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1.
Environ Sci Atmos ; 4(5): 531-546, 2024 May 16.
Artigo em Inglês | MEDLINE | ID: mdl-38764888

RESUMO

Iodine oxoacids are recognised for their significant contribution to the formation of new particles in marine and polar atmospheres. Nevertheless, to incorporate the iodine oxoacid nucleation mechanism into global simulations, it is essential to comprehend how this mechanism varies under various atmospheric conditions. In this study, we combined measurements from the CLOUD (Cosmic Leaving OUtdoor Droplets) chamber at CERN and simulations with a kinetic model to investigate the impact of temperature, ionisation, and humidity on iodine oxoacid nucleation. Our findings reveal that ion-induced particle formation rates remain largely unaffected by changes in temperature. However, neutral particle formation rates experience a significant increase when the temperature drops from +10 °C to -10 °C. Running the kinetic model with varying ionisation rates demonstrates that the particle formation rate only increases with a higher ionisation rate when the iodic acid concentration exceeds 1.5 × 107 cm-3, a concentration rarely reached in pristine marine atmospheres. Consequently, our simulations suggest that, despite higher ionisation rates, the charged cluster nucleation pathway of iodic acid is unlikely to be enhanced in the upper troposphere by higher ionisation rates. Instead, the neutral nucleation channel is likely to be the dominant channel in that region. Notably, the iodine oxoacid nucleation mechanism remains unaffected by changes in relative humidity from 2% to 80%. However, under unrealistically dry conditions (below 0.008% RH at +10 °C), iodine oxides (I2O4 and I2O5) significantly enhance formation rates. Therefore, we conclude that iodine oxoacid nucleation is the dominant nucleation mechanism for iodine nucleation in the marine and polar boundary layer atmosphere.

2.
Anal Chem ; 2024 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-38691094

RESUMO

Chemical ionization (CI) atmospheric pressure interface mass spectrometry is a unique analytical technique for its low detection limits, softness to preserve molecular information, and selectivity for particular classes of species. Here, we present a fast polarity switching approach for highly sensitive online analysis of a wide range of trace species in complex samples using selective CI chemistries and high-resolution mass spectrometry. It is achieved by successfully coupling a multischeme chemical ionization inlet (MION) and an Orbitrap Fourier transform mass spectrometer. The capability to flexibly combine ionization chemistries from both polarities effectively extends the detectability compared to using only one ionization chemistry, as commonly used positive and negative reagent ions tend to be sensitive to different classes of species. We tested the performance of the MION-Orbitrap using reactive gaseous organic species generated by α-pinene ozonolysis in an environmental chamber and a standard mixture of 71 pesticides. Diethylammonium and nitrate are used as reagent ions in positive and negative polarities. We show that with a mass resolving power of 280,000, the MION-Orbitrap can switch and measure both polarities within 1 min, which is sufficiently fast and stable to follow the temporal evolution of reactive organic species and the thermal desorption profile of pesticides. We detected 23 of the 71 pesticides in the mixture using only nitrate as the reagent ion. Facilitated by polarity switching, we also detected 47 pesticides using diethylammonium, improving the total number of detected species to 59. For reactive organic species generated by α-pinene ozonolysis, we show that combining diethylammonium and nitrate addresses the need to measure oxygenated molecules in atmospheric environments with a wide range of oxidation states. These results indicate that the polarity switching MION-Orbitrap can promisingly serve as a versatile tool for the nontargeted chemical analysis of trace species in various applications.

3.
Sci Adv ; 10(14): eadm9191, 2024 Apr 05.
Artigo em Inglês | MEDLINE | ID: mdl-38569045

RESUMO

Pure biogenic new particle formation (NPF) induced by highly oxygenated organic molecules (HOMs) could be an important mechanism for pre-industrial aerosol formation. However, it has not been unambiguously confirmed in the ambient due to the scarcity of truly pristine continental locations in the present-day atmosphere or the lack of chemical characterization of NPF precursors. Here, we report ambient observations of pure biogenic HOM-driven NPF over a peatland in southern Finland. Meteorological decoupling processes formed an "air pocket" (i.e., a very shallow surface layer) at night and favored NPF initiated entirely by biogenic HOM from this peatland, whose atmospheric environment closely resembles that of the pre-industrial era. Our study sheds light on pre-industrial aerosol formation, which represents the baseline for estimating the impact of present and future aerosol on climate, as well as on future NPF, the features of which may revert toward pre-industrial-like conditions due to air pollution mitigation.

