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1.
Environ Int ; 186: 108632, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38583296

RESUMO

Plastic fragments are widely found in the soil profile of terrestrial ecosystems, forming plastic footprint and posing increasing threat to soil functionality and carbon (C) footprint. It is unclear how plastic footprint affects C cycling, and in particularly permanent C sequestration. Integrated field observations (including 13C labelling) were made using polyethylene and polylactic acid plastic fragments (low-, medium- and high-concentrations as intensifying footprint) landfilling in soil, to track C flow along soil-plant-atmosphere continuum (SPAC). The result indicated that increased plastic fragments substantially reduced photosynthetic C assimilation (p < 0.05), regardless of fragment degradability. Besides reducing C sink strength, relative intensity of C emission increased significantly, displaying elevated C source. Moreover, root C fixation declined significantly from 21.95 to 19.2 mg m-2, and simultaneously root length density, root weight density, specific root length and root diameter and surface area were clearly reduced. Similar trends were observed in the two types of plastic fragments (p > 0.05). Particularly, soil aggregate stability was significantly lowered as affected by plastic fragments, which accelerated the decomposition rate of newly sequestered C (p < 0.05). More importantly, net C rhizodeposition declined averagely from 39.77 to 29.41 mg m-2, which directly led to significant decline of permanent C sequestration in soil. Therefore, increasing plastic footprint considerably worsened C footprint regardless of polythene and biodegradable fragments. The findings unveiled the serious effects of plastic residues on permanent C sequestration across SPAC, implying that current C assessment methods clearly overlook plastic footprint and their global impact effects.


Assuntos
Pegada de Carbono , Plásticos , Solo , Solo/química , Carbono/análise , Atmosfera/química , Ciclo do Carbono , Ecossistema , Plantas , Sequestro de Carbono , Monitoramento Ambiental/métodos
2.
Nature ; 628(8009): 693, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38641727
3.
Methods Mol Biol ; 2787: 69-80, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38656482

RESUMO

This chapter presents a holistic and quantitative approach to the carbon cycle in plant systems biology. It includes (rapid) phenotyping and monitoring of physiological key interactions of plants with its respective soil and atmospheric environment (soil plant atmospheric continuum-SPAC). The approach aims at qualifying and quantifying key components of this microhabitat as influenced by a single plant or a local group of plants in order to contribute to a flux-based modelling approach. The toolset consists of plant biometry, gas exchange, metabolomics, ionomics, root exudate characterization as well as soil biological and physical-chemical characterization. The results are presented as a basic interaction and input-output model aka conceptual system model employing H. T. Odum-style plots based on empirical data.


Assuntos
Atmosfera , Plantas , Solo , Solo/química , Plantas/metabolismo , Atmosfera/química , Fenótipo , Modelos Biológicos , Ciclo do Carbono , Metabolômica/métodos , Raízes de Plantas/metabolismo , Ecossistema
4.
Environ Sci Technol ; 58(16): 6934-6944, 2024 Apr 23.
Artigo em Inglês | MEDLINE | ID: mdl-38651174

RESUMO

Stratospheric aerosol injection (SAI) is proposed as a means of reducing global warming and climate change impacts. Similar to aerosol enhancements produced by volcanic eruptions, introducing particles into the stratosphere would reflect sunlight and reduce the level of warming. However, uncertainties remain about the roles of nucleation mechanisms, ionized molecules, impurities (unevaporated residuals of injected precursors), and ambient conditions in the generation of SAI particles optimally sized to reflect sunlight. Here, we use a kinetic ion-mediated and homogeneous nucleation model to study the formation of H2SO4 particles in aircraft exhaust plumes with direct injection of H2SO4 vapor. We find that under the conditions that produce particles of desired sizes (diameter ∼200-300 nm), nucleation occurs in the nascent (t < 0.01 s), hot (T = 360-445 K), and dry (RH = 0.01-0.1%) plume and is predominantly unary. Nucleation on chemiions occurs first, followed by neutral new particle formation, which converts most of the injected H2SO4 vapor to particles. Coagulation in the aging and diluting plumes governs the subsequent evolution to a narrow (σg = 1.3) particle size distribution. Scavenging by exhaust soot is negligible, but scavenging by acid impurities or incomplete H2SO4 evaporation in the hot exhaust plume and enhanced background aerosols can matter. This research highlights the need to obtain laboratory and/or real-world experiment data to verify the model prediction.


