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1.
Anal Chem ; 95(6): 3371-3378, 2023 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-36719775

RESUMO

The family of atmospheric oxides of nitrogen, NOy (e.g., nitrogen oxides (NOx) + nitric acid (HNO3) + nitrous acid (HONO) + peroxyacetyl nitrate (PAN) + particulate nitrate (pNO3-) + other), have an influential role in atmospheric chemistry, climate, and the environment. The nitrogen (δ15N) and oxygen (δ18O and Δ17O) stable isotopes of NOy are novel tools for potentially tracking emission sources and quantifying oxidation chemistry. However, there is a lack of well-established methods, particularly for speciated gas-phase components of NOy, to accurately quantify δ15N, δ18O, and Δ17O. This work presents controlled laboratory experiments and complex chamber α-pinene/NOx oxidation experiments of a sampling apparatus constructed for the simultaneous capture of multiple NOy species for isotope analysis using a series of coated denuders, with a focus on nitrogen dioxide (NO2•). The laboratory tests indicate complete NO2• capture for the targeted concentration of 15 ppbv for at least 24 h collections at 10 liters per minute, with δ15N and δ18O precisions of ±1.3‰ and 1.0‰, respectively, and minimal (2.2% ± 0.1%) NO2• collection on upstream denuders utilized for the capture of HNO3 and other acidic gases. The multispecies NOy collection system showed excellent concentration correlations with online instrumentation for both HNO3 and NO2• and isotope reproducibility of ±1.7‰, ±1.8‰, and ±0.7‰ for δ15N, δ18O, and Δ17O, respectively, for replicate experiments and highly time-resolved collections. This work demonstrates a new method that can enable the simultaneous collection of HNO3 and NO2• for accurate quantification of concentration and isotopic composition.

2.
Environ Sci Technol ; 57(2): 1039-1048, 2023 01 17.
Artigo em Inglês | MEDLINE | ID: mdl-36580374

RESUMO

Oxidative stress is a possible mechanism by which ambient fine particulate matter (PM) exerts adverse biological effects. While multiple biological effects and reactive oxygen species (ROS) production have been observed upon PM exposure, whether the biological effects are ROS-mediated remains unclear. Secondary organic aerosols (SOA) constitute a major fraction of fine PM and can contribute substantially to its toxicity. In this work, we measured three types of cell responses (mitochondrial membrane potential (MMP), caspase 3/7 activity, and ROS) and investigated their associations upon exposure to SOA formed from anthropogenic (naphthalene) and biogenic (α-pinene) precursors. MMP and caspase 3/7 activity (an early indicator of apoptosis) are key indicators of cell health, and changes of them could occur downstream of ROS-mediated pathways. We observed a significant increase in caspase 3/7 activity after SOA exposure, suggesting that apoptosis is an important pathway of cell death induced by SOA. We further found strong associations between a decrease in MMP and increase in caspase 3/7 activity with an increase in cellular ROS level. These results suggest that cell health is largely dependent on the cellular ROS level, highlighting oxidative stress as a key mechanism for biological effects from SOA exposure. Linear regression analyses reveal greater changes of the three cellular responses with increasing carbon oxidation state (OSc) of SOA, suggesting that SOA are more toxic when they are more oxidized. Overall, our work provides critical insights into the associations between cell health and ROS level upon SOA exposure and proposes that OSc could be a suitable proxy to assess the overall SOA toxicity.


Assuntos
Poluentes Atmosféricos , Espécies Reativas de Oxigênio/análise , Poluentes Atmosféricos/toxicidade , Poluentes Atmosféricos/análise , Caspase 3/análise , Material Particulado/análise , Aerossóis/análise
3.
Environ Sci Technol ; 57(1): 53-63, 2023 01 10.
Artigo em Inglês | MEDLINE | ID: mdl-36563184

