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1.
Environ Sci Technol ; 56(22): 15328-15336, 2022 11 15.
Artigo em Inglês | MEDLINE | ID: mdl-36215417

RESUMO

Secondary organic aerosol (SOA) is a significant component of atmospheric fine particulate matter. Mobile sources have historically been a major source of SOA precursors in urban environments, but decades of regulations have reduced their emissions. Less regulated sources, such as volatile chemical products (VCPs), are of growing importance. We analyzed ambient and emissions data to assess the contribution of mobile sources to SOA formation in Los Angeles during the period of 2009-2019. During this period, air quality in the Los Angeles region has improved, but organic aerosol (OA) concentrations did not decrease as much as primary pollutants. This appears to be largely due to SOA, whose mass fraction in OA increased over this period. In 2010, about half of the freshly formed SOA measured in Pasadena, CA appears to be formed from hydrocarbon (non-oxygenated) precursors. Chemical mass balance analysis indicates that these hydrocarbon SOA precursors (including intermediate volatility organic compounds) can largely be explained by emissions from mobile sources in 2010. Our analysis indicates that continued reduction in emissions from mobile sources should lead to additional significant decreases in atmospheric SOA and PM2.5 mass in the Los Angeles region.


Assuntos
Poluentes Atmosféricos , Poluição do Ar , Material Particulado/análise , Poluentes Atmosféricos/análise , Los Angeles , Aerossóis/química , Poluição do Ar/análise , Emissões de Veículos/análise , Monitoramento Ambiental
2.
J Environ Manage ; 302(Pt A): 114002, 2022 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-34731707

RESUMO

In this work, the iron-containing smectite nontronite (NNT) was artificially prepared by hydrothermal process and used as a heterogeneous catalyst to activate bisulfite (BS) for degradation of tetracycline (TC). Two NNT samples with different iron content (NNT1 and NNT2) were characterized by XRD, FTIR, XPS and SEM-EDS analysis. Under dark condition, the TC removal rates of NNT1/BS and NNT2/BS reached about 91.7% and 95.5% respectively at 60 min. Due to the heterogeneous catalysis of structural Fe(III), the NNT catalysts showed great catalytic activity and low iron leaching at the pH range 3.0-7.5. In addition, NNT particles were also stable and reusable in activating BS for TC removal. According to the EPR and radical quenching experiments, it could be proved that the precursor radical •SO3- was first generated in NNT/BS system, then •SO4- and •OH were the active species that played a role in TC degradation. The synthetic NNT clay is a promising Fe-based catalyst for treatment of TC wastewater thanks to its high activity, good stability and effective reusability.


Assuntos
Compostos Férricos , Peróxido de Hidrogênio , Catálise , Sulfitos , Tetraciclina
3.
Langmuir ; 36(36): 10860-10867, 2020 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-32813528

RESUMO

It is widely acknowledged that clay minerals have detrimental effects on the process of flotation, but the mechanisms involved are still not fully understood. In this work, the effects of montmorillonite, kaolinite, and illite on pyrite flotation were investigated from the perspective of various structures of clay minerals. Flotation tests suggested that the detrimental effect of clay minerals on the flotation of pyrite increased as follows: montmorillonite > kaolinite > illite. With the help of rheology measurements, it was found that montmorillonite significantly increased pulp viscosity, which in turn substantially reduced pyrite recovery and grade. Scanning electron microscopy (SEM) images suggested that montmorillonite formed the "house-of-cards" structure by edge-to-edge and edge-to-face contact, while kaolinite and illite platelets were associated mainly in the face-to-face mode. In addition, it was clearly observed by SEM-energy dispersive spectrometry that montmorillonite and kaolinite coat on the pyrite surfaces, which would lower the surface hydrophobicity of pyrite. Kaolinite covered much larger area of pyrite surface than montmorillonite owing to the positive charge occurring at the exposed aluminum-oxygen octahedral sheet of kaolinite. Although illite has a similar 2:1 structure to montmorillonite, it showed little or no effect on pyrite flotation, which was attributed to its poor swelling nature. These findings shed light on the root cause of the adverse effect of clay minerals on pyrite flotation and are expected to provide theoretical guidance for mitigating the negative effects on flotation caused by clays.

