Molecular-Level Insights into the Relationship between Volatility of Organic Aerosol Constituents and PM2.5 Air Pollution Levels: A Study with Ultrahigh-Resolution Mass Spectrometry.

Volatility of organic aerosols (OAs) significantly influences new particle formation and the occurrence of particulate air pollution. However, the relationship between the volatility of OA and the level of particulate air pollution (i.e., particulate matter concentration) is not well understood. In this study, we compared the chemical composition (identified by an ultrahigh-resolution Orbitrap mass spectrometer) and volatility (estimated based on a predeveloped parametrization method) of OAs in urban PM2.5 (particulate matter with aerodynamic diameter ≤ 2.5 µm) samples from seven German and Chinese cities, where the PM2.5 concentration ranged from a light (14 µg m-3) to heavy (319 µg m-3) pollution level. A large fraction (71-98%) of compounds in PM2.5 samples were attributable to intermediate-volatility organic compounds (IVOCs) and semivolatile organic compounds (SVOCs). The fraction of low-volatility organic compounds (LVOCs) and extremely low-volatility organic compounds (ELVOCs) decreased from clean (28%) to heavily polluted urban regions (2%), while that of IVOCs increased from 34 to 62%. We found that the average peak area-weighted volatility of organic compounds in different cities showed a logarithmic correlation with the average PM2.5 concentration, indicating that the volatility of urban OAs increases with the increase of air pollution level. Our results provide new insights into the relationship between OA volatility and PM pollution levels and deepen the understanding of urban air pollutant evolution.

Linked fire activity and climate whiplash in California during the early Holocene.

Recent wildfire activity in semi-arid regions like western North America exceeds the range of historical records. High-resolution paleoclimate archives such as stalagmites could illuminate the link between hydroclimate, vegetation change, and fire activity in pre-anthropogenic climate states beyond the timescale of existing tree-ring records. Here we present an analysis of levoglucosan, a combustion-sensitive anhydrosugar, and lignin oxidation products (LOPs) in a stalagmite, reconstructing fire activity and vegetation composition in the California Coast Range across the 8.2 kyr event. Elevated levoglucosan concentrations suggest increased fire activity while altered LOP compositions indicate a shift toward more woody vegetation during the event. These changes are concurrent with increased hydroclimate volatility as shown by carbon and calcium isotope proxies. Together, these records suggest that climate whiplash (oscillations between extreme wetness and aridity) and fire activity in California, both projected to increase with anthropogenic climate change, were tightly coupled during the early Holocene.

Ozonolysis of α-Pinene and Δ3-Carene Mixtures: Formation of Dimers with Two Precursors.

The formation of secondary organic aerosol (SOA) from the structurally similar monoterpenes, α-pinene and Δ3-carene, differs substantially. The aerosol phase is already complex for a single precursor, and when mixtures are oxidized, products, e.g., dimers, may form between different volatile organic compounds (VOCs). This work investigates whether differences in SOA formation and properties from the oxidation of individual monoterpenes persist when a mixture of the monoterpenes is oxidized. Ozonolysis of α-pinene, Δ3-carene, and a 1:1 mixture of them was performed in the Aarhus University Research on Aerosol (AURA) atmospheric simulation chamber. Here, ∼100 ppb of monoterpene was oxidized by 200 ppb O3 under dark conditions at 20 °C. The particle number concentration and particle mass concentration for ozonolysis of α-pinene exceed those from ozonolysis of Δ3-carene alone, while their mixture results in concentrations similar to α-pinene ozonolysis. Detailed offline analysis reveals evidence of VOC-cross-product dimers in SOA from ozonolysis of the monoterpene mixture: a VOC-cross-product dimer likely composed of the monomeric units cis-caric acid and 10-hydroxy-pinonic acid and a VOC-cross-product dimer ester likely from the monomeric units caronaldehyde and terpenylic acid were tentatively identified by liquid chromatography-mass spectrometry. To improve the understanding of chemical mechanisms determining SOA, it is relevant to identify VOC-cross-products.

Observing volcanoes with drones: studies of volcanic plume chemistry with ultralight sensor systems.