RESUMO

Atmospheric models of secondary organic aerosol (OA) (SOA) typically rely on parameters derived from environmental chambers. Chambers are subject to experimental artifacts, including losses of (1) particles to the walls (PWL), (2) vapors to the particles on the wall (V2PWL), and (3) vapors to the wall directly (VWL). We present a method for deriving artifact-corrected SOA parameters and translating these to volatility basis set (VBS) parameters for use in chemical transport models (CTMs). Our process involves combining a box model that accounts for chamber artifacts (Statistical Oxidation Model with a TwO-Moment Aerosol Sectional model (SOM-TOMAS)) with a pseudo-atmospheric simulation to develop VBS parameters that are fit across a range of OA mass concentrations. We found that VWL led to the highest percentage change in chamber SOA mass yields (high NOx: 36-680%; low NOx: 55-250%), followed by PWL (high NOx: 8-39%; low NOx: 10-37%), while the effects of V2PWL are negligible. In contrast to earlier work that assumed that V2PWL was a meaningful loss pathway, we show that V2PWL is an unimportant SOA loss pathway and can be ignored when analyzing chamber data. Using our updated VBS parameters, we found that not accounting for VWL may lead surface-level OA to be underestimated by 24% (0.25 µg m-3) as a global average or up to 130% (9.0 µg m-3) in regions of high biogenic or anthropogenic activity. Finally, we found that accurately accounting for PWL and VWL improves model-measurement agreement for fine mode aerosol mass concentrations (PM2.5) in the GEOS-Chem model.


Assuntos
Poluentes Atmosféricos , Poluentes Atmosféricos/análise , Artefatos , Gases , Modelos Químicos , Aerossóis/análise
4.
J Phys Chem A ; 127(4): 987-999, 2023 Feb 02.
Artigo em Inglês | MEDLINE | ID: mdl-36651914

RESUMO

Organic nitrates (ONs) can impact spatial distribution of reactive nitrogen species and ozone formation in the atmosphere. While photolysis of ONs is known to result in the release of NO2 back to the atmosphere, the photolysis rate constants and mechanisms of monoterpene-derived ONs (MT-ONs) have not been well constrained. We investigated the gas-phase photolysis of three synthetic ONs derived from α-pinene, ß-pinene, and d-limonene through chamber experiments. The measured photolysis rate constants ranged from (0.55 ± 0.10) × 10-5 to (2.3 ± 0.80) × 10-5 s-1 under chamber black lights. When extrapolated to solar spectral photon flux at a solar zenith angle of 28.14° in summer, the photolysis rate constants were in the range of (4.1 ± 1.4) × 10-5 to (14 ± 6.7) × 10-5 s-1 (corresponding to lifetimes of 2.0 ± 0.96 to 6.8 ± 2.4 h) and (1.7 ± 0.60) × 10-5 to (8.3 ± 4.0) ×10-5 s-1 (3.3 ± 1.6 to 17 ± 6.0 h lifetimes) by using wavelength-dependent and average quantum yields, respectively. Photolysis mechanisms were proposed based on major products detected during photolysis. A zero-dimensional box model was further employed to simulate the photolysis of α-pinene-derived ON under ambient conditions. We found that more than 99% of α-pinene-derived ON can be converted to inorganic nitrogen within 12 h of irradiation and ozone was formed correspondingly. Together, these findings show that photolysis is an important atmospheric sink for MT-ONs and highlight their role in NOx recycling and ozone chemistry.

5.
J Occup Environ Hyg ; 20(1): 23-32, 2023 01.
Artigo em Inglês | MEDLINE | ID: mdl-36344309

RESUMO

Cloth masks are a tool for controlling community transmission during pandemics, as well as during other outbreak situations. However, cloth masks vary in their designs, and the consequences of this variability for their effectiveness as source control have received little attention, particularly in terms of user discomfort and problematic mask-wearing behaviors. In the present studies, common design parameters of cloth masks were systematically varied to ascertain their effect(s) on the subjective discomfort and frequency of problematic mask-wearing behaviors, which detract from the effectiveness of cloth masks as source control. The type of fabric comprising a mask (flannel or twill made of 100% cotton) and the attachment-style of a mask (i.e., ear loops or fabric ties) were varied in adults (18 to 65 years) and children (ages 6 to 11 years). For adults, ear loops were less comfortable than ties (p = .035) and were associated with greater face- (p = .005) and mask-touching (p = .001). Children, however, found flannel masks to be more breathable than twill masks (p = .007) but touched their masks more frequently when wearing a mask made of flannel than twill (p = .033). Common design parameters of cloth masks not only affect user discomfort and behavior but do so differently in adults and children. To improve the effectiveness of cloth masks as source control, the present studies highlight the importance of measuring the effect(s) of design decisions on user discomfort and behavior in different populations.