4.
Sci Total Environ ; 923: 171323, 2024 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-38438031

RESUMO

Particulate matter represents one of the most severe air pollutants globally. Organic aerosol (OA) comprises 30-70 % of submicron particle mass in urban areas. An effective way to mitigate OA particulate pollutants is to reduce the formation of secondary organic aerosol (SOA). Here, we studied the effect of titanium dioxide (TiO2) photocatalytic seeds on the formation and mitigation of SOA particles from α-pinene or toluene oxidation in chamber. For the first time, we discovered that under ultraviolet (UV) irradiation, the presence of TiO2 directly removed internally mixed α-pinene SOA mass by 53.7 % within 200 mins, and also directly removed SOA matter in an externally mixed state that is not in direct contact with TiO2 surface: the mass of externally mixed α-pinene SOA was reduced by 21.9 % within 81 mins, and the toluene SOA mass was reduced by 46.6 % in 145mins. In addition, the presence of TiO2 effectively inhibited the formation of SOA particles with a SOA mass yield of zero. This study brings up an innovative concept for air pollution control - the direct photocatalytic degradation of OA with aid of TiO2-based photocatalysts. Our novel findings will potentially bring practical applications in air pollution abatement and regional, even global aerosol-climate interactions.

5.
Environ Sci Atmos ; 4(2): 265-274, 2024 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-38371605

RESUMO

Aerosols formed and grown by gas-to-particle processes are a major contributor to smog and haze in megacities, despite the competition between growth and loss rates. Rapid growth rates from ammonium nitrate formation have the potential to sustain particle number in typical urban polluted conditions. This process requires supersaturation of gas-phase ammonia and nitric acid with respect to ammonium nitrate saturation ratios. Urban environments are inhomogeneous. In the troposphere, vertical mixing is fast, and aerosols may experience rapidly changing temperatures. In areas close to sources of pollution, gas-phase concentrations can also be highly variable. In this work we present results from nucleation experiments at -10 °C and 5 °C in the CLOUD chamber at CERN. We verify, using a kinetic model, how long supersaturation is likely to be sustained under urban conditions with temperature and concentration inhomogeneities, and the impact it may have on the particle size distribution. We show that rapid and strong temperature changes of 1 °C min-1 are needed to cause rapid growth of nanoparticles through ammonium nitrate formation. Furthermore, inhomogeneous emissions of ammonia in cities may also cause rapid growth of particles.

6.
Sci Total Environ ; 919: 170633, 2024 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-38340865

RESUMO

Biogenic and anthropogenic organic vapors are crucial precursors of ozone and secondary organic aerosol (SOA) in the atmosphere. Here we conducted real-time measurements of gaseous organic compounds using a Vocus proton-transfer-reaction mass spectrometer (Vocus PTR-MS) at the Shanghuang mountain site (1128 m a.s.l.) in southeastern China during November 2022. Our results revealed a substantial impact of mixed biogenic and anthropogenic compounds at the mountain site, with oxygenated volatile organic compounds (OVOCs) comprising 74 % of the organic vapors. Two distinct periods, characterized by sunny days (P1) and persistent cloud events (P2), were observed. P1 exhibited higher concentrations of biogenic-related emissions compared to P2. For instance, isoprene, monoterpenes, and sesquiterpenes during P1 were 2.4-2.9 times higher than those during P2. OVOCs such as acetaldehyde, MVK + MACR, acetone, and MEK also showed higher concentrations during P1, indicating a dominant source from the photochemical oxidation of biogenic VOCs. Anthropogenic-related VOCs like benzene and toluene had higher concentrations during P2, displaying different diurnal cycles compared to P1. Our analysis identified four biogenic-related factors dominated by isoprene and sesquiterpene oxidation products, and two anthropogenic-related factors. During P1, biogenic sources contributed approximately 80 % to total organic compounds, while during P2, anthropogenic sources, particularly the aromatic-related factor, increased from 16 % to 35 %. Furthermore, a unique factor characterized by C2 amines and C3 amides and periodic plumes indicated the influence of industrial emissions from regional transport. The study highlights the significant variations in sources and compositions of gaseous organic compounds at regional mountain sites due to changes in meteorology and photochemical processing, potentially impacting regional ozone and SOA formation.