The study of the chemical composition of volcanic emissions is an important method for obtaining information about volcanic systems and providing indirect and unique insights into magmatic processes. However, there is a non-negligible risk associated with sampling directly at volcanic craters or maintaining geochemical monitoring stations at such locations. Spectroscopic remote sensing methods, in turn, can measure only a few species. Here, drones offer the opportunity to bring measurement systems to the scene. Standard parameters that are commonly measured are SO2 and CO2 concentrations, as well as a number of meteorological parameters. The in-flight transmission of data by radio telemetry plays an important role, since visual localization of the volcanic plume from a distance of several kilometers is practically impossible. Until now, larger and quite cost-intensive drones have been used for this purpose, which must first be transported to the site of operation at great expense. Here, we present the development and successful deployment of a very small drone system (empty weight < 0.9 kg) for chemical characterization of volcanic plumes that can be easily transported on foot to difficult-to-access terrain and, moreover, requires only minimal flight and administrative preparations for operation as an aerial observation platform.

Heterogeneous iodine-organic chemistry fast-tracks marine new particle formation.

The gas-phase formation of new particles less than 1 nm in size and their subsequent growth significantly alters the availability of cloud condensation nuclei (CCN, >30-50 nm), leading to impacts on cloud reflectance and the global radiative budget. However, this growth cannot be accounted for by condensation of typical species driving the initial nucleation. Here, we present evidence that nucleated iodine oxide clusters provide unique sites for the accelerated growth of organic vapors to overcome the coagulation sink. Heterogeneous reactions form low-volatility organic acids and alkylaminium salts in the particle phase, while further oligomerization of small α-dicarbonyls (e.g., glyoxal) drives the particle growth. This identified heterogeneous mechanism explains the occurrence of particle production events at organic vapor concentrations almost an order of magnitude lower than those required for growth via condensation alone. A notable fraction of iodine associated with these growing particles is recycled back into the gas phase, suggesting an effective transport mechanism for iodine to remote regions, acting as a "catalyst" for nucleation and subsequent new particle production in marine air.

Towards comprehensive non-target screening using heart-cut two-dimensional liquid chromatography for the analysis of organic atmospheric tracers in ice cores.

Non-target screening of secondary organic aerosol compounds in ice cores is used to reconstruct atmospheric conditions and sources and is a valuable tool to elucidate the chemical profiles of samples with the aim to obtain as much information as possible from one mass spectrometric measurement. The coupling of mass spectrometry to chromatography limits the results of a non-target screening to signals of compounds within a certain polarity range based on the utilized stationary phases of the columns. Comprehensive two-dimensional liquid chromatography (LCxLC) introduces a second column of different functionality to enable the analysis of a broader range of analytes. Conventional LCxLC requires complex instrumental setups and is difficult to implement for most laboratories. In this work we demonstrate an approach to approximate a comprehensive non-target screening using a simple instrumental setup employing two columns of orthogonal functionalities (HILIC and reversed-phase), an additional pump, and an additional six-port valve. The void volume of the first dimension is transferred to the reversed-phase column to analyze low-polarity compounds during the re-equilibration of the HILIC. Method validation showed adequate repeatability and detection limits for two selected void volume markers and application to snow samples collected at the high-alpine research station Jungfraujoch yielded a total of 270 signals. Comparison to the one-dimensional HILIC approach revealed 175 signals exclusively detected in the two-dimensional method, of which 23 were detected in the second dimension. Detailed analysis of the chemical composition showed consistency with expected compounds in snow samples like lignin or cellulose combustion products from biomass burning or secondary organic aerosol constituents. The results confirmed that one-dimensional chromatography was not sufficient to cover the entire range of compounds and the developed two-dimensional approach will improve the information content from non-target screening while maintaining time of analysis and a simple instrumental setup.

High-Resolution Fluorescence Spectra of Airborne Biogenic Secondary Organic Aerosols: Comparisons to Primary Biological Aerosol Particles and Implications for Single-Particle Measurements.