Assuntos
COVID-19 , Adulto , Criança , Humanos , COVID-19/prevenção & controle , SARS-CoV-2 , Têxteis , Pandemias/prevenção & controle , Tato
6.
Environ Sci Technol ; 56(11): 7063-7073, 2022 06 07.
Artigo em Inglês | MEDLINE | ID: mdl-35357805

RESUMO

Advances in low-cost sensors (LCS) for monitoring air quality have opened new opportunities to characterize air quality in finer spatial and temporal resolutions. In this study, we deployed LCS that measure both gas (CO, NO, NO2, and O3) and particle concentrations and co-located research-grade instruments in Atlanta, GA, to investigate the capability of LCS in resolving air pollutant sources using non-negative matrix factorization (NMF) in a moderately polluted urban area. We provide a comparison of applying the NMF technique to both normalized and non-normalized data sets. We identify four factors with different temporal trends and properties for both normalized and non-normalized data sets. Both normalized and non-normalized LCS data sets can resolve primary organic aerosol (POA) factors identified from research-grade instruments. However, applying normalization provides factors with more diverse compositions and can resolve secondary organic aerosol (SOA). Results from this study demonstrate that LCS not only can be used to provide basic mass concentration information but also can be used for in-depth source apportionment studies even in an urban setting with complex pollution mixtures and relatively low aerosol loadings.


Assuntos
Poluentes Atmosféricos , Poluição do Ar , Aerossóis/análise , Poluentes Atmosféricos/análise , Poluição do Ar/análise , Monitoramento Ambiental/métodos , Material Particulado/análise
7.
Environ Sci Technol ; 55(21): 14595-14606, 2021 11 02.
Artigo em Inglês | MEDLINE | ID: mdl-34668375

RESUMO

The partition of gas-phase organic nitrates (ONs) to aerosols and subsequent hydrolysis are regarded as important loss mechanisms for ON species. However, the hydrolysis mechanisms and the major factors controlling the hydrolysis lifetime are not fully understood. In this work, we synthesized seven monoterpene-derived ONs and systematically investigated their hydrolysis in bulk solutions at different pH values. The hydrolysis lifetimes ranged from 12.9 min to 8.5 h for allylic primary ON and tertiary ONs, but secondary ONs were stable at neutral pH. The alkyl substitution numbers, functional groups, and carbon skeletons were three important factors controlling hydrolysis rates. Tertiary and secondary ONs were found to hydrolyze via the acid-catalyzed unimolecular (SN1) mechanism, while a competition of SN1 and bimolecular (SN2) mechanisms accounted for the hydrolysis of primary ONs. The consistency of experimental and theoretical hydrolysis rates calculated by density functional theory further supported the proposed mechanisms. Reversible reactions including hydrolysis and nitration were first reported to explain the hydrolysis of ONs, highlighting the possibility that particulate nitric acid can participate in nitration to generate new nitrogen-containing compounds. These findings demonstrate that ON hydrolysis is a complex reaction that proceeds via different mechanisms and is controlled by various parameters.


Assuntos
Monoterpenos , Nitratos , Ácidos , Aerossóis , Hidrólise
8.
Environ Sci Technol ; 55(17): 11557-11567, 2021 Sep 07.
Artigo em Inglês | MEDLINE | ID: mdl-34431667

RESUMO

The lockdown due to COVID-19 created a rare opportunity to examine the nonlinear responses of secondary aerosols, which are formed through atmospheric oxidation of gaseous precursors, to intensive precursor emission reductions. Based on unique observational data sets from six supersites in eastern China during 2019-2021, we found that the lockdown caused considerable decreases (32-61%) in different secondary aerosol components in the study region because of similar-degree precursor reductions. However, due to insufficient combustion-related volatile organic compound (VOC) reduction, odd oxygen (Ox = O3 + NO2) concentration, an indicator of the extent of photochemical processing, showed little change and did not promote more decreases in secondary aerosols. We also found that the Chinese provinces and international cities that experienced reduced Ox during the lockdown usually gained a greater simultaneous PM2.5 decrease than other provinces and cities with an increased Ox. Therefore, we argue that strict VOC control in winter, which has been largely ignored so far, is critical in future policies to mitigate winter haze more efficiently by reducing Ox simultaneously.