Assuntos
Aerossóis , Aeronaves , Tamanho da Partícula , Emissões de Veículos , Atmosfera/química , Poluentes Atmosféricos/química
5.
Astrobiology ; 24(S1): S76-S106, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38498817

RESUMO

Within the first billion years of Earth's history, the planet transformed from a hot, barren, and inhospitable landscape to an environment conducive to the emergence and persistence of life. This chapter will review the state of knowledge concerning early Earth's (Hadean/Eoarchean) geochemical environment, including the origin and composition of the planet's moon, crust, oceans, atmosphere, and organic content. It will also discuss abiotic geochemical cycling of the CHONPS elements and how these species could have been converted to biologically relevant building blocks, polymers, and chemical networks. Proposed environments for abiogenesis events are also described and evaluated. An understanding of the geochemical processes under which life may have emerged can better inform our assessment of the habitability of other worlds, the potential complexity that abiotic chemistry can achieve (which has implications for putative biosignatures), and the possibility for biochemistries that are vastly different from those on Earth.


Assuntos
Planeta Terra , Planetas , Lua , Atmosfera/química , Oceanos e Mares
6.
Astrobiology ; 24(S1): S57-S75, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38498821

RESUMO

The materials that form the diverse chemicals and structures on Earth-from mountains to oceans and biological organisms-all originated in a universe dominated by hydrogen and helium. Over billions of years, the composition and structure of the galaxies and stars evolved, and the elements of life, CHONPS, were formed through nucleosynthesis in stellar cores. Climactic events such as supernovae and stellar collisions produced heavier elements and spread them throughout the cosmos, often to be incorporated into new, more metal-rich stars. Stars typically form in molecular clouds containing small amounts of dust through the collapse of a high-density core. The surrounding nebular material is then pulled into a protoplanetary disk, from which planets, moons, asteroids, and comets eventually accrete. During the accretion of planetary systems, turbulent mixing can expose matter to a variety of different thermal and radiative environments. Chemical and physical changes in planetary system materials occur before and throughout the process of accretion, though many factors such as distance from the star, impact history, and level of heating experienced combine to ultimately determine the final geophysical characteristics. In Earth's planetary system, called the Solar System, after the orbits of the planets had settled into their current configuration, large impacts became rare, and the composition of and relative positions of objects became largely fixed. Further evolution of the respective chemical and physical environments of the planets-geosphere, hydrosphere, and atmosphere-then became dependent on their local geochemistry, their atmospheric interactions with solar radiation, and smaller asteroid impacts. On Earth, the presence of land, air, and water, along with an abundance of important geophysical and geochemical phenomena, led to a habitable planet where conditions were right for life to thrive.


Assuntos
Planetas , Sistema Solar , Planeta Terra , Atmosfera/química , Planetas Menores , Evolução Planetária , Meio Ambiente Extraterreno/química
7.
Astrobiology ; 24(4): 343-370, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38452176

RESUMO

Long-standing unexplained Venus atmosphere observations and chemical anomalies point to unknown chemistry but also leave room for the possibility of life. The unexplained observations include several gases out of thermodynamic equilibrium (e.g., tens of ppm O2, the possible presence of PH3 and NH3, SO2 and H2O vertical abundance profiles), an unknown composition of large, lower cloud particles, and the "unknown absorber(s)." Here we first review relevant properties of the venusian atmosphere and then describe the atmospheric chemical anomalies and how they motivate future astrobiology missions to Venus.


Assuntos
Vênus , Exobiologia , Meio Ambiente Extraterreno , Gases/química , Atmosfera/química
8.
Chemosphere ; 354: 141630, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38462185