4.
Proc Natl Acad Sci U S A ; 114(27): 6984-6989, 2017 07 03.
Artigo em Inglês | MEDLINE | ID: mdl-28630318

RESUMO

On-road gasoline vehicles are a major source of secondary organic aerosol (SOA) in urban areas. We investigated SOA formation by oxidizing dilute, ambient-level exhaust concentrations from a fleet of on-road gasoline vehicles in a smog chamber. We measured less SOA formation from newer vehicles meeting more stringent emissions standards. This suggests that the natural replacement of older vehicles with newer ones that meet more stringent emissions standards should reduce SOA levels in urban environments. However, SOA production depends on both precursor concentrations (emissions) and atmospheric chemistry (SOA yields). We found a strongly nonlinear relationship between SOA formation and the ratio of nonmethane organic gas to oxides of nitrogen (NOx) (NMOG:NOx), which affects the fate of peroxy radicals. For example, changing the NMOG:NOx from 4 to 10 ppbC/ppbNOx increased the SOA yield from dilute gasoline vehicle exhaust by a factor of 8. We investigated the implications of this relationship for the Los Angeles area. Although organic gas emissions from gasoline vehicles in Los Angeles are expected to fall by almost 80% over the next two decades, we predict no reduction in SOA production from these emissions due to the effects of rising NMOG:NOx on SOA yields. This highlights the importance of integrated emission control policies for NOx and organic gases.

5.
Langmuir ; 35(6): 2368-2374, 2019 Feb 12.
Artigo em Inglês | MEDLINE | ID: mdl-30645941

RESUMO

The exfoliation of layered montmorillonite (MMT) into mono- or few-layer sheets is of significance for both fundamental studies and potential applications. In this report, exfoliated MMT nanosheets with different aspect ratios have been prepared via a new freezing/thawing-ultrasonic exfoliation method. Freezing/thawing processing can exfoliate MMT tactoids with low efficiency while virtually retaining the original lateral size. The ultrasonic method has better exfoliation efficiency but tends to damage the nanosheets. By combining them and reasonably controlling the cycle index of freezing/thawing and ultrasonic power, the MMT nanosheets with different aspect ratios have been prepared efficiently. Such a unique exfoliation method has broad applicability for layered materials to produce monolayer nanosheets on a large scale.

6.
Environ Sci Technol ; 53(3): 1706-1714, 2019 02 05.
Artigo em Inglês | MEDLINE | ID: mdl-30583696

RESUMO

Over the past two decades vehicle emission standards in the United States have been dramatically tightened with the goal of reducing urban air pollution. Secondary organic aerosol (SOA) is the dominant contributor to urban organic aerosol. Experiments were conducted at the California Air Resources Board Haagen-Smit Laboratory to characterize exhaust organics from 20 gasoline vehicles recruited from the California in-use fleet. The vehicles spanned a wide range of emission certification standards. We comprehensively characterized intermediate volatility and semivolatile organic compound emissions using thermal desorption two-dimensional gas-chromatography-mass-spectrometry with electron impact (GC × GC-EI-MS) and vacuum-ultraviolet (GC × GC-VUV-MS) ionization. Single-ring aromatic compounds with unsaturated C4 and C5 substituents contribute a large fraction of the intermediate volatility organic compound (IVOC) emissions in gasoline vehicle exhaust. The analyses of quartz filters used in GC × GC-VUV-MS show that primary organic aerosol emissions were dominated by motor oil. We combined our new emissions data with published SOA yield parametrizations to estimate SOA formation potential. After 24 h of oxidation, IVOC emissions contributed 45% of  SOA formation;  BTEX compounds (benzene, toluene, xylenes, and ethylbenzene), 40%;  other VOC aromatics, 15%. The composition of IVOC emissions was consistent across the test fleet, suggesting that future reductions in vehicular emissions will continue to reduce SOA formation and ambient particulate mass levels.