7.
Environ Sci Technol ; 58(3): 1601-1614, 2024 Jan 23.
Artigo em Inglês | MEDLINE | ID: mdl-38185880

RESUMO

Highly oxygenated organic molecules (HOMs) are a major source of new particles that affect the Earth's climate. HOM production from the oxidation of volatile organic compounds (VOCs) occurs during both the day and night and can lead to new particle formation (NPF). However, NPF involving organic vapors has been reported much more often during the daytime than during nighttime. Here, we show that the nitrate radicals (NO3), which arise predominantly at night, inhibit NPF during the oxidation of monoterpenes based on three lines of observational evidence: NPF experiments in the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber at CERN (European Organization for Nuclear Research), radical chemistry experiments using an oxidation flow reactor, and field observations in a wetland that occasionally exhibits nocturnal NPF. Nitrooxy-peroxy radicals formed from NO3 chemistry suppress the production of ultralow-volatility organic compounds (ULVOCs) responsible for biogenic NPF, which are covalently bound peroxy radical (RO2) dimer association products. The ULVOC yield of α-pinene in the presence of NO3 is one-fifth of that resulting from ozone chemistry alone. Even trace amounts of NO3 radicals, at sub-parts per trillion level, suppress the NPF rate by a factor of 4. Ambient observations further confirm that when NO3 chemistry is involved, monoterpene NPF is completely turned off. Our results explain the frequent absence of nocturnal biogenic NPF in monoterpene (α-pinene)-rich environments.


Assuntos
Poluentes Atmosféricos , Monoterpenos Bicíclicos , Ozônio , Compostos Orgânicos Voláteis , Monoterpenos/química , Nitratos/química , Aerossóis/análise , Compostos Orgânicos Voláteis/química
8.
Natl Sci Rev ; 11(1): nwad138, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-38116089

RESUMO

New particle formation (NPF) in the tropical free troposphere (FT) is a globally important source of cloud condensation nuclei, affecting cloud properties and climate. Oxidized organic molecules (OOMs) produced from biogenic volatile organic compounds are believed to contribute to aerosol formation in the tropical FT, but without direct chemical observations. We performed in situ molecular-level OOMs measurements at the Bolivian station Chacaltaya at 5240 m above sea level, on the western edge of Amazonia. For the first time, we demonstrate the presence of OOMs, mainly with 4-5 carbon atoms, in both gas-phase and particle-phase (in terms of mass contribution) measurements in tropical FT air from Amazonia. These observations, combined with air mass history analyses, indicate that the observed OOMs are linked to isoprene emitted from the rainforests hundreds of kilometers away. Based on particle-phase measurements, we find that these compounds can contribute to NPF, at least the growth of newly formed nanoparticles, in the tropical FT on a continental scale. Thus, our study is a fundamental and significant step in understanding the aerosol formation process in the tropical FT.

9.
Sci Adv ; 9(36): eadi5297, 2023 Sep 08.
Artigo em Inglês | MEDLINE | ID: mdl-37682996

RESUMO

Biogenic vapors form new particles in the atmosphere, affecting global climate. The contributions of monoterpenes and isoprene to new particle formation (NPF) have been extensively studied. However, sesquiterpenes have received little attention despite a potentially important role due to their high molecular weight. Via chamber experiments performed under atmospheric conditions, we report biogenic NPF resulting from the oxidation of pure mixtures of ß-caryophyllene, α-pinene, and isoprene, which produces oxygenated compounds over a wide range of volatilities. We find that a class of vapors termed ultralow-volatility organic compounds (ULVOCs) are highly efficient nucleators and quantitatively determine NPF efficiency. When compared with a mixture of isoprene and monoterpene alone, adding only 2% sesquiterpene increases the ULVOC yield and doubles the formation rate. Thus, sesquiterpene emissions need to be included in assessments of global aerosol concentrations in pristine climates where biogenic NPF is expected to be a major source of cloud condensation nuclei.