RESUMO

Aminoamides are formed in the atmospheric environments by the auto-oxidation of the parent diamines. In this work, the oxidation chemistry of diamine (1,3-Diaminopropane, Dap) to the amino amide (3- aminopropanamide, 3-APA) and its new particle formation potential with small atmospheric molecules such as NH3 (A), H2O (W) and H2SO4 (SA) are theoretically investigated using the M062X/6-311++G** theory. The bimolecular rate coefficient of the ·OH initiated H-atom abstraction is computed to be 1.01 × 10-11 cm3 molecule-1 s-1. Further reaction of the peroxy radical intermediate indicates that the pathway involving γ H- shift of the initially formed radical intermediates to be more favourable on kinetic grounds with the effective bimolecular rate coefficient of 3.87 × 10-14 cm3 molecule-1s-1. The thermodynamic barrier associated with the H-shifts involved in this pathway is in the range of 13-20 kcal/mol. The cluster formation of APA with SA is more favourable than the clusters with W and A, wherein the free energy of formation of (APA)(SA) and (APA)(SA)2 are -11.3 and -22.6 kcal/mol, respectively. However, the feasibility of cluster formation with W and A increases with the altitude and becomes spontaneous in the case of water at an altitude of 12 km. The present work indicates that aminoamides like 3-APA can participate in the initial stages of new particle formation events by forming clusters with SA molecules. The scattering parameters and topological analysis of different (Amide)(SA) clusters indicate more scattering properties for the (APA)(SA) cluster, which has an adverse effect on the atmosphere. Furthermore, topological analysis indicates that H-bond formation is more prominent in the (APA)(SA) cluster.


Assuntos
Atmosfera , Termodinâmica , Atmosfera/química , Oxirredução
9.
Environ Sci Process Impacts ; 26(4): 734-750, 2024 Apr 24.
Artigo em Inglês | MEDLINE | ID: mdl-38426396

RESUMO

To give a comprehensive account of the environmental acceptability of 1,1,2,3-tetrafluoropropene (CF2CF-CH2F) in the troposphere, we have examined the oxidation reaction pathways and kinetics of CF2CF-CH2F initiated by Cl-atoms using the second-order Møller-Plesset perturbation (MP2) theory along with the 6-31+G(d,p) basis set. We also performed single-point energy calculations to further refine the energies at the CCSD(T) level along with the basis sets 6-31+G(d,p) and 6-311++G(d,p). The estimation of the relative energies and thermodynamic parameters of the CF2CF-CH2F + Cl reaction clearly shows that Cl-atom addition reaction pathways are more dominant compared to H-abstraction reaction pathways. The value of the rate coefficient for each reaction channel is calculated using the conventional transition state theory (TST) over the temperature range of 200-1000 K at 1 atm. The estimated overall rate coefficients for the title reaction are found to be 1.10 × 10-12, 1.21 × 10-10, and 1.13 × 10-8 cm3 per molecule per s via the respective calculation methods viz. MP2/6-31+G(d,p), CCSD(T)//MP2/6-31+G(d,p), and CCSD(T)/6-311++G(d,p)//MP2/6-31+G(d,p), at 298.15 K. Moreover, the calculated rate coefficients and percentage branching ratio values suggest that the Cl-atom addition reaction at the ß-carbon atom is more preferable to that of the α-carbon addition to CF2CF-CH2F. Based on the rate coefficient values calculated by the three different methods, the atmospheric lifetime for the title reaction at 298.15 K is estimated. The radiative efficiency (RE) and Global Warming Potential (GWP) results of the title molecule show that its GWP would be negligible. Further, we have explored the degradation of its product radicals in the presence of O2 and NO. From the degradation results, we have found that CF2(Cl)COF, FCOCH2F, FCFO and FCOCl are formed as stable end products along with various radicals such as ˙CF2Cl and ˙CH2F. Therefore, these findings of kinetic and mechanistic data can be applied to the development and implementation of a novel CFC replacement.


Assuntos
Modelos Químicos , Oxirredução , Cinética , Poluentes Atmosféricos/química , Poluentes Atmosféricos/análise , Fluorocarbonos/química , Termodinâmica , Atmosfera/química , Hidrocarbonetos Fluorados/química
10.
J Environ Radioact ; 275: 107416, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38520991

RESUMO

In September 2017, numerous measurement stations recorded large surface concentrations of Ru106 in Europe. This event was well recorded by various monitoring stations worldwide and offer a valuable framework to compare the modelling strategies deployed to quickly evaluate where the plume goes and with what concentrations. In general, the source and its intensity are not known and hypotheses have to be done. Models have to be fast and accurate: Lagrangian and Eulerian are often used but rarely compared. In this study, the FLEXPART Lagrangian model and the WRF-CHIMERE Eulerian models are used to simulate the emissions, transport and deposition of this source of Ru106. First, it is shown that the hypothesis of location, timing and intensity of the source is realistic, by comparison to surface measurements. Second, sensitivity analysis performed with the Eulerian model and several transport scheme showed that this model may provide better results than the Lagrangian one. It opens the door to further development, including chemistry and mixing with other pollutants during these specific events.