Assuntos
Poluentes Atmosféricos , Gasolina , Aerossóis , California , Emissões de Veículos , Volatilização
7.
Nanotechnology ; 29(2): 025605, 2018 01 12.
Artigo em Inglês | MEDLINE | ID: mdl-29154254

RESUMO

Novel montmorillonite-nanosheet/chitosan (MMTNS/CS) hydrogels fabricated via the self-assembly of exfoliated MMTNS and CS chains were investigated. The exfoliation of MMTNS, self-assembly mechanism and structure of MMTNS/CS hydrogels were characterized by an atomic force microscope, scanning electron microscope, transmission electron microscope, Fourier transform infrared spectroscope, energy-dispersive x-ray spectroscope and Brunauer-Emmett-Teller analyzer, respectively. The results indicated that MMT could be easily exfoliated to nanosheets with a thickness of 1 âˆ¼ 5 nm in aqueous solution by an ultrasonic base upon interlayer hydration. The formation mechanism of the self-assembly hydrogels was due to the hydrogen bond (-OH ··· +NH3-) and electrostatic interaction between the MMTNS and CS. The MMTNSs were connected consecutively by CS in-plane to form a huge slice. The porous structure of the hydrogels was controllable by adjusting the MMTNS/CS mass ratio. The hydrogels could be used as adsorbents for sewage treatments, carriers for drugs, microorganisms and catalyzers due to their controllable porous structure and tremendous specific surface area which were derived from the completely exfoliated MMTNS.

8.
Environ Sci Technol ; 52(3): 1253-1261, 2018 02 06.
Artigo em Inglês | MEDLINE | ID: mdl-29303572

RESUMO

Secondary organic aerosol (SOA) formation from dilute exhaust from 16 gasoline vehicles was investigated using a potential aerosol mass (PAM) oxidation flow reactor during chassis dynamometer testing using the cold-start unified cycle (UC). Ten vehicles were equipped with gasoline direct injection engines (GDI vehicles) and six with port fuel injection engines (PFI vehicles) certified to a wide range of emissions standards. We measured similar SOA production from GDI and PFI vehicles certified to the same emissions standard; less SOA production from vehicles certified to stricter emissions standards; and, after accounting for differences in gas-particle partitioning, similar effective SOA yields across different engine technologies and certification standards. Therefore the ongoing, dramatic shift from PFI to GDI vehicles in the United States should not alter the contribution of gasoline vehicles to ambient SOA and the natural replacement of older vehicles with newer ones certified to stricter emissions standards should reduce atmospheric SOA levels. Compared to hot operations, cold-start exhaust had lower effective SOA yields, but still contributed more SOA overall because of substantially higher organic gas emissions. We demonstrate that the PAM reactor can be used as a screening tool for vehicle SOA production by carefully accounting for the effects of the large variations in emission rates.


Assuntos
Gasolina , Emissões de Veículos , Aerossóis , Certificação , Oxirredução , Estados Unidos
9.
Environ Sci Technol ; 52(21): 12934-12942, 2018 11 06.
Artigo em Inglês | MEDLINE | ID: mdl-30351037