Assuntos
Poluentes Atmosféricos , Poluição do Ar , COVID-19 , Aerossóis/análise , Poluentes Atmosféricos/análise , Poluição do Ar/análise , Poluição do Ar/prevenção & controle , China , Controle de Doenças Transmissíveis , Monitoramento Ambiental , Humanos , Oxigênio , Material Particulado/análise , SARS-CoV-2
9.
Indoor Air ; 31(5): 1484-1494, 2021 09.
Artigo em Inglês | MEDLINE | ID: mdl-33647175

RESUMO

Air quality in indoor environments can have significant impacts on people's health, comfort, and productivity. Particulate matter (PM; also referred to as aerosols) is an important type of air pollutant, and exposure to outdoor PM has been associated with a variety of diseases. In addition, there is increasing recognition and concern of airborne transmission of viruses, including severe acute respiratory syndrome corona-virus 2 (SARS-CoV-2), especially in indoor environments. Despite its importance, indoor PM data during the COVID-19 pandemic are scarce. In this work, we measured and compared particle number and mass concentrations in aircraft cabins during commercial flights with various indoor environments in Atlanta, GA, during July 2020, including retail stores, grocery stores, restaurants, offices, transportation, and homes. Restaurants had the highest particle number and mass concentrations, dominated by cooking emissions, while in-flight aircraft cabins had the lowest observed concentrations out of all surveyed spaces.


Assuntos
Poluição do Ar em Ambientes Fechados/análise , Poluição do Ar , Material Particulado/análise , Aeronaves/estatística & dados numéricos , COVID-19/epidemiologia , Culinária , Monitoramento Ambiental , Habitação/estatística & dados numéricos , Humanos , Tamanho da Partícula , Restaurantes/estatística & dados numéricos , SARS-CoV-2 , Supermercados
10.
Environ Sci Technol ; 54(20): 13121-13130, 2020 10 20.
Artigo em Inglês | MEDLINE | ID: mdl-32914962

RESUMO

Health risks associated with exposure to ambient particulate matter (PM) are a major concern around the world. Adverse PM health effects have been proposed to be linked to oxidative stress through the generation of reactive oxygen species (ROS). In vitro cellular assays can provide insights into components or characteristics of PM that best account for its toxicity at a cellular level. However, most current assays report cell population averages and are mostly time endpoint measurements and thus provide no temporal information. This poses limitations on our understanding of PM health effects. In this study, we developed a microfluidic assay that can measure cellular ROS responses at the single-cell level and evaluate temporal dynamic behavior of single cells. We first established a protocol that enables culturing cells in our microfluidic platform and that can provide reproducible ROS readouts. We further examined the heterogeneous ROS responses of cell populations and tracked the dynamics of individual cellular responses upon exposure to different concentrations of PM extracts. Our results show that in an alveolar macrophage cell line, cellular ROS responses are highly heterogeneous. ROS responses from different cells can vary over an order of magnitude, and large coefficients of variation at each timepoint measurement indicate a high variability. The dynamic behavior of single-cell responses is strongly dependent on PM concentrations. Our work serves as a proof-of-principle demonstration of the capability of our microfluidic technology to study time-resolved single-cell responses upon PM exposure. We envision applying this high-resolution, high-content assay to investigate a wide array of single-cell responses (beyond ROS) upon exposure to different types of PM in the future.


Assuntos
Poluentes Atmosféricos , Material Particulado , Poluentes Atmosféricos/análise , Macrófagos Alveolares , Estresse Oxidativo , Material Particulado/análise , Material Particulado/toxicidade , Espécies Reativas de Oxigênio/farmacologia
11.
Environ Sci Technol ; 53(9): 5176-5186, 2019 05 07.
Artigo em Inglês | MEDLINE | ID: mdl-30939000

RESUMO

Organosulfur compounds are important components of secondary organic aerosols (SOA). While the Aerodyne high-resolution time-of-flight aerosol mass spectrometer (AMS) has been extensively used in aerosol studies, the response of the AMS to organosulfur compounds is not well-understood. Here, we investigated the fragmentation patterns of organosulfurs and inorganic sulfates in the AMS, developed a method to deconvolve total sulfate into components of inorganic and organic origins, and applied this method in both laboratory and field measurements. Apportionment results from laboratory isoprene photooxidation experiment showed that with inorganic sulfate seed, sulfate functionality of organic origins can contribute ∼7% of SOA mass at peak growth. Results from measurements in the Southeastern U.S. showed that 4% of measured sulfate is from organosulfur compounds. Methanesulfonic acid was estimated for measurements in the coastal and remote marine boundary layer. We explored the application of this method to unit mass-resolution data, where it performed less well due to interferences. Our apportionment results demonstrate that organosulfur compounds could be a non-negligible source of sulfate fragments in AMS laboratory and field data sets. A reevaluation of previous AMS measurements over the full range of atmospheric conditions using this method could provide a global estimate/constraint on the contribution of organosulfur compounds.