Assuntos
Poluentes Radioativos do Ar , Atmosfera , Monitoramento de Radiação , Monitoramento de Radiação/métodos , Poluentes Radioativos do Ar/análise , Atmosfera/química , Rutênio , Modelos Teóricos , Modelos Químicos , Europa (Continente)
11.
Environ Sci Technol ; 58(16): 7099-7112, 2024 Apr 23.
Artigo em Inglês | MEDLINE | ID: mdl-38536960

RESUMO

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


Assuntos
Aerossóis , Poluentes Atmosféricos , Atmosfera , China , Atmosfera/química , Poluentes Atmosféricos/análise , Compostos Orgânicos/análise , Monitoramento Ambiental , Nitrogênio/análise
12.
Ann Work Expo Health ; 68(4): 420-426, 2024 Apr 22.
Artigo em Inglês | MEDLINE | ID: mdl-38438299

RESUMO

Since the manufacture, import, and use of asbestos products have been completely abolished in Japan, the main cause of asbestos emissions into the atmosphere is the demolition and removal of buildings built with asbestos-containing materials. To detect and correct asbestos emissions from inappropriate demolition and removal operations at an early stage, a rapid method to measure atmospheric asbestos fibers is required. The current rapid measurement method is a combination of short-term atmospheric sampling and phase-contrast microscopy counting. However, visual counting takes a considerable amount of time and is not sufficiently fast. Using artificial intelligence (AI) to analyze microscope images to detect fibers may greatly reduce the time required for counting. Therefore, in this study, we investigated the use of AI image analysis for detecting fibers in phase-contrast microscope images. A series of simulated atmospheric samples prepared from standard samples of amosite and chrysotile were observed using a phase-contrast microscope. Images were captured, and training datasets were created from the counting results of expert analysts. We adopted 2 types of AI models-an instance segmentation model, namely the mask region-based convolutional neural network (Mask R-CNN), and a semantic segmentation model, namely the multi-level aggregation network (MA-Net)-that were trained to detect asbestos fibers. The accuracy of fiber detection achieved with the Mask R-CNN model was 57% for recall and 46% for precision, whereas the accuracy achieved with the MA-Net model was 95% for recall and 91% for precision. Therefore, satisfactory results were obtained with the MA-Net model. The time required for fiber detection was less than 1 s per image in both AI models, which was faster than the time required for counting by an expert analyst.


Assuntos
Inteligência Artificial , Amianto , Microscopia de Contraste de Fase , Microscopia de Contraste de Fase/métodos , Amianto/análise , Monitoramento Ambiental/métodos , Humanos , Japão , Atmosfera/química , Redes Neurais de Computação , Asbestos Serpentinas/análise
13.
Environ Sci Process Impacts ; 26(4): 751-764, 2024 Apr 24.
Artigo em Inglês | MEDLINE | ID: mdl-38465670

RESUMO

In this work, we have investigated the mechanism, thermochemistry and kinetics of the reaction of syn-cis-CH2RzCRyCO+O- (where Rz, Ry = H, CH3-) unsaturated Criegee intermediates (CIs) with CF3COOH using quantum chemical methods. The rate coefficients for the barrierless reactions were calculated using variable reaction coordinate variational transition state theory (VRC-VTST). For the syn-cis-CH2RzCRyCO+O- conformation in which conjugated CC and CO double bonds are aligned with each other, we propose a new pathway for the unidirectional addition of an OC-OH molecule (CF3COOH) to the CC double bond of syn-cis-CH2RzCRyCO+O-. The rate coefficient for the 1,4-CC addition reaction at 298 K is ∼10-10 to 10-11 cm3 s-1, resulting in the formation of CF3C(O)OCH2CRzRyCOOH trifluoroacetate alkyl allyl hydroperoxide (TFAAAH) as a new transitory adduct. It can act as a precursor for the formation of secondary organic aerosols (SOAs). This novel TFAAAH hydroperoxide was identified through a detailed quantum chemical study of the 1,4-addition mechanism and will provide new insights into the significance of the 1,4-addition reaction of unsaturated Cls with trace tropospheric gases on -CRzCH2 vinyl carbon atoms.