Aqueous extracts of biogenic secondary organic aerosols (BSOAs) have been found to exhibit fluorescence that may interfere with the laser/light-induced fluorescence (LIF) detection of primary biological aerosol particles (PBAPs). In this study, we quantified the interference of BSOAs to PBAPs by directly measuring airborne BSOA particles, rather than aqueous extracts. BSOAs were generated by the reaction of d-limonene (LIM) or α-pinene (PIN) and ozone (O3) with or without ammonia in a chamber under controlled conditions. With an excitation wavelength of 355 nm, BSOAs exhibited peak emissions at 464-475 nm, while fungal spores exhibited peak emissions at 460-483 nm; the fluorescence intensity of BSOAs with diameters of 0.7 µm was in the same order of magnitude as that of fungal spores with diameters of 3 µm. The number fraction of 0.7 µm BSOAs that exhibited fluorescence above the threshold was in the range of 1.9-15.9%, depending on the species of precursors, relative humidity (RH), and ammonia. Similarly, the number fraction of 3 µm fungal spores that exhibited fluorescence above the threshold was 4.9-36.2%, depending on the species of fungal spores. Normalized fluorescence by particle volumes suggests that BSOAs exhibited fluorescence in the same order of magnitude as pollen and 10-100 times higher than that of fungal spores. A comparison with ambient particles suggests that BSOAs caused significant interference to ambient fine particles (15 of 16 ambient fine particle measurements likely detected BSOAs) and the interference was smaller for ambient coarse particles (4 of 16 ambient coarse particle measurements likely detected BSOAs) when using LIF instruments.

High Pressure Inside Nanometer-Sized Particles Influences the Rate and Products of Chemical Reactions.

The composition of organic aerosol has a pivotal influence on aerosol properties such as toxicity and cloud droplet formation capability, which could affect both climate and air quality. However, a comprehensive and fundamental understanding of the chemical and physical processes that occur in nanometer-sized atmospheric particles remains a challenge that severely limits the quantification and predictive capabilities of aerosol formation pathways. Here, we investigated the effects of a fundamental and hitherto unconsidered physical property of nanoparticles-the Laplace pressure. By studying the reaction of glyoxal with ammonium sulfate, both ubiquitous and important atmospheric constituents, we show that high pressure can significantly affect the chemical processes that occur in atmospheric ultrafine particles (i.e., particles < 100 nm). Using high-resolution mass spectrometry and UV-vis spectroscopy, we demonstrated that the formation of reaction products is strongly (i.e., up to a factor of 2) slowed down under high pressures typical of atmospheric nanoparticles. A size-dependent relative rate constant is determined and numerical simulations illustrate the reduction in the production of the main glyoxal reaction products. These results established that the high pressure inside nanometer-sized aerosols must be considered as a key property that significantly impacts chemical processes that govern atmospheric aerosol growth and evolution.

Measurement report of the change of PM2.5 composition during the COVID-19 lockdown in urban Xi'an: Enhanced secondary formation and oxidation.

Enhanced secondary aerosol formation was observed during the COVID-19 lockdown in Xi'an, especially for polluted episodes. More oxidized­oxygenated organic aerosol (MO-OOA) and sulfate showed the dominant enhancements, especially in large particle-mode. Meanwhile, relative humidity (RH) showed a positive promotion on the formation of sulfate and MO-OOA during the lockdown, but had no obvious correlation with less oxidized­oxygenated organic aerosol (LO-OOA) or nitrate. Organosulfurs (OS) displayed a higher contribution (~58%) than inorganic sulfate to total sulfate enhancement in the polluted episode during the lockdown. Although the total nitrate (TN) decreased during the lockdown ascribing to a larger reduction of inorganic nitrate, organic nitrate (ON) showed an obvious increase from pre-lockdown (0.5 ± 0.6 µg m-3 and 1 ± 2% of TN) to lockdown (5.3 ± 3.1 µg m-3 and 17 ± 9% of TN) in the polluted case (P < 0.05). In addition, RH also displayed a positive promotion on the formation of ON and OS, and the increases of both OS and ON were much efficient in the nighttime than in the daytime. These results suggest that higher RH and stagnant meteorology might facilitate the sulfate and MO-OOA enhancement, especially in the nighttime, which dominated the secondary aerosol enhancement in haze pollution during the lockdown.

Concentrations, optical properties and sources of humic-like substances (HULIS) in fine particulate matter in Xi'an, Northwest China.