10.
Nat Commun ; 14(1): 3347, 2023 Jun 08.
Artigo em Inglês | MEDLINE | ID: mdl-37291087

RESUMO

The interaction between nitrogen monoxide (NO) and organic peroxy radicals (RO2) greatly impacts the formation of highly oxygenated organic molecules (HOM), the key precursors of secondary organic aerosols. It has been thought that HOM production can be significantly suppressed by NO even at low concentrations. Here, we perform dedicated experiments focusing on HOM formation from monoterpenes at low NO concentrations (0 - 82 pptv). We demonstrate that such low NO can enhance HOM production by modulating the RO2 loss and favoring the formation of alkoxy radicals that can continue to autoxidize through isomerization. These insights suggest that HOM yields from typical boreal forest emissions can vary between 2.5%-6.5%, and HOM formation will not be completely inhibited even at high NO concentrations. Our findings challenge the notion that NO monotonically reduces HOM yields by extending the knowledge of RO2-NO interactions to the low-NO regime. This represents a major advance towards an accurate assessment of HOM budgets, especially in low-NO environments, which prevails in the pre-industrial atmosphere, pristine areas, and the upper boundary layer.


Assuntos
Atmosfera , Óxido Nítrico , Monoterpenos , Oxirredução , Aerossóis
11.
Environ Sci Technol ; 57(20): 7764-7776, 2023 05 23.
Artigo em Inglês | MEDLINE | ID: mdl-37155674

RESUMO

Oxygenated organic molecules (OOMs) are critical intermediates linking volatile organic compound oxidation and secondary organic aerosol (SOA) formation. Yet, the understanding of OOM components, formation mechanism, and impacts are still limited, especially for urbanized regions with a cocktail of anthropogenic emissions. Herein, ambient measurements of OOMs were conducted at a regional background site in South China in 2018. The molecular characteristics of OOMs revealed dominant nitrogen-containing products, and the influences of different factors on OOM composition and oxidation state were elucidated. Positive matrix factorization analysis resolved the complex OOM species to factors featured with fingerprint species from different oxidation pathways. A new method was developed to identify the key functional groups of OOMs, which successfully classified the majority species into carbonyls (8%), hydroperoxides (7%), nitrates (17%), peroxyl nitrates (10%), dinitrates (13%), aromatic ring-retaining species (6%), and terpenes (7%). The volatility estimation of OOMs was improved based on their identified functional groups and was used to simulate the aerosol growth process contributed by the condensation of those low-volatile OOMs. The results demonstrate the predominant role of OOMs in contributing sub-100 nm particle growth and SOA formation and highlight the importance of dinitrates and anthropogenic products from multistep oxidation.


Assuntos
Poluentes Atmosféricos , Poluentes Atmosféricos/análise , Hong Kong , Nitratos , Terpenos , Aerossóis/análise
12.
Environ Sci Technol ; 57(6): 2297-2309, 2023 02 14.
Artigo em Inglês | MEDLINE | ID: mdl-36716278

RESUMO

The mechanistic pathway by which high relative humidity (RH) affects gas-particle partitioning remains poorly understood, although many studies report increased secondary organic aerosol (SOA) yields at high RH. Here, we use real-time, molecular measurements of both the gas and particle phase to provide a mechanistic understanding of the effect of RH on the partitioning of biogenic oxidized organic molecules (from α-pinene and isoprene) at low temperatures (243 and 263 K) at the CLOUD chamber at CERN. We observe increases in SOA mass of 45 and 85% with increasing RH from 10-20 to 60-80% at 243 and 263 K, respectively, and attribute it to the increased partitioning of semi-volatile compounds. At 263 K, we measure an increase of a factor 2-4 in the concentration of C10H16O2-3, while the particle-phase concentrations of low-volatility species, such as C10H16O6-8, remain almost constant. This results in a substantial shift in the chemical composition and volatility distribution toward less oxygenated and more volatile species at higher RH (e.g., at 263 K, O/C ratio = 0.55 and 0.40, at RH = 10 and 80%, respectively). By modeling particle growth using an aerosol growth model, which accounts for kinetic limitations, we can explain the enhancement in the semi-volatile fraction through the complementary effect of decreased compound activity and increased bulk-phase diffusivity. Our results highlight the importance of particle water content as a diluting agent and a plasticizer for organic aerosol growth.


