global , Fotólise
18.
J Environ Sci (China) ; 71: 271-282, 2018 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-30195685

RESUMO

The rate constants for the Cl atom reaction with three branched ketones have been measured at 298±2K and 760Torr using the relative rate method in the absence of NO. The rate constants values obtained (in units of 10-10cm3/(molecule·sec)) are: k(2-methyl-3-pentanone)=1.07±0.26, k(3-methyl-2-pentanone)=1.21±0.26, and k(4-methyl-2-pentanone)=1.35±0.27. Combining the chemical kinetic data obtained by this study with those reported for other ketones, a revised Structure Activity Relationship (SAR) parameter and R group reactivity (kR) of R(O)R' and CHx (x=1, 2, 3) group reactivity (kCHx) toward Cl atoms were proposed. In addition, the products from the three reactions in the presence of NO were also identified and quantified by using PTR-ToF-MS and GC-FID, and the yields of the identified products are: acetone (39%±8%)+ethanal (78%±12%), 2-butanone (22%±2%)+ethanal (75%±10%)+propanal (14%±1%) and acetone (26%±3%)+2-methylpropanal (24%±2%), for Cl atoms reaction with 2-methyl-3-pentanone, 3-methyl-2-pentanone and 4-methyl-2-pentanone, respectively. Based on the obtained results, the reaction mechanisms of Cl atoms with these three ketones are proposed.


Assuntos
Cloro/química , Cetonas/química , Modelos Químicos , Aldeídos , Pressão Atmosférica , Cinética , Pentanonas , Temperatura
19.
Faraday Discuss ; 200: 289-311, 2017 08 24.
Artigo em Inglês | MEDLINE | ID: mdl-28581006

RESUMO

The rate constants for the ozonolysis of isoprene (ISO), methacrolein (MACR) and methyl vinyl ketone (MVK) have been measured using the newly built large volume atmospheric simulation chamber at CNRS-Orleans (France), HELIOS (Chambre de simulation atmosphérique à irradiation naturelle d'Orléans). The OH radical yields from the ozonolysis of isoprene, MACR and MVK have also been determined, as well as the gas phase stable products and their yields. The secondary organic aerosol yield for the ozonolysis of isoprene has been tentatively measured in the presence and absence of an OH radical scavenger. The measurements were performed under different experimental conditions with and without adding cyclohexane (cHX) as an OH radical scavenger. All experiments have been conducted at 760 torr of purified dry air (RH < 1%) and ambient temperature (T = 281-295 K). The data obtained are discussed and compared with those from the literature. The use of the HELIOS facility and its associated analytical equipment enables the derivation of kinetic parameters as well as mechanistic information under near realistic atmospheric conditions.

20.
J Thorac Dis ; 8(6): 1297-305, 2016 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-27293850

RESUMO

BACKGROUND: MicroRNAs (miRNAs) may play an important role in organ development, cell differentiation, apoptosis, proliferation, cell growth regulation and act as tumor suppressor genes or proto-oncogenes. Single nucleotide polymorphisms (SNPs) in miRNAs are considered to be genetic factors to influence the susceptibility to lung cancer (LC). Rs2910164 in miR-146a and rs11614913 in miR-196a2 are shown to be associated with increased/decreased LC risk. The aim of this meta-analysis was to systematically summarize the possible association. METHODS: The relevant articles were retrieved from several important databases. Studies were selected using specific inclusion and exclusion criteria. Odds ratios (ORs) and 95% confidence intervals (CIs) were calculated to assess the strength of association between miRNA polymorphism and susceptibility to LC. All analyses were performed using the Stata software. RESULTS: Seven studies were included in this meta-analysis. There were 3,225 cases and 3,268 controls for SNP rs2910164 and 2,794 cases and 2,840 controls for SNP rs11614913. The significant associations between SNP rs2910164 and LC risk were observed (CC vs. GG: OR =1.30, 95% CI: 1.13-1.50; CC + GC vs. GG: OR =1.15, 95% CI: 1.02-1.29; CC vs. GC + GG: OR =1.27, 95% CI: 1.13-1.42; C vs. G: OR =1.15, 95% CI: 1.08-1.24). SNP rs11614913 was found to be associated with LC risk in most genetic models (TC vs. TT: OR =1.16, 95% CI: 1.02-1.32; CC vs. TT: OR =1.24, 95% CI: 1.06-1.44; CC + TC vs. TT: OR =1.19, 95% CI: 1.06-1.34; C vs. T: OR =1.11, 95% CI: 1.03-1.20). In the subgroup analysis by ethnicity, genotyping method and control characteristics, significantly affected LC risks were also suggested. CONCLUSIONS: The rs2910164 in miR-146a and the rs11614913 in miR-196a2 are likely to be associated with LC risks.

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