Shape and Compliance of Endothelial Cells after Shear Stress In Vitro or from Different Aortic Regions: Scanning Ion Conductance Microscopy Study

Objective: To measure the elongation and compliance of endothelial cells subjected to different patterns of shear stress in vitro, and to compare these parameters with the elongation and compliance of endothelial cells from different regions of the intact aorta. Materials and Methods: Porcine aortic endothelial cells were cultured for 6 days under static conditions or on an orbital shaker. The shaker generated a wave of medium, inducing pulsatile shear stress with a preferred orientation at the edge of the well or steadier shear stress with changing orientation at its centre. The topography and compliance of these cells and cells from the inner and outer curvature of ex vivo porcine aortic arches were measured by scanning ion conductance microscopy (SICM). Results: Cells cultured under oriented shear stress were more elongated and less compliant than cells grown under static conditions or under shear stress with no preferred orientation. Cells from the outer curvature of the aorta were more elongated and less compliant than cells from the inner curvature. Conclusion: The elongation and compliance of cultured endothelial cells vary according to the pattern of applied shear stress, and are inversely correlated. A similar inverse correlation occurs in the aortic arch, with variation between region

Composition and temporal behavior of ambient ions in the boreal forest

A recently developed atmospheric pressure interface mass spectrometer (APi-TOF) measured the negative and positive ambient ion composition at a boreal forest site. As observed in previous studies, the negative ions were dominated by strong organic and inorganic acids (e.g. malonic, nitric and sulfuric acid), whereas the positive ions consisted of strong bases (e.g. alkyl pyridines and quinolines). Several new ions and clusters of ions were identified based on their exact masses, made possible by the high resolution, mass accuracy and sensitivity of the APi-TOF. Time series correlograms aided in peak identification and assigning the atomic compositions to molecules. Quantum chemical calculations of proton affinities and cluster stabilities were also used to confirm the plausibility of the assignments. Acids in the gas phase are predominantly formed by oxidation in the gas phase, and thus the concentrations are expected to vary strongly between day and night. This was also the case in this study, where the negative ions showed strong diurnal behavior, whereas the daily changes in the positive ions were considerably smaller. A special focus in this work was the changes in the ion distributions occurring during new particle formation events. We found that sulfuric acid, together with its clusters, dominated the negative ion spectrum during these events. The monomer (HSO<sub>4</sub><sup>−</sup>) was the largest peak, together with the dimer (H<sub>2</sub>SO<sub>4</sub> · HSO<sub>4</sub><sup>−</sup>) and trimer ((H<sub>2</sub>SO<sub>4</sub>)<sub>2</sub> · HSO<sub>4</sub><sup>−</sup>). SO<sub>5</sub><sup>−</sup> also tracked HSO<sub>4</sub><sup>−</sup> at around 20% of the HSO<sub>4</sub><sup>−</sup> concentration at all times. During the strongest events, the tetramer and a cluster with the tetramer and ammonia were also detected. Quantum chemical calculations predict that sulfuric acid clusters containing ammonia are much more stable when neutral, thus the detection of a single ion cluster implies that ammonia can be an important compound in the nucleation process. We also believe to have made the first observations of an organosulfate (glycolic acid sulfate) in the gas phase. This ion, and its cluster with sulfuric acid, correlates with the HSO<sub>4</sub><sup>−</sup>, but peaks in the early afternoon, some hours later than HSO<sub>4</sub><sup>−</sup> itself. A list of all identified ions is presented in the supplementary material, and also a list of all detected masses not yet identified

Airborne flux measurements of ammonia over the southern Great Plains using chemical ionization mass spectrometry

Peer reviewe

Gas phase formation of extremely oxidized pinene reaction products in chamber and ambient air