Assuntos
Poluentes Atmosféricos , Monoterpenos , Monoterpenos/química , Umidade , Aerossóis
13.
Environ Sci Technol ; 56(24): 17545-17555, 2022 12 20.
Artigo em Inglês | MEDLINE | ID: mdl-36441962

RESUMO

Alkaline gases, including NH3, C1-3-amines, C1-3-amides, and C1-3-imines, were measured in situ using a water cluster-CIMS in urban Beijing during the wintertime of 2018, with a campaign average of 2.8 ± 2.0 ppbv, 5.2 ± 4.3, 101.1 ± 94.5, and 5.2 ± 5.4 pptv, respectively. Source apportionment analysis constrained by emission profiles of in-use motor vehicles was performed using a SoFi-PMF software package, and five emission sources were identified as gasoline-powered vehicles (GV), diesel-powered vehicles (DV), septic system emission (SS), soil emission (SE), and combustion-related sources (CS). SS was the dominant NH3 source (60.0%), followed by DV (18.6%), SE (13.1%), CS (4.3%), and GV (4.0%). GV and DV were responsible for 69.9 and 85.2% of C1- and C2-amines emissions, respectively. Most of the C3-amines were emitted from nonmotor vehicular sources (SS = 61.3%; SE = 17.8%; CS = 9.1%). DV accounted for 71.9 and 34.1% of C1- and C2-amides emissions, respectively. CS was mainly comprised of amides and imines, likely originating from the pyrolysis of nitrogen-containing compounds. Our results suggested that motor vehicle exhausts can not only contribute to criteria air pollutants emission but also promote new particle formation, which has not been well recognized and considered in current regulations. Urban residential septic system was the predominant contributor to background NH3. Enhanced NH3 emissions from soil and combustion-related sources were the major cause of PM2.5 buildup during the haze events. Combustion-related sources, together with motor vehicles, were responsible for most of the observed amides and imines and may be of public health concern within the vicinity of these sources.


Assuntos
Poluentes Atmosféricos , Gases , Pequim , Poluentes Atmosféricos/análise , Emissões de Veículos/análise , Amidas , Iminas , Aminas , Monitoramento Ambiental , Material Particulado/análise , China
14.
Natl Sci Rev ; 9(10): nwac137, 2022 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-36196118

RESUMO

Transformation of low-volatility gaseous precursors to new particles affects aerosol number concentration, cloud formation and hence the climate. The clustering of acid and base molecules is a major mechanism driving fast nucleation and initial growth of new particles in the atmosphere. However, the acid-base cluster composition, measured using state-of-the-art mass spectrometers, cannot explain the measured high formation rate of new particles. Here we present strong evidence for the existence of base molecules such as amines in the smallest atmospheric sulfuric acid clusters prior to their detection by mass spectrometers. We demonstrate that forming (H2SO4)1(amine)1 is the rate-limiting step in atmospheric H2SO4-amine nucleation and the uptake of (H2SO4)1(amine)1 is a major pathway for the initial growth of H2SO4 clusters. The proposed mechanism is very consistent with measured new particle formation in urban Beijing, in which dimethylamine is the key base for H2SO4 nucleation while other bases such as ammonia may contribute to the growth of larger clusters. Our findings further underline the fact that strong amines, even at low concentrations and when undetected in the smallest clusters, can be crucial to particle formation in the planetary boundary layer.