RESUMO

Intermediate volatility organic compound (IVOC) emissions from a large cargo vessel were characterized under real-world operating conditions using an on-board measurement system. Test ship fuel-based emission factors (EFs) of total IVOCs were determined for two fuel types and seven operating conditions. The average total IVOC EF was 1003 ± 581 mg·kg-fuel-1, approximately 0.76 and 0.29 times the EFs of primary organic aerosol (POA) emissions from low-sulfur fuel (LSF, 0.38 wt % S) and high-sulfur fuel (HSF, 1.12 wt % S), respectively. The average total IVOC EF from LSF was 2.4 times that from HSF. The average IVOC EF under low engine load (15%) was 0.5-1.6 times higher than those under 36%-74% loads. An unresolved complex mixture (UCM) contributed 86.1 ± 1.9% of the total IVOC emissions. Ship secondary organic aerosol (SOA) production was estimated to be 546.5 ± 284.1 mg·kg-fuel-1; IVOCs contributed 98.9 ± 0.9% of the produced SOA on average. Fuel type was the dominant determinant of ship IVOC emissions, IVOC volatility distributions, and SOA production. The ship emitted more IVOC mass, produced higher proportions of volatile organic components, and produced more SOA mass when fueled with LSF than when fueled with HSF. When reducing ship POA emissions, more attention should be paid to commensurate control of ship SOA formation potential.


Assuntos
Poluentes Atmosféricos , Emissões de Veículos , Aerossóis , Compostos Orgânicos , Navios , Volatilização
10.
Environ Sci Technol ; 51(11): 6542-6552, 2017 Jun 06.
Artigo em Inglês | MEDLINE | ID: mdl-28441489

RESUMO

Recent increases in the Corporate Average Fuel Economy standards have led to widespread adoption of vehicles equipped with gasoline direct-injection (GDI) engines. Changes in engine technologies can alter emissions. To quantify these effects, we measured gas- and particle-phase emissions from 82 light-duty gasoline vehicles recruited from the California in-use fleet tested on a chassis dynamometer using the cold-start unified cycle. The fleet included 15 GDI vehicles, including 8 GDIs certified to the most-stringent emissions standard, superultra-low-emission vehicles (SULEV). We quantified the effects of engine technology, emission certification standards, and cold-start on emissions. For vehicles certified to the same emissions standard, there is no statistical difference of regulated gas-phase pollutant emissions between PFIs and GDIs. However, GDIs had, on average, a factor of 2 higher particulate matter (PM) mass emissions than PFIs due to higher elemental carbon (EC) emissions. SULEV certified GDIs have a factor of 2 lower PM mass emissions than GDIs certified as ultralow-emission vehicles (3.0 ± 1.1 versus 6.3 ± 1.1 mg/mi), suggesting improvements in engine design and calibration. Comprehensive organic speciation revealed no statistically significant differences in the composition of the volatile organic compounds emissions between PFI and GDIs, including benzene, toluene, ethylbenzene, and xylenes (BTEX). Therefore, the secondary organic aerosol and ozone formation potential of the exhaust does not depend on engine technology. Cold-start contributes a larger fraction of the total unified cycle emissions for vehicles meeting more-stringent emission standards. Organic gas emissions were the most sensitive to cold-start compared to the other pollutants tested here. There were no statistically significant differences in the effects of cold-start on GDIs and PFIs. For our test fleet, the measured 14.5% decrease in CO2 emissions from GDIs was much greater than the potential climate forcing associated with higher black carbon emissions. Thus, switching from PFI to GDI vehicles will likely lead to a reduction in net global warming.


Assuntos
Aerossóis , Gasolina , Emissões de Veículos , Poluentes Atmosféricos , California , Certificação , Clima , Veículos Automotores
11.
Environ Sci Technol ; 50(8): 4554-63, 2016 Apr 19.
Artigo em Inglês | MEDLINE | ID: mdl-27023443