Assuntos
Poluentes Atmosféricos , Sulfatos , Aerossóis , Espectrometria de Massas , Sudeste dos Estados Unidos , Compostos de Enxofre
12.
Proc Natl Acad Sci U S A ; 113(6): 1516-21, 2016 Feb 09.
Artigo em Inglês | MEDLINE | ID: mdl-26811465

RESUMO

Speciated particle-phase organic nitrates (pONs) were quantified using online chemical ionization MS during June and July of 2013 in rural Alabama as part of the Southern Oxidant and Aerosol Study. A large fraction of pONs is highly functionalized, possessing between six and eight oxygen atoms within each carbon number group, and is not the common first generation alkyl nitrates previously reported. Using calibrations for isoprene hydroxynitrates and the measured molecular compositions, we estimate that pONs account for 3% and 8% of total submicrometer organic aerosol mass, on average, during the day and night, respectively. Each of the isoprene- and monoterpenes-derived groups exhibited a strong diel trend consistent with the emission patterns of likely biogenic hydrocarbon precursors. An observationally constrained diel box model can replicate the observed pON assuming that pONs (i) are produced in the gas phase and rapidly establish gas-particle equilibrium and (ii) have a short particle-phase lifetime (∼2-4 h). Such dynamic behavior has significant implications for the production and phase partitioning of pONs, organic aerosol mass, and reactive nitrogen speciation in a forested environment.

13.
Proc Natl Acad Sci U S A ; 112(1): 37-42, 2015 Jan 06.
Artigo em Inglês | MEDLINE | ID: mdl-25535345

RESUMO

Secondary organic aerosol (SOA) constitutes a substantial fraction of fine particulate matter and has important impacts on climate and human health. The extent to which human activities alter SOA formation from biogenic emissions in the atmosphere is largely undetermined. Here, we present direct observational evidence on the magnitude of anthropogenic influence on biogenic SOA formation based on comprehensive ambient measurements in the southeastern United States (US). Multiple high-time-resolution mass spectrometry organic aerosol measurements were made during different seasons at various locations, including urban and rural sites in the greater Atlanta area and Centreville in rural Alabama. Our results provide a quantitative understanding of the roles of anthropogenic SO2 and NOx in ambient SOA formation. We show that isoprene-derived SOA is directly mediated by the abundance of sulfate, instead of the particle water content and/or particle acidity as suggested by prior laboratory studies. Anthropogenic NOx is shown to enhance nighttime SOA formation via nitrate radical oxidation of monoterpenes, resulting in the formation of condensable organic nitrates. Together, anthropogenic sulfate and NOx can mediate 43-70% of total measured organic aerosol (29-49% of submicron particulate matter, PM1) in the southeastern US during summer. These measurements imply that future reduction in SO2 and NOx emissions can considerably reduce the SOA burden in the southeastern US. Updating current modeling frameworks with these observational constraints will also lead to more accurate treatment of aerosol formation for regions with substantial anthropogenic-biogenic interactions and consequently improve air quality and climate simulations.

15.
Environ Sci Technol ; 51(1): 78-88, 2017 01 03.
Artigo em Inglês | MEDLINE | ID: mdl-27997132

RESUMO

We developed a novel system for direct and online characterization of water-solubility of organic aerosol (OA) by coupling a Particle Into Liquid Sampler (PILS) to a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). We showed that approximately 88% and 77% of OA are water-soluble in rural Centreville, Alabama and urban Atlanta, Georgia, respectively. The water-solubility of OA factors, resolved with Positive Matrix Factorization analysis of AMS data, is directly investigated for the first time. Above 80% of isoprene-derived OA is water-soluble and its water-soluble fraction has the least variability among all OA factors. This is consistent with that the majority of this factor represents OA formed through the aqueous-phase reaction of isoprene epoxydiols. More-oxidized oxygenated OA is dominantly water-soluble, consistent with this factor representing highly oxidized compounds. Less-oxidized oxygenated OA has the lowest water-solubility among all secondary OA factors, which agrees with the hypothesis that this factor in the southeastern U.S. includes contributions from organic nitrates. While hydrocarbon-like OA is largely water-insoluble, biomass burning OA and cooking OA have the largest range of water-soluble fraction. This study on the water-solubility of OA factors provides insights for interpretation of OA factors and improves understanding of the complex OA sources in the atmosphere.