15.
Environ Sci Technol ; 56(19): 14166-14177, 2022 Oct 04.
Artigo em Inglês | MEDLINE | ID: mdl-36126141

RESUMO

Nucleation of neutral iodine particles has recently been found to involve both iodic acid (HIO3) and iodous acid (HIO2). However, the precise role of HIO2 in iodine oxoacid nucleation remains unclear. Herein, we probe such a role by investigating the cluster formation mechanisms and kinetics of (HIO3)m(HIO2)n (m = 0-4, n = 0-4) clusters with quantum chemical calculations and atmospheric cluster dynamics modeling. When compared with HIO3, we find that HIO2 binds more strongly with HIO3 and also more strongly with HIO2. After accounting for ambient vapor concentrations, the fastest nucleation rate is predicted for mixed HIO3-HIO2 clusters rather than for pure HIO3 or HIO2 ones. Our calculations reveal that the strong binding results from HIO2 exhibiting a base behavior (accepting a proton from HIO3) and forming stronger halogen bonds. Moreover, the binding energies of (HIO3)m(HIO2)n clusters show a far more tolerant choice of growth paths when compared with the strict stoichiometry required for sulfuric acid-base nucleation. Our predicted cluster formation rates and dimer concentrations are acceptably consistent with those measured by the Cosmic Leaving Outdoor Droplets (CLOUD) experiment. This study suggests that HIO2 could facilitate the nucleation of other acids beyond HIO3 in regions where base vapors such as ammonia or amines are scarce.

16.
Environ Sci Technol ; 56(2): 770-778, 2022 01 18.
Artigo em Inglês | MEDLINE | ID: mdl-34806377

RESUMO

The understanding at a molecular level of ambient secondary organic aerosol (SOA) formation is hampered by poorly constrained formation mechanisms and insufficient analytical methods. Especially in developing countries, SOA related haze is a great concern due to its significant effects on climate and human health. We present simultaneous measurements of gas-phase volatile organic compounds (VOCs), oxygenated organic molecules (OOMs), and particle-phase SOA in Beijing. We show that condensation of the measured OOMs explains 26-39% of the organic aerosol mass growth, with the contribution of OOMs to SOA enhanced during severe haze episodes. Our novel results provide a quantitative molecular connection from anthropogenic emissions to condensable organic oxidation product vapors, their concentration in particle-phase SOA, and ultimately to haze formation.


Assuntos
Poluentes Atmosféricos , Compostos Orgânicos Voláteis , Aerossóis/análise , Poluentes Atmosféricos/análise , Pequim , Humanos
17.
Environ Sci Technol ; 56(11): 6880-6893, 2022 06 07.
Artigo em Inglês | MEDLINE | ID: mdl-34898185

RESUMO

Oxygenated volatile organic compounds (OVOCs) and secondary organic aerosol (SOA) formation potential of ambient air in Guangzhou, China was investigated using a field-deployed oxidation flow reactor (OFR). The OFR was used to mimic hours to weeks of atmospheric exposure to hydroxyl (OH) radicals within the 2-3 min residence time. A comprehensive investigation on the variation of VOCs and OVOCs as a function of OH exposure is shown. Substantial formation of organic acids and nitrogen-containing OVOC species were observed. Maximum SOA formation in the OFR was observed following 1-4 equiv days' OH exposure. SOA produced from known/measured VOC/IVOC precursors such as single-ring aromatics and long-chain alkanes can account for 52-75% of measured SOA under low NOx and 26-60% under high NOx conditions based on laboratory SOA yield parametrizations. To our knowledge, this is the first time that the contribution (8-20%) of long-chain (C8-C20) alkane oxidation to OFR SOA formation was quantified from direct measurement. By additionally estimating contribution from unmeasured semivolatile and intermediate volatility compounds (S/IVOCs) that are committed with C8-C20 alkanes, 64-100% of the SOA formation observed in the OFR can be explained, signifying the important contribution of S/IVOCs such as large cyclic alkanes to ambient SOA.