Humic-like substances (HULIS) are ubiquitous in the atmospheric environment, which affects both human health and climate. We present here the mass concentration and optical characteristics of HULIS isolated from aerosol samples collected in Xi'an, China. Both mass concentration and absorption coefficient (Abs365) of HULIS show clear seasonal differences, with the highest average in winter (3.91 µgC m-3 and 4.78 M m-1, respectively) and the lowest in summer (0.65 µgC m-3 and 0.55 M m-1, respectively). The sources of HULIS_C and light absorption of HULIS were analyzed by positive matrix factorization (PMF) and four major sources were resolved, including secondary formation, biomass burning, coal burning, and vehicle emission. Our results show that secondary formation (i.e., gas-to-particle conversion from e.g., photochemical oxidation) was the major contributor to both HULIS_C (50%) and light absorption (55%) of HULIS in summer, biomass burning and coal burning were major sources of HULIS_C (~70%) and light absorption (~80%) of HULIS in winter. It is worth noting that biomass burning and coal burning had higher contribution to HULIS light absorption (47% in spring, 37% in summer, 73% in fall, and 77% in winter) than their corresponding contribution to HULIS_C concentration (41% in spring, 37% in summer, 54% in fall, and 69% in winter). However, vehicle emission had lower contribution to HULIS light absorption (26% in spring, 8% in summer, 18% in fall, and 11% in winter) than to HULIS_C concentration (24% in spring, 13% in summer, 28% in fall, and 18% in winter). These results suggest that HULIS from biomass burning and coal burning have higher light absorption ability than from vehicle emission.

The maximum carbonyl ratio (MCR) as a new index for the structural classification of secondary organic aerosol components.

RATIONALE: Organic aerosols (OA) account for a large fraction of atmospheric fine particulate matter and thus are affecting climate and public health. Elucidation of the chemical composition of OA is the key for addressing the role of ambient fine particles at the atmosphere-biosphere interface and mass spectrometry is the main method to achieve this goal. METHODS: High-resolution mass spectrometry (HRMS) is on its way to becoming one of the most prominent analytical techniques, also for the analysis of atmospheric aerosols. The combination of high mass resolution and accurate mass determination allows the elemental compositions of numerous compounds to be easily elucidated. Here a new parameter for the improved classification of OA is introduced - the maximum carbonyl ratio (MCR) - which is directly derived from the molecular composition and is particularly suitable for the identification and characterization of secondary organic aerosols (SOA). RESULTS: The concept is exemplified by the analysis of ambient OA samples from two measurement sites (Hyytiälä, Finland; Beijing, China) and of laboratory-generated SOA based on ultrahigh-performance liquid chromatography (UHPLC) coupled to Orbitrap MS. To interpret the results, MCR-Van Krevelen (VK) diagrams are generated for the different OA samples and the individual compounds are categorized into specific areas in the diagrams. The results show that the MCR index is a valuable parameter for representing atmospheric SOA components in composition and structure-dependent visualization tools such as VK diagrams. CONCLUSIONS: The MCR index is suggested as a tool for a better characterization of the sources and the processing of atmospheric OA components based on HRMS data. Since the MCR contains information on the concentration of highly electrophilic organic compounds in particulate matter (PM) as well as on the concentration of organic (hydro)peroxides, the MCR could be a promising metric for identifying health-related particulate matter parameters by HRMS.

One-year characterization of organic aerosol markers in urban Beijing: Seasonal variation and spatiotemporal comparison.

Organic aerosol (OA) is a major component of fine particulate matter (PM); however, only 10%-30% of OA have been identified as individual compounds, and some are used as markers to trace the sources and formation mechanisms of OA. The temporal and spatial coverage of these OA markers nonetheless remain inadequately characterized. This study presents a year-long measurement of 92 organic markers in PM2.5 samples collected at an urban site in Beijing from 2014 to 2015. Saccharides were the most abundant (340.1 ng m-3) species detected, followed by phthalic acids (283.4 ng m-3). In summer, high proportions (8%-24%) of phthalic acids, n-alkanes, fatty acids, and n-alcohols indicate dominant contributions of biogenic emission and atmospheric oxidation to OA in Beijing. In winter, when anthropogenic sources prevail, saccharides, polycyclic aromatic hydrocarbons, and hopanes are more prominent (4%-25%). The spatial distributions of these OA markers in China show higher concentrations in northern cities (mainly from coal combustion and biomass burning) than in southern cities (mainly from vehicular emission). The inter-annual variations of OA markers, except for hopanes, from 2001 to 2015 suggest significant alleviation of the primary OA pollution in Beijing, with an average reduction of 35%-89% compared with those before 2008. The diagnostic ratio analyses between OA markers indicate that contributions from coal combustion and biomass burning decreased, whereas those from vehicular emission increased. Increasingly large vehicle fleets have increased hopane concentrations since 2008, but the levels were 35% lower in 2015 than those in 2010-2011 because of the tightening of emission controls for vehicles. This study provides a long-term and geographical comparison (from Beijing to other locations in China and beyond) of OA markers, demonstrating the temporal and spatial variations in primary OA, and calls for more studies on secondary OA.