Assuntos
Aerossóis , Água , Atmosfera , Espectrometria de Massas , Compostos Orgânicos , Solubilidade
16.
Environ Sci Technol ; 51(14): 7831-7841, 2017 Jul 18.
Artigo em Inglês | MEDLINE | ID: mdl-28628304

RESUMO

Nitrate radical (NO3) oxidation of biogenic volatile organic compounds (BVOC) is important for nighttime secondary organic aerosol (SOA) formation. SOA produced at night may evaporate the following morning due to increasing temperatures or dilution of semivolatile compounds. We isothermally dilute the oxidation products from the limonene+NO3 reaction at 25 °C and observe negligible evaporation of organic aerosol via dilution. The SOA yields from limonene+NO3 are approximately constant (∼174%) at 25 °C and range from 81 to 148% at 40 °C. Based on the difference in yields between the two temperatures, we calculated an effective enthalpy of vaporization of 117-237 kJ mol-1. The aerosol yields at 40 °C can be as much as 50% lower compared to 25 °C. However, when aerosol formed at 25 °C is heated to 40 °C, only about 20% of the aerosol evaporates, which could indicate a resistance to aerosol evaporation. To better understand this, we probe the possibility that SOA from limonene+NO3 and ß-pinene+NO3 reactions is highly viscous. We demonstrate that particle morphology and evaporation is dependent on whether SOA from limonene is formed before or during the formation of SOA from ß-pinene. This difference in particle morphology is present even at high relative humidity (∼70%).


Assuntos
Aerossóis , Poluentes Atmosféricos , Monoterpenos , Umidade , Temperatura
17.
Environ Sci Technol ; 51(5): 2519-2528, 2017 03 07.
Artigo em Inglês | MEDLINE | ID: mdl-28169528

RESUMO

Laboratory studies of atmospheric chemistry characterize the nature of atmospherically relevant processes down to the molecular level, providing fundamental information used to assess how human activities drive environmental phenomena such as climate change, urban air pollution, ecosystem health, indoor air quality, and stratospheric ozone depletion. Laboratory studies have a central role in addressing the incomplete fundamental knowledge of atmospheric chemistry. This article highlights the evolving science needs for this community and emphasizes how our knowledge is far from complete, hindering our ability to predict the future state of our atmosphere and to respond to emerging global environmental change issues. Laboratory studies provide rich opportunities to expand our understanding of the atmosphere via collaborative research with the modeling and field measurement communities, and with neighboring disciplines.


Assuntos
Mudança Climática , Ozônio/química , Poluição do Ar , Atmosfera/química , Ecossistema , Humanos
18.
Environ Sci Technol ; 50(1): 222-31, 2016 Jan 05.
Artigo em Inglês | MEDLINE | ID: mdl-26618657

RESUMO

The nitrate radical (NO3) is the dominant nighttime oxidant in most urban and rural environments and reacts rapidly with biogenic volatile organic compounds to form secondary organic aerosol (SOA) and organic nitrates (ON). Here, we study the formation of SOA and ON from the NO3 oxidation of two monoterpenes (α-pinene and ß-pinene) and investigate how they evolve during photochemical aging. High SOA mass loadings are produced in the NO3+ß-pinene reaction, during which we detected 41 highly oxygenated gas- and particle-phase ON possessing 4 to 9 oxygen atoms. The fraction of particle-phase ON in the ß-pinene SOA remains fairly constant during photochemical aging. In contrast to the NO3+ß-pinene reaction, low SOA mass loadings are produced during the NO3+α-pinene reaction, during which only 5 highly oxygenated gas- and particle-phase ON are detected. The majority of the particle-phase ON evaporates from the α-pinene SOA during photochemical aging, thus exhibiting a drastically different behavior from that of ß-pinene SOA. Our results indicate that nighttime ON formed by NO3+monoterpene chemistry can serve as either permanent or temporary NOx sinks depending on the monoterpene precursor.