RESUMO

Dynamometer experiments were conducted to characterize the intermediate volatility organic compound (IVOC) emissions from a fleet of on-road gasoline vehicles and small off-road gasoline engines. IVOCs were quantified through gas chromatography/mass spectrometry analysis of adsorbent samples collected from a constant volume sampler. The dominant fraction (>80%, on average) of IVOCs could not be resolved on a molecular level. These unspeciated IVOCs were quantified as two chemical classes (unspeciated branched alkanes and cyclic compounds) in 11 retention-time-based bins. IVOC emission factors (mg kg-fuel(-1)) from on-road vehicles varied widely from vehicle to vehicle, but showed a general trend of lower emissions for newer vehicles that met more stringent emission standards. IVOC emission factors for 2-stroke off-road engines were substantially higher than 4-stroke off-road engines and on-road vehicles. Despite large variations in the magnitude of emissions, the IVOC volatility distribution and chemical characteristics were consistent across all tests and IVOC emissions were strongly correlated with nonmethane hydrocarbons (NMHCs), primary organic aerosol and speciated IVOCs. Although IVOC emissions only correspond to approximately 4% of NMHC emissions from on-road vehicles over the cold-start unified cycle, they are estimated to produce as much or more SOA than single-ring aromatics. Our results clearly demonstrate that IVOCs from gasoline engines are an important class of SOA precursors and provide observational constraints on IVOC emission factors and chemical composition to facilitate their inclusion into atmospheric chemistry models.


Assuntos
Gasolina/análise , Veículos Automotores , Emissões de Veículos/análise , Compostos Orgânicos Voláteis/análise , Aerossóis , Alcanos/análise , California , Cromatografia Gasosa-Espectrometria de Massas , Modelos Teóricos , Veículos Off-Road
12.
Environ Sci Technol ; 50(24): 13592-13599, 2016 12 20.
Artigo em Inglês | MEDLINE | ID: mdl-27993057

RESUMO

Experiments were conducted at the California Air Resources Board Haagen-Smit Laboratory to understand changes in vehicle emissions in response to stricter emissions standards over the past 25 years. Measurements included a wide range of volatile organic compounds (VOCs) for a wide range of spark ignition gasoline vehicles meeting varying levels of emissions standards, including all certifications from Tier 0 up to Partial Zero Emission Vehicle. Standard gas chromatography (GC) and high performance liquid chromatography (HLPC) analyses were employed for drive-cycle phase emissions. A proton-transfer-reaction mass spectrometer measured time-resolved emissions for a wide range of VOCs. Cold-start emissions occur almost entirely in the first 30-60 s for newer vehicles. Cold-start emissions have compositions that are not significantly different across all vehicles tested and are markedly different from neat fuel. Hot-stabilized emissions have varying importance depending on species and may require a driving distance of 200 miles to equal the emissions from a single cold start. Average commute distances in the U.S. suggest the majority of in-use vehicles have emissions dominated by cold starts. The distribution of vehicle ages in the U.S. suggests that within several years only a few percent of vehicles will have significant driving emissions compared to cold-start emissions.


Assuntos
Poluentes Atmosféricos , Veículos Automotores , Gasolina , Emissões de Veículos , Compostos Orgânicos Voláteis
13.
Environ Sci Technol ; 49(19): 11516-26, 2015 Oct 06.
Artigo em Inglês | MEDLINE | ID: mdl-26322746

RESUMO

Emissions of intermediate-volatility organic compounds (IVOCs) from five on-road diesel vehicles and one off-road diesel engine were characterized during dynamometer testing. The testing evaluated the effects of driving cycles, fuel composition and exhaust aftertreatment devices. On average, more than 90% of the IVOC emissions were not identified on a molecular basis, instead appearing as an unresolved complex mixture (UCM) during gas-chromatography mass-spectrometry analysis. Fuel-based emissions factors (EFs) of total IVOCs (speciated + unspeciated) depend strongly on aftertreatment technology and driving cycle. Total-IVOC emissions from vehicles equipped with catalyzed diesel particulate filters (DPF) are substantially lower (factor of 7 to 28, depending on driving cycle) than from vehicles without any exhaust aftertreatment. Total-IVOC emissions from creep and idle operations are substantially higher than emissions from high-speed operations. Although the magnitude of the total-IVOC emissions can vary widely, there is little variation in the IVOC composition across the set of tests. The new emissions data are combined with published yield data to investigate secondary organic aerosol (SOA) formation. SOA production from unspeciated IVOCs is estimated using surrogate compounds, which are assigned based on gas-chromatograph retention time and mass spectral signature of the IVOC UCM. IVOCs contribute the vast majority of the SOA formed from exhaust from on-road diesel vehicles. The estimated SOA production is greater than predictions by previous studies and substantially higher than primary organic aerosol. Catalyzed DPFs substantially reduce SOA formation potential of diesel exhaust, except at low speed operations.