High molecular weight (300–650 Da) naturally charged negative ions have previously been observed at a boreal forest site in Hyytiälä, Finland. The long-term measurements conducted in this work showed that these ions are observed practically every night between spring and autumn in Hyytiälä. The ambient mass spectral patterns could be reproduced in striking detail during additional measurements of α-pinene (C<sub>10</sub>H<sub>16</sub>) oxidation at low-OH conditions in the Jülich Plant Atmosphere Chamber (JPAC). The ions were identified as clusters of the nitrate ion (NO<sub>3</sub><sup>−</sup>) and α-pinene oxidation products reaching oxygen to carbon ratios of 0.7–1.3, while retaining most of the initial ten carbon atoms. Attributing the ions to clusters instead of single molecules was based on additional observations of the same extremely oxidized organics in clusters with HSO<sub>4</sub><sup>−</sup> (Hyytiälä) and C<sub>3</sub>F<sub>5</sub>O<sub>2</sub><sup>−</sup> (JPAC). The most abundant products in the ion spectra were identified as C<sub>10</sub>H<sub>14</sub>O<sub>7</sub>, C<sub>10</sub>H<sub>14</sub>O<sub>9</sub>, C<sub>10</sub>H<sub>16</sub>O<sub>9</sub>, and C<sub>10</sub>H<sub>14</sub>O<sub>11</sub>. The mechanism responsible for forming these molecules is still not clear, but the initial reaction is most likely ozone attack at the double bond, as the ions are mainly observed under dark conditions. β-pinene also formed highly oxidized products under the same conditions, but less efficiently, and mainly C<sub>9</sub> compounds which were not observed in Hyytiälä, where β-pinene on average is 4–5 times less abundant than α-pinene. Further, to explain the high O/C together with the relatively high H/C, we propose that geminal diols and/or hydroperoxide groups may be important. We estimate that the night-time concentration of the sum of the neutral extremely oxidized products is on the order of 0.1–1 ppt (~10<sup>6</sup>–10<sup>7</sup> molec cm<sup>−3</sup>). This is in a similar range as the amount of gaseous H<sub>2</sub>SO<sub>4</sub> in Hyytiälä during day-time. As these highly oxidized organics are roughly 3 times heavier, likely with extremely low vapor pressures, their role in the initial steps of new aerosol particle formation and growth may be important and needs to be explored in more detail in the future

Pathways to Highly Oxidized Products in the Delta 3-Carene + OH System

Oxidation of the monoterpene Delta 3-carene (C10H16) is a potentially important and understudied source of atmospheric secondary organic aerosol (SOA). We present chamber-based measurements of speciated gas and particle phases during photochemical oxidation of Delta 3-carene. We find evidence of highly oxidized organic molecules (HOMs) in the gas phase and relatively low-volatility SOA dominated by C-7-C-10 species. We then use computational methods to develop the first stages of a Delta 3-carene photochemical oxidation mechanism and explain some of our measured compositions. We find that alkoxy bond scission of the cyclohexyl ring likely leads to efficient HOM formation, in line with previous studies. We also find a surprising role for the abstraction of primary hydrogens from methyl groups, which has been calculated to be rapid in the alpha-pinene system, and suggest more research is required to determine if this is more general to other systems and a feature of autoxidation. This work develops a more comprehensive view of Delta 3-carene photochemical oxidation products via measurements and lays out a suggested mechanism of oxidation via computationally derived rate coefficients.Peer reviewe

Variation in chemical composition and volatility of oxygenated organic aerosol in different rural, urban, and mountain environments

The apparent volatility of atmospheric organic aerosol (OA) particles is determined by their chemical composition and environmental conditions (e.g., ambient temperature). A quantitative, experimental assessment of volatility and the respective importance of these two factors remains challenging, especially in ambient measurements. We present molecular composition and volatility of oxygenated OA (OOA) particles in different rural, urban, and mountain environments (including Chacaltaya, Bolivia; Alabama, US; Hyytiälä, Finland; Stuttgart and Karlsruhe, Germany; and Delhi, India) based on deployments of a filter inlet for gases and aerosols coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (FIGAERO-CIMS). We find on average larger carbon numbers (nC) and lower oxygen-to-carbon (O : C) ratios at the urban sites (nC: 9.8 ± 0.7; O : C: 0.76 ± 0.03; average ±1 standard deviation) compared to the rural (nC: 8.8 ± 0.6; O : C: 0.80 ± 0.05) and mountain stations (nC: 8.1 ± 0.8; O : C: 0.91 ± 0.07), indicative of different emission sources and chemistry

Molecular composition and volatility of isoprene photochemical oxidation secondary organic aerosol under low- and high-NOx conditions