Assuntos
Aerossóis/química , Poluentes Atmosféricos/química , Compostos Bicíclicos com Pontes/química , Monoterpenos/química , Nitratos/química , Monoterpenos Bicíclicos , Compostos Orgânicos Voláteis/química
19.
Environ Sci Technol ; 49(7): 4646-56, 2015 Apr 07.
Artigo em Inglês | MEDLINE | ID: mdl-25748105

RESUMO

We compare the relative toxicity of various organic aerosol (OA) components identified by an aerosol mass spectrometer (AMS) based on their ability to generate reactive oxygen species (ROS). Ambient fine aerosols were collected from urban (three in Atlanta, GA and one in Birmingham, AL) and rural (Yorkville, GA and Centerville, AL) sites in the Southeastern United States. The ROS generating capability of the water-soluble fraction of the particles was measured by the dithiothreitol (DTT) assay. Water-soluble PM extracts were further separated into the hydrophobic and hydrophilic fractions using a C-18 column, and both fractions were analyzed for DTT activity and water-soluble metals. Organic aerosol composition was measured at selected sites using a high-resolution time-of-flight AMS. Positive matrix factorization of the AMS spectra resolved the organic aerosol into isoprene-derived OA (Isop_OA), hydrocarbon-like OA (HOA), less-oxidized oxygenated OA, (LO-OOA), more-oxidized OOA (MO-OOA), cooking OA (COA), and biomass burning OA (BBOA). The association of the DTT activity of water-soluble PM2.5 (WS_DTT) with these factors was investigated by linear regression techniques. BBOA and MO-OOA were most consistently linked with WS_DTT, with intrinsic water-soluble activities of 151 ± 20 and 36 ± 22 pmol/min/µg, respectively. Although less toxic, MO-OOA was most widespread, contributing to WS_DTT activity at all sites and during all seasons. WS_DTT activity was least associated with biogenic secondary organic aerosol. The OA components contributing to WS_DTT were humic-like substances (HULIS), which are abundantly emitted in biomass burning (BBOA) and include highly oxidized OA from multiple sources (MO-OOA). Overall, OA contributed approximately 60% to the WS_DTT activity, with the remaining probably from water-soluble metals, which were mostly associated with the hydrophilic WS_DTT fraction.


Assuntos
Aerossóis/toxicidade , Poluentes Atmosféricos/toxicidade , Espécies Reativas de Oxigênio/análise , Alabama , Cidades , Ditiotreitol/química , Georgia , Espectrometria de Massas , Modelos Teóricos , Compostos Orgânicos/toxicidade , Solubilidade
20.
bioRxiv ; 2024 May 14.
Artigo em Inglês | MEDLINE | ID: mdl-38798413

RESUMO

Dysregulated neutrophil recruitment drives many pulmonary diseases, but most preclinical screening methods are unsuited to evaluate pulmonary neutrophilia, limiting progress towards therapeutics. Namely, high throughput therapeutic screening systems typically exclude critical neutrophilic pathophysiology, including blood-to-lung recruitment, dysfunctional activation, and resulting impacts on the air-blood barrier. To meet the conflicting demands of physiological complexity and high throughput, we developed an assay of 96-well Leukocyte recruitment in an Air-Blood Barrier Array (L-ABBA-96) that enables in vivo -like neutrophil recruitment compatible with downstream phenotyping by automated flow cytometry. We modeled acute respiratory distress syndrome (ARDS) with neutrophil recruitment to 20 ng/mL epithelial-side interleukin 8 (IL-8) and found a dose dependent reduction in recruitment with physiologic doses of baricitinib, a JAK1/2 inhibitor recently FDA-approved for severe COVID-19 ARDS. Additionally, neutrophil recruitment to patient-derived cystic fibrosis sputum supernatant induced disease-mimetic recruitment and activation of healthy donor neutrophils and upregulated endothelial e-selectin. Compared to 24-well assays, the L-ABBA-96 reduces required patient sample volumes by 25 times per well and quadruples throughput per plate. Compared to microfluidic assays, the L-ABBA-96 recruits two orders of magnitude more neutrophils per well, enabling downstream flow cytometry and other standard biochemical assays. This novel pairing of high-throughput in vitro modeling of organ-level lung function with parallel high-throughput leukocyte phenotyping substantially advances opportunities for pathophysiological studies, personalized medicine, and drug testing applications.

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