Assuntos
Aerossóis/química , Veículos Automotores , Emissões de Veículos/análise , Compostos Orgânicos Voláteis/análise , Aerossóis/análise , Cromatografia Gasosa-Espectrometria de Massas , Compostos Orgânicos Voláteis/química
15.
Environ Sci Technol ; 48(23): 13743-50, 2014 Dec 02.
Artigo em Inglês | MEDLINE | ID: mdl-25375804

RESUMO

Secondary organic aerosol (SOA) is a major component of atmospheric fine particle mass. Intermediate-volatility organic compounds (IVOCs) have been proposed to be an important source of SOA. We present a comprehensive analysis of atmospheric IVOC concentrations and their SOA production using measurements made in Pasadena, California during the California at the Nexus of Air Quality and Climate Change (CalNex) study. The campaign-average concentration of primary IVOCs was 6.3 ± 1.9 µg m(-3) (average ± standard deviation), which is comparable to the concentration of organic aerosol but only 7.4 ± 1.2% of the concentration of speciated volatile organic compounds. Only 8.6 ± 2.2% of the mass of the primary IVOCs was speciated. Almost no weekend/weekday variation in the ambient concentration of both speciated and total primary IVOCs was observed, suggesting that petroleum-related sources other than on-road diesel vehicles contribute substantially to the IVOC emissions. Primary IVOCs are estimated to produce about 30% of newly formed SOA in the afternoon during CalNex, about 5 times that from single-ring aromatics. The importance of IVOCs in SOA formation is expected to be similar in many urban environments.


Assuntos
Aerossóis/análise , Poluentes Atmosféricos/análise , Compostos Orgânicos Voláteis/análise , California , Monitoramento Ambiental , Modelos Teóricos , Fatores de Tempo
16.
Environ Sci Technol ; 48(19): 11235-42, 2014 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-25188317

RESUMO

Secondary organic aerosol (SOA) formation from in-use vehicle emissions was investigated using a potential aerosol mass (PAM) flow reactor deployed in a highway tunnel in Pittsburgh, Pennsylvania. Experiments consisted of passing exhaust-dominated tunnel air through a PAM reactor over integrated hydroxyl radical (OH) exposures ranging from ∼ 0.3 to 9.3 days of equivalent atmospheric oxidation. Experiments were performed during heavy traffic periods when the fleet was at least 80% light-duty gasoline vehicles on a fuel-consumption basis. The peak SOA production occurred after 2-3 days of equivalent atmospheric oxidation. Additional OH exposure decreased the SOA production presumably due to a shift from functionalization to fragmentation dominated reaction mechanisms. Photo-oxidation also produced substantial ammonium nitrate, often exceeding the mass of SOA. Analysis with an SOA model highlight that unspeciated organics (i.e., unresolved complex mixture) are a very important class of precursors and that multigenerational processing of both gases and particles is important at longer time scales. The chemical evolution of the organic aerosol inside the PAM reactor appears to be similar to that observed in the atmosphere. The mass spectrum of the unoxidized primary organic aerosol closely resembles ambient hydrocarbon-like organic aerosol (HOA). After aging the exhaust equivalent to a few hours of atmospheric oxidation, the organic aerosol most closely resembles semivolatile oxygenated organic aerosol (SV-OOA) and then low-volatility organic aerosol (LV-OOA) at higher OH exposures. Scaling the data suggests that mobile sources contribute ∼ 2.9 ± 1.6 Tg SOA yr(-1) in the United States, which is a factor of 6 greater than all mobile source particulate matter emissions reported by the National Emissions Inventory. This highlights the important contribution of SOA formation from vehicle exhaust to ambient particulate matter concentrations in urban areas.