Water-Insoluble Organics Dominate Brown Carbon in Wintertime Urban Aerosol of China: Chemical Characteristics and Optical Properties.

The chromophores responsible for light absorption in atmospheric brown carbon (BrC) are not well characterized, which hinders our understanding of BrC chemistry, the links with optical properties, and accurate model representations of BrC to global climate and atmospheric oxidative capacity. In this study, the light absorption properties and chromophore composition of three BrC fractions of different polarities were characterized for urban aerosol collected in Xi'an and Beijing in winter 2013-2014. These three BrC fractions show large differences in light absorption and chromophore composition, but the chromophores responsible for light absorption are similar in Xi'an and Beijing. Water-insoluble BrC (WI-BrC) fraction dominates the total BrC absorption at 365 nm in both Xi'an (51 ± 5%) and Beijing (62 ± 13%), followed by a humic-like fraction (HULIS-BrC) and high-polarity water-soluble BrC. The major chromophores identified in HULIS-BrC are nitrophenols and carbonyl oxygenated polycyclic aromatic hydrocarbons (OPAHs) with 2-3 aromatic rings (in total 18 species), accounting for 10% and 14% of the light absorption of HULIS-BrC at 365 nm in Xi'an and Beijing, respectively. In comparison, the major chromophores identified in WI-BrC are PAHs and OPAHs with 4-6 aromatic rings (in total 16 species), contributing 6% and 8% of the light absorption of WI-BrC at 365 nm in Xi'an and Beijing, respectively.

Charged Tags for the Identification of Oxidative Drug Metabolites Based on Electrochemistry and Mass Spectrometry.

Most of the active pharmaceutical ingredients like Metoprolol are oxidatively metabolized by liver enzymes, such as Cytochrome P450 monooxygenases into oxygenates and therefore hydrophilic products. It is of utmost importance to identify the metabolites and to gain knowledge on their toxic impacts. By using electrochemistry, it is possible to mimic enzymatic transformations and to identify metabolic hot spots. By introducing charged-tags into the intermediate, it is possible to detect and isolate metabolic products. The identification and synthesis of initially oxidized metabolites are important to understand possible toxic activities. The gained knowledge about the metabolism will simplify interpretation and predictions of metabolitic pathways. The oxidized products were analyzed with high performance liquid chromatography-mass spectrometry using electrospray ionization (HPLC-ESI-MS) and nuclear magnetic resonance (NMR) spectroscopy. For proof-of-principle, we present a synthesis of one pyridinated main oxidation product of Metoprolol.

Effects of NH3 and alkaline metals on the formation of particulate sulfate and nitrate in wintertime Beijing.

Sulfate and nitrate from secondary reactions remain as the most abundant inorganic species in atmospheric particle matter (PM). Their formation is initiated by oxidation (either in gas phase or particle phase), followed by neutralization reaction primarily by NH3, or by other alkaline species such as alkaline metal ions if available. The different roles of NH3 and metal ions in neutralizing H2SO4 or HNO3, however, are seldom investigated. Here we conducted semi-continuous measurements of SO42-, NO3-, NH4+, and their gaseous precursors, as well as alkaline metal ions (Na+, K+, Ca2+, and Mg2+) in wintertime Beijing. Analysis of aerosol acidity (estimated from a thermodynamic model) indicated that preferable sulfate formation was related to low pH conditions, while high pH conditions promote nitrate formation. Data in different mass fraction ranges of alkaline metal ions showed that in some ranges the role of NH3 was replaced by alkaline metal ions in the neutralization reaction of H2SO4 and HNO3 to form particulate SO42- and NO3-. The relationships between mass fractions of SO42- and NO3- in those ranges of different alkaline metal ion content also suggested that alkaline metal ions participate in the competing neutralization reaction of sulfate and nitrate. The implication of the current study is that in some regions the chemistry to incorporate sulfur and nitrogen into particle phase might be largely affected by desert/fugitive dust and sea salt, besides NH3. This implication is particularly relevant in coastal China and those areas with strong influence of dust storm in the North China Plain (NCP), both of which host a number of megacities with deteriorating air quality.