Assuntos
Poluentes Atmosféricos , Compostos Orgânicos Voláteis , Aerossóis/análise , Poluentes Atmosféricos/análise , Alcanos , China
18.
ACS Omega ; 6(45): 30726-30733, 2021 Nov 16.
Artigo em Inglês | MEDLINE | ID: mdl-34805700

RESUMO

Medical shortages during the COVID-19 pandemic saw numerous efforts to 3D print personal protective equipment and treatment supplies. There is, however, little research on the potential biocompatibility of 3D-printed parts using typical polymeric resins as pertaining to volatile organic compounds (VOCs), which have specific relevance for respiratory circuit equipment. Here, we measured VOCs emitted from freshly printed stereolithography (SLA) replacement medical parts using proton transfer reaction mass spectrometry and infrared differential absorption spectroscopy, and particulates using a scanning mobility particle sizer. We observed emission factors for individual VOCs ranging from ∼0.001 to ∼10 ng cm-3 min-1. Emissions were heavily dependent on postprint curing and mildly dependent on the type of SLA resin. Curing reduced the emission of all observed chemicals, and no compounds exceeded the recommended dose of 360 µg/d. VOC emissions steadily decreased for all parts over time, with an average e-folding time scale (time to decrease to 1/e of the starting value) of 2.6 ± 0.9 h.

19.
Environ Sci Atmos ; 1(6): 434-448, 2021 Sep 23.
Artigo em Inglês | MEDLINE | ID: mdl-34604755

RESUMO

Aerosol particles negatively affect human health while also having climatic relevance due to, for example, their ability to act as cloud condensation nuclei. Ultrafine particles (diameter D p < 100 nm) typically comprise the largest fraction of the total number concentration, however, their chemical characterization is difficult because of their low mass. Using an extractive electrospray time-of-flight mass spectrometer (EESI-TOF), we characterize the molecular composition of freshly nucleated particles from naphthalene and ß-caryophyllene oxidation products at the CLOUD chamber at CERN. We perform a detailed intercomparison of the organic aerosol chemical composition measured by the EESI-TOF and an iodide adduct chemical ionization mass spectrometer equipped with a filter inlet for gases and aerosols (FIGAERO-I-CIMS). We also use an aerosol growth model based on the condensation of organic vapors to show that the chemical composition measured by the EESI-TOF is consistent with the expected condensed oxidation products. This agreement could be further improved by constraining the EESI-TOF compound-specific sensitivity or considering condensed-phase processes. Our results show that the EESI-TOF can obtain the chemical composition of particles as small as 20 nm in diameter with mass loadings as low as hundreds of ng m-3 in real time. This was until now difficult to achieve, as other online instruments are often limited by size cutoffs, ionization/thermal fragmentation and/or semi-continuous sampling. Using real-time simultaneous gas- and particle-phase data, we discuss the condensation of naphthalene oxidation products on a molecular level.

20.
Environ Sci Technol ; 55(20): 13646-13656, 2021 10 19.
Artigo em Inglês | MEDLINE | ID: mdl-34585932

RESUMO

Gas-phase oxygenated organic molecules (OOMs) can contribute substantially to the growth of newly formed particles. However, the characteristics of OOMs and their contributions to particle growth rate are not well understood in urban areas, which have complex anthropogenic emissions and atmospheric conditions. We performed long-term measurement of gas-phase OOMs in urban Beijing during 2018-2019 using nitrate-based chemical ionization mass spectrometry. OOM concentrations showed clear seasonal variations, with the highest in the summer and the lowest in the winter. Correspondingly, calculated particle growth rates due to OOM condensation were highest in summer, followed by spring, autumn, and winter. One prominent feature of OOMs in this urban environment was a high fraction (∼75%) of nitrogen-containing OOMs. These nitrogen-containing OOMs contributed only 50-60% of the total growth rate led by OOM condensation, owing to their slightly higher volatility than non-nitrate OOMs. By comparing the calculated condensation growth rates and the observed particle growth rates, we showed that sulfuric acid and its clusters are the main contributors to the growth of sub-3 nm particles, with OOMs significantly promoting the growth of 3-25 nm particles. In wintertime Beijing, however, there are missing contributors to the growth of particles above 3 nm, which remain to be further investigated.


Assuntos
Poluentes Atmosféricos , Aerossóis/análise , Poluentes Atmosféricos/análise , Monitoramento Ambiental , Compostos Orgânicos/análise , Tamanho da Partícula , Material Particulado/análise , Estações do Ano
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