Assuntos
Aerossóis/análise , Aerossóis/química , Poluentes Atmosféricos/análise , Emissões de Veículos/análise , Atmosfera/análise , Cidades , Gasolina/análise , Radical Hidroxila/análise , Nitratos/análise , Compostos Orgânicos/análise , Oxirredução , Material Particulado/análise , Pennsylvania , Estados Unidos , Compostos Orgânicos Voláteis/química
17.
Environ Sci Technol ; 47(8): 3781-7, 2013 Apr 16.
Artigo em Inglês | MEDLINE | ID: mdl-23448102

RESUMO

In situ measurements of organic compounds in both gas and particle phases were made with a thermal desorption aerosol gas chromatography (TAG) instrument. The gas/particle partitioning of phthalic acid, pinonaldehyde, and 6,10,14-trimethyl-2-pentadecanone is discussed in detail to explore secondary organic aerosol (SOA) formation mechanisms. Measured fractions in the particle phase (f(part)) of 6,10,14-trimethyl-2-pentadecanone were similar to those expected from the absorptive gas/particle partitioning theory, suggesting that its partitioning is dominated by absorption processes. However, f(part) of phthalic acid and pinonaldehyde were substantially higher than predicted. The formation of low-volatility products from reactions of phthalic acid with ammonia is proposed as one possible mechanism to explain the high f(part) of phthalic acid. The observations of particle-phase pinonaldehyde when inorganic acids were fully neutralized indicate that inorganic acids are not required for the occurrence of reactive uptake of pinonaldehyde on particles. The observed relationship between f(part) of pinonaldehyde and relative humidity suggests that the aerosol water plays a significant role in the formation of particle-phase pinonaldehyde. Our results clearly show it is necessary to include multiple gas/particle partitioning pathways in models to predict SOA and multiple SOA tracers in source apportionment models to reconstruct SOA.


Assuntos
Aerossóis/análise , Gases/análise , Compostos Orgânicos/análise , Material Particulado/análise , Aldeídos , Ânions/análise , Carbono/análise , Cátions/análise , Cromatografia Gasosa , Ciclobutanos , Cetonas/análise , Oxigênio/análise , Ácidos Ftálicos , Fatores de Tempo , Pressão de Vapor
18.
Environ Sci Technol ; 47(20): 11403-13, 2013 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-24004194

RESUMO

Atmospheric photooxidation of isoprene is an important source of secondary organic aerosol (SOA) and there is increasing evidence that anthropogenic oxidant emissions can enhance this SOA formation. In this work, we use ambient observations of organosulfates formed from isoprene epoxydiols (IEPOX) and methacrylic acid epoxide (MAE) and a broad suite of chemical measurements to investigate the relative importance of nitrogen oxide (NO/NO2) and hydroperoxyl (HO2) SOA formation pathways from isoprene at a forested site in California. In contrast to IEPOX, the calculated production rate of MAE was observed to be independent of temperature. This is the result of the very fast thermolysis of MPAN at high temperatures that affects the distribution of the MPAN reservoir (MPAN / MPA radical) reducing the fraction that can react with OH to form MAE and subsequently SOA (F(MAE formation)). The strong temperature dependence of F(MAE formation) helps to explain our observations of similar concentrations of IEPOX-derived organosulfates (IEPOX-OS; ~1 ng m(-3)) and MAE-derived organosulfates (MAE-OS; ~1 ng m(-3)) under cooler conditions (lower isoprene concentrations) and much higher IEPOX-OS (~20 ng m(-3)) relative to MAE-OS (<0.0005 ng m(-3)) at higher temperatures (higher isoprene concentrations). A kinetic model of IEPOX and MAE loss showed that MAE forms 10-100 times more ring-opening products than IEPOX and that both are strongly dependent on aerosol water content when aerosol pH is constant. However, the higher fraction of MAE ring opening products does not compensate for the lower MAE production under warmer conditions (higher isoprene concentrations) resulting in lower formation of MAE-derived products relative to IEPOX at the surface. In regions of high NOx, high isoprene emissions and strong vertical mixing the slower MPAN thermolysis rate aloft could increase the fraction of MPAN that forms MAE resulting in a vertically varying isoprene SOA source.