Short-term e-cigarette vapour exposure causes vascular oxidative stress and dysfunction: evidence for a close connection to brain damage and a key role of the phagocytic NADPH oxidase (NOX-2).

AIMS: Electronic (e)-cigarettes have been marketed as a 'healthy' alternative to traditional combustible cigarettes and as an effective method of smoking cessation. There are, however, a paucity of data to support these claims. In fact, e-cigarettes are implicated in endothelial dysfunction and oxidative stress in the vasculature and the lungs. The mechanisms underlying these side effects remain unclear. Here, we investigated the effects of e-cigarette vapour on vascular function in smokers and experimental animals to determine the underlying mechanisms. METHODS AND RESULTS: Acute e-cigarette smoking produced a marked impairment of endothelial function in chronic smokers determined by flow-mediated dilation. In mice, e-cigarette vapour without nicotine had more detrimental effects on endothelial function, markers of oxidative stress, inflammation, and lipid peroxidation than vapour containing nicotine. These effects of e-cigarette vapour were largely absent in mice lacking phagocytic NADPH oxidase (NOX-2) or upon treatment with the endothelin receptor blocker macitentan or the FOXO3 activator bepridil. We also established that the e-cigarette product acrolein, a reactive aldehyde, recapitulated many of the NOX-2-dependent effects of e-cigarette vapour using in vitro blood vessel incubation. CONCLUSIONS: E-cigarette vapour exposure increases vascular, cerebral, and pulmonary oxidative stress via a NOX-2-dependent mechanism. Our study identifies the toxic aldehyde acrolein as a key mediator of the observed adverse vascular consequences. Thus, e-cigarettes have the potential to induce marked adverse cardiovascular, pulmonary, and cerebrovascular consequences. Since e-cigarette use is increasing, particularly amongst youth, our data suggest that aggressive steps are warranted to limit their health risks.

Radical Formation by Fine Particulate Matter Associated with Highly Oxygenated Molecules.

Highly oxygenated molecules (HOMs) play an important role in the formation and evolution of secondary organic aerosols (SOA). However, the abundance of HOMs in different environments and their relation to the oxidative potential of fine particulate matter (PM) are largely unknown. Here, we investigated the relative HOM abundance and radical yield of laboratory-generated SOA and fine PM in ambient air ranging from remote forest areas to highly polluted megacities. By electron paramagnetic resonance and mass spectrometric investigations, we found that the relative abundance of HOMs, especially the dimeric and low-volatility types, in ambient fine PM was positively correlated with the formation of radicals in aqueous PM extracts. SOA from photooxidation of isoprene, ozonolysis of α- and ß-pinene, and fine PM from tropical (central Amazon) and boreal (Hyytiälä, Finland) forests exhibited a higher HOM abundance and radical yield than SOA from photooxidation of naphthalene and fine PM from urban sites (Beijing, Guangzhou, Mainz, Shanghai, and Xi'an), confirming that HOMs are important constituents of biogenic SOA to generate radicals. Our study provides new insights into the chemical relationship of HOM abundance, composition, and sources with the yield of radicals by laboratory and ambient aerosols, enabling better quantification of the component-specific contribution of source- or site-specific fine PM to its climate and health effects.

Molecular Characterization and Source Identification of Atmospheric Particulate Organosulfates Using Ultrahigh Resolution Mass Spectrometry.