Here, we present measurements of secondary organic aerosol (SOA) formation from isoprene photochemical oxidation in an environmental simulation chamber at a variety of oxidant conditions and using dry neutral seed particles to suppress acid-catalyzed multiphase chemistry. A high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) utilizing iodide-adduct ionization coupled to the Filter Inlet for Gases and Aerosols (FIGAERO) allowed for simultaneous online sampling of the gas and particle composition. Under high-HO 2 and low-NO conditions, highly oxygenated (O : C ≥ 1) C 5 compounds were major components (~50%) of SOA. The SOA composition and effective volatility evolved both as a function of time and as a function of input NO concentrations. Organic nitrates increased in both the gas and particle phases as input NO increased, but the dominant non-nitrate particle-phase components monotonically decreased. We use comparisons of measured and predicted gas-particle partitioning of individual components to assess the validity of literature-based group-contribution methods for estimating saturation vapor concentrations. While there is evidence for equilibrium partitioning being achieved on the chamber residence timescale (5.2 h) for some individual components, significant errors in group-contribution methods are revealed. In addition, >30% of the SOA mass, detected as low-molecular-weight semivolatile compounds, cannot be reconciled withmore » equilibrium partitioning. These compounds desorb from the FIGAERO at unexpectedly high temperatures given their molecular composition, which is indicative of thermal decomposition of effectively lower-volatility components such as larger molecular weight oligomers.« les

Molecular composition and volatility of isoprene photochemical oxidation secondary organic aerosol under low- and high-NOx conditions

Here, we present measurements of secondary organic aerosol (SOA) formation from isoprene photochemical oxidation in an environmental simulation chamber at a variety of oxidant conditions and using dry neutral seed particles to suppress acid-catalyzed multiphase chemistry. A high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) utilizing iodide-adduct ionization coupled to the Filter Inlet for Gases and Aerosols (FIGAERO) allowed for simultaneous online sampling of the gas and particle composition. Under high-HO 2 and low-NO conditions, highly oxygenated (O : C ≥ 1) C 5 compounds were major components (~50%) of SOA. The SOA composition and effective volatility evolved both as a function of time and as a function of input NO concentrations. Organic nitrates increased in both the gas and particle phases as input NO increased, but the dominant non-nitrate particle-phase components monotonically decreased. We use comparisons of measured and predicted gas-particle partitioning of individual components to assess the validity of literature-based group-contribution methods for estimating saturation vapor concentrations. While there is evidence for equilibrium partitioning being achieved on the chamber residence timescale (5.2 h) for some individual components, significant errors in group-contribution methods are revealed. In addition, >30% of the SOA mass, detected as low-molecular-weight semivolatile compounds, cannot be reconciled withmore » equilibrium partitioning. These compounds desorb from the FIGAERO at unexpectedly high temperatures given their molecular composition, which is indicative of thermal decomposition of effectively lower-volatility components such as larger molecular weight oligomers.« les

Source characterization of highly oxidized multifunctional compounds in a boreal forest environment using positive matrix factorization

Highly oxidized multifunctional compounds (HOMs) have been demonstrated to be important for atmospheric secondary organic aerosols (SOA) and new-particle formation (NPF), yet it remains unclear which the main atmospheric HOM formation pathways are. In this study, a nitrate-ion-based chemical ionization atmospheric-pressure-interface time-of-flight mass spectrometer (CI-APi-TOF) was deployed to measure HOMs in the boreal forest in Hyytiala, southern Finland. Positive matrix factorization (PMF) was applied to separate the detected HOM species into several factors, relating these "factors" to plausible formation pathways. PMF was performed with a revised error estimation derived from laboratory data, which agrees well with an estimate based on ambient data. Three factors explained the majority (> 95 %) of the data variation, but the optimal solution found six factors, including two night-time factors, three daytime factors, and a transport factor. One nighttime factor is almost identical to laboratory spectra generated from monoterpene ozonolysis, while the second likely represents monoterpene oxidation initiated by NO3. The exact chemical processes forming the different daytime factors remain unclear, but they all have clearly distinct diurnal profiles, very likely related to monoterpene oxidation with a strong influence from NO, presumably through its effect on peroxy radical (RO2 / chemistry. Apart from these five "local" factors, the sixth factor is interpreted as a transport related factor. These findings improve our understanding of HOM production by confirming current knowledge and inspiring future research directions and provide new perspectives on using factorization methods to understand short-lived atmospheric species.Peer reviewe