Assuntos
Aerossóis/análise , Aerossóis/química , Butadienos/química , Hemiterpenos/química , Pentanos/química , Anidridos/química , Atmosfera/química , Compostos de Epóxi/química , Radical Hidroxila/química , Metacrilatos/química , Oxirredução , Sulfatos/química , Temperatura , Fatores de Tempo
19.
J Colloid Interface Sci ; 652(Pt B): 1620-1630, 2023 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-37666194

RESUMO

Two-dimensional montmorillonite nanosheet (MMTNS) is desirable building block for fabricating multifunctional materials as due to its extraordinary properties. In practical applications, however, the concentration of MMTNS prepared by exfoliation is normally too low to be used for material assembling. The general thermal-concentration method is effective, however, it can be time-consuming and require a lot of energy. In this case, the remarkable dispersion stability of MMTNS is worth noting. Herein, the extraordinary dispersion stability of MMTNS derived from electrostatic and hydration repulsion was firstly revealed by molecular dynamics (MD) simulation, which caused the poor dewatering of MMTNS. Further, based on the surface and structural chemistry of MMTNS, a series of strategies, involving charge and cross-linked structure regulation on the edge surface, as well as electrical double-layer modulation and calcification modification based on the electrolytes, were proposed to inhibit the dispersion and enhance the aggregation of MMTNS. Intriguingly, a novel chemical, Tetraethylenepentamine (TEPA) was applied in the dewatering of MMTNS. The TEPA not only act as a cross-linker to bond with MMTNS into an easy-to-dewatering 3D network structure, but also act as a switch for effortless viscosity tuning. Meanwhile, the dual function of electrolytes for electrical double layer compression and calcification modification of MMTNS was investigated by DLVO theory and structural analyses. This work offers explicit directions for improving the dewatering performance of MMTNS to meet the requirements of practical implementation.

20.
Materials (Basel) ; 16(7)2023 Mar 29.
Artigo em Inglês | MEDLINE | ID: mdl-37049036

RESUMO

It is crucial but challenging to detect intermediate or end products promptly. Traditional chemical detection methods are time-consuming and cannot detect mineral phase content. Thermal infrared hyperspectral (TIH) technology is an effective means of real-time imaging and can precisely capture the emissivity characteristics of objects. This study introduces TIH to estimate the content of potassium salts, with a model based on Competitive Adaptive Reweighted Sampling (CARS) and Partial Least Squares Regression (PLSR). The model takes the emissivity spectrum of potassium salt into account and accurately predicts the content of Mixing Potassium (MP), a mineral mixture produced in Lop Nur, Xinjiang. The main mineral content in MP was measured by Mineral Liberation Analyzer (MLA), mainly including picromerite, potassium chloride, magnesium sulfate, and less sodium chloride. 129 configured MP samples were divided into calibration (97 samples) and prediction (32 samples) sets. The CARS-PLSR method achieved good prediction results for MP mineral content (picromerite: correlation coefficient of correction set (Rp2) = 0.943, predicted root mean square error (RMSEP) = 2.72%, relative predictive deviation (RPD) = 4.24; potassium chloride: Rp2 = 0.948, RMSEP = 2.86%, RPD = 4.42). Experimental results convey that TIH technology can effectively identify the emissivity characteristics of MP minerals, facilitating quantitative detection of MP mineral content.

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