Organosulfates (OSs) have been observed as substantial constituents of atmospheric organic aerosol (OA) in a wide range of environments; however, the chemical composition, sources, and formation mechanism of OSs are still not well understood. In this study, we first created an "OS precursor map" based on the elemental composition of previous OS chamber experiments. Then, according to this "OS precursor map", we estimated the possible sources and molecular structures of OSs in atmospheric PM2.5 (particles with aerodynamic diameter ≤ 2.5 µm) samples, which were collected in urban areas of Beijing (China) and Mainz (Germany) and analyzed by ultrahigh-performance liquid chromatography (UHPLC) coupled with an Orbitrap mass spectrometer. On the basis of the "OS precursor map", together with the polarity information provided by UHPLC, OSs in Mainz samples are suggested to be mainly derived from isoprene/glyoxal or other unknown small polar organic compounds, while OSs in Beijing samples were generated from both isoprene/glyoxal and anthropogenic sources (e.g., long-chain alkanes and aromatics). The nitrooxy-OSs in the clean aerosol samples were mainly derived from monoterpenes, while much fewer monoterpene-derived nitrooxy-OSs were obtained in the polluted aerosol samples, showing that nitrooxy-OS formation is affected by different precursors in clean and polluted air conditions.

CDK7 is a component of the integrated stress response regulating SNAT2 (SLC38A2)/System A adaptation in response to cellular amino acid deprivation.

Extracellular amino acid (AA) withdrawal/restriction invokes an integrated stress response (ISR) that induces global suppression of protein synthesis whilst allowing transcription and translation of a select group of genes, whose protein products facilitate cellular adaptation to AA insufficiency. Transcriptional induction of the System A/SNAT2 AA transporter represents a classic adaptation response and crucially depends upon activation of the General Control Nonderepressible-2 kinase/Activating transcription factor 4 (GCN2/ATF4) pathway. However, the ISR may also include additional signalling inputs operating in conjunction or independently of GCN2/ATF4 to upregulate SNAT2. Herein, we show that whilst pharmacological inhibition of MEK-ERK, mTORC1 and p38 MAP kinase signalling has no detectable effect on System A upregulation, inhibitors targeting GSK3 (e.g. SB415286) caused significant repression of the SNAT2 adaptation response. Strikingly, the effects of SB415286 persist in cells in which GSK3α/ß have been stably silenced indicating an off-target effect. We show that SB415286 can also inhibit cyclin-dependent kinases (CDK) and that roscovitine and flavopiridol (two pan CDK inhibitors) are effective repressors of the SNAT2 adaptive response. In particular, our work reveals that CDK7 activity is upregulated in AA-deprived cells in a GCN-2-dependent manner and that a potent and selective CDK7 inhibitor, THZ-1, not only attenuates the increase in ATF4 expression but blocks System A adaptation. Importantly, the inhibitory effects of THZ-1 on System A adaptation are mitigated in cells expressing a doxycycline-inducible drug-resistant form of CDK7. Our data identify CDK7 as a novel component of the ISR regulating System A adaptation in response to AA insufficiency.

Ultrahigh-Resolution Mass Spectrometry in Real Time: Atmospheric Pressure Chemical Ionization Orbitrap Mass Spectrometry of Atmospheric Organic Aerosol.

The accurate and precise mass spectrometric measurement of organic compounds in atmospheric aerosol particles is a challenging task that requires analytical developments and adaptations of existing techniques for the atmospheric application. Here we describe the development and characterization of an atmospheric pressure chemical ionization Orbitrap mass spectrometer (APCI-Orbitrap-MS) for the measurement of organic aerosol in real time. APCI is a well-known ionization technique, featuring minimal fragmentation and matrix dependencies, and allows rapid alternation between the positive and negative ionization mode. As a proof of principle, we report ambient organic aerosol composition in real-time, with alternating ionization, high mass resolution ( R = 140 000) and accuracy (<2 ppm). The instrument was calibrated in the negative ion mode using 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA) model aerosol. We obtain a detection limit of 1.3 ng/m3. Based on the performed calibration using MBTCA particles, the ambient concentration of MBTCA in the particle phase measured in an urban area in Mainz, Germany, ranged between 10 and 80 ng/m3. For the first time, we apply a nontarget screening approach on real-time data, showing molecular variability between ambient day- and nighttime aerosol composition. The detected compounds were grouped in the night- and daytime and analyzed by ultrahigh-resolution MS (UHRMS) visualization methods. Among several prevalent biogenic secondary organic aerosol (BSOA) markers, 24 organic mononitrates and one organic dinitrate were detected. We further estimate that, on average, organic nitrates contribute to 5% and 14% of the measured particulate organic aerosol at day and night, respectively.