Assuntos
Atmosfera , Cinética , Atmosfera/química , Poluentes Atmosféricos/química , Modelos Químicos , Aerossóis/química
14.
Astrobiology ; 24(4): 386-396, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38498680

RESUMO

Scientists have long speculated about the potential habitability of Venus, not at the 700K surface, but in the cloud layers located at 48-60 km altitudes, where temperatures match those found on Earth's surface. However, the prevailing belief has been that Venus' clouds cannot support life due to the cloud chemical composition of concentrated sulfuric acid-a highly aggressive solvent. In this work, we study 20 biogenic amino acids at the range of Venus' cloud sulfuric acid concentrations (81% and 98% w/w, the rest water) and temperatures. We find 19 of the biogenic amino acids we tested are either unreactive (13 in 98% w/w and 12 in 81% w/w) or chemically modified in the side chain only, after 4 weeks. Our major finding, therefore, is that the amino acid backbone remains intact in concentrated sulfuric acid. These findings significantly broaden the range of biologically relevant molecules that could be components of a biochemistry based on a concentrated sulfuric acid solvent.


Assuntos
Vênus , Aminoácidos , Atmosfera/química , Solventes , Ácidos Sulfúricos/química
15.
J Chem Ecol ; 50(3-4): 129-142, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38195852

RESUMO

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


Assuntos
Monoterpenos Acíclicos , Alcenos , Cetonas , Ozônio , Sesquiterpenos , Compostos Orgânicos Voláteis , Ozônio/química , Compostos Orgânicos Voláteis/química , Compostos Orgânicos Voláteis/metabolismo , Alcenos/química , Sesquiterpenos/química , Sesquiterpenos/metabolismo , Atmosfera/química , Monoterpenos/química , Monoterpenos/metabolismo , Monoterpenos Cicloexânicos/química , Cromatografia Gasosa-Espectrometria de Massas , Isomerismo , Poluentes Atmosféricos/química , Poluentes Atmosféricos/análise
16.
Environ Pollut ; 344: 123351, 2024 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-38272169

RESUMO

Pesticides in the atmosphere can exist in both gaseous and particulate phases due to their semi-volatile properties. They can undergo degradation when exposed to atmospheric oxidants like ozone and hydroxyl radicals. The majority of studies on the atmospheric reactivity of pesticides study them in combination, without considering potential mixture effects that could induce uncertainties in the results. Therefore, this study aims to address this gap, through laboratory studies using a flow reactor, and by evaluating the degradation kinetics of pendimethalin mixed with folpet, tebuconazole, and S-metolachlor, which were simultaneously adsorbed on hydrophobic silica particles that mimic atmospheric aerosols. The comparison with other mixtures, including pendimethalin, from the literature has shown similar reactivity with ozone and hydroxyl radicals, indicating that the degradation kinetics of pesticides is independent of the mixture. Moreover, the degradation rates of the four pesticides under study indicate that they are not or slightly degraded by ozone, with half-lives ranging from 29 days to over 800 days. In contrast, when exposed to hydroxyl radicals, tebuconazole exhibited the fastest reactivity, with a half-life of 4 days, while pendimethalin had a half-life of 17 days.


Assuntos
Ozônio , Praguicidas , Praguicidas/química , Ozônio/química , Compostos de Anilina , Oxidantes/química , Radical Hidroxila/química , Atmosfera/química
17.
Chemosphere ; 352: 141243, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38246501

RESUMO

As volatile organic compounds (VOCs), pentamethylbenzene (5-PeMB) and hexamethylbenzene (6-HeMB) are found widely in petroleum and coal tar. Through combustion and industrial generation entering into the atmosphere, they can produce photochemical smog and secondary organic aerosols (SOA) to endanger human health and ecoenvironment eventually. In order to reveal their environmental chemistry, the OH-initiated degradation mechanisms of 5-PeMB and 6-HeMB were studied based on density functional theory (DFT). Result showed that addition pathways were the most favorable with energy barriers of 20.7 and 25.3 kJ/mol, respectively, in the two reactions. The degradation rate constants at 298 K were calculated to be 2.69 × 10-10 and 1.28 × 10-10 cm3 molecule-1 ·s-1, coinciding with the available experimental values. In the presence of OH radicals, the atmospheric lifetimes were estimated to be 2.17 and 2.78 h, respectively, for 5-PeMB and 6-HeMB. According to the quantitative structure-activity relationship (QSAR) model, the toxicity during the degradation process is decreased to fish, daphnia, and green algae.


Assuntos
Benzeno , Modelos Teóricos , Humanos , Atmosfera/química , Radical Hidroxila/química , Cinética
18.
Sci Total Environ ; 912: 168478, 2024 Feb 20.
Artigo em Inglês | MEDLINE | ID: mdl-37967625

RESUMO

Airborne microorganisms and biological matter (bioaerosols) play a key role in global biogeochemical cycling, human and crop health trends, and climate patterns. Their presence in the atmosphere is controlled by three main stages: emission, transport, and deposition. Aerial survival rates of bioaerosols are increased through adaptations such as ultra-violet radiation and desiccation resistance or association with particulate matter. Current research into modern concerns such as climate change, global gene transfer, and pathogenicity often neglects to consider atmospheric involvement. This comprehensive review outlines the transpiring of bioaerosols across taxa in the atmosphere, with significant focus on their interactions with environmental elements including abiotic factors (e.g., atmospheric composition, water cycle, and pollution) and events (e.g., dust storms, hurricanes, and wildfires). The aim of this review is to increase understanding and shed light on needed research regarding the interplay between global atmospheric phenomena and the aeromicrobiome. The abundantly documented bacteria and fungi are discussed in context of their cycling and human health impacts. Gaps in knowledge regarding airborne viral community, the challenges and importance of studying their composition, concentrations and survival in the air are addressed, along with understudied plant pathogenic oomycetes, and archaea cycling. Key methodologies in sampling, collection, and processing are described to provide an up-to-date picture of ameliorations in the field. We propose optimization to microbiological methods, commonly used in soil and water analysis, that adjust them to the context of aerobiology, along with other directions towards novel and necessary advancements. This review offers new perspectives into aeromicrobiology and calls for advancements in global-scale bioremediation, insights into ecology, climate change impacts, and pathogenicity transmittance.


Assuntos
Bactérias , Material Particulado , Humanos , Material Particulado/análise , Bactérias/genética , Monitoramento Ambiental , Fungos/genética , Atmosfera/química , Aerossóis/análise , Microbiologia do Ar
19.
J Mol Graph Model ; 126: 108651, 2024 01.
Artigo em Inglês | MEDLINE | ID: mdl-37865033

RESUMO

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


Assuntos
Atmosfera , Radical Hidroxila , Isomerismo , Atmosfera/química , Oxirredução , Radical Hidroxila/química , Cinética
20.
Environ Sci Technol ; 58(2): 1223-1235, 2024 Jan 16.
Artigo em Inglês | MEDLINE | ID: mdl-38117938

RESUMO

Nanoparticle growth influences atmospheric particles' climatic effects, and it is largely driven by low-volatility organic vapors. However, the magnitude and mechanism of organics' contribution to nanoparticle growth in polluted environments remain unclear because current observations and models cannot capture organics across full volatility ranges or track their formation chemistry. Here, we develop a mechanistic model that characterizes the full volatility spectrum of organic vapors and their contributions to nanoparticle growth by coupling advanced organic oxidation modeling and kinetic gas-particle partitioning. The model is applied to Nanjing, a typical polluted city, and it effectively captures the volatility distribution of low-volatility organics (with saturation vapor concentrations <0.3 µg/m3), thus accurately reproducing growth rates (GRs), with a 4.91% normalized mean bias. Simulations indicate that as particles grow from 4 to 40 nm, the relative fractions of GRs attributable to organics increase from 59 to 86%, with the remaining contribution from H2SO4 and its clusters. Aromatics contribute much to condensable organic vapors (∼37%), especially low-volatility vapors (∼61%), thus contributing the most to GRs (32-46%) as 4-40 nm particles grow. Alkanes also contribute 19-35% of GRs, while biogenic volatile organic compounds contribute minimally (<13%). Our model helps assess the climatic impacts of particles and predict future changes.


Assuntos
Compostos Orgânicos Voláteis , Atmosfera/química , Gases , Alcanos , Oxirredução , Aerossóis
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