Temperature and volatile organic compound concentrations as controlling factors for chemical composition of alpha-pinene-derived secondary organic aerosol

This work investigates the individual and combined effects of temperature and volatile organic compound precursor concentrations on the chemical composition of particles formed in the dark ozonolysis of alpha-pinene. All experiments were conducted in a 5m(3) Teflon chamber at an initial ozone concentration of 100 ppb and initial alpha-pinene concentrations of 10 and 50 ppb, respectively; at constant temperatures of 20, 0, or -15 degrees C; and at changing temperatures (ramps) from -15 to 20 and from 20 to -15 degrees C. The chemical composition of the particles was probed using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). A four-factor solution of a positive matrix factorization (PMF) analysis of the combined HR-ToF-AMS data is presented. The PMF analysis and the elemental composition analysis of individual experiments show that secondary organic aerosol particles with the highest oxidation level are formed from the lowest initial alpha-pinene concentration (10 ppb) and at the highest temperature (20 degrees C). A higher initial alpha-pinene concentration (50 ppb) and/or lower temperature (0 or -15 degrees C) results in a lower oxidation level of the molecules contained in the particles. With respect to the carbon oxidation state, particles formed at 0 degrees C are more comparable to particles formed at 15 degrees C than to those formed at 20 degrees C. A remarkable observation is that changes in temperature during particle formation result in only minor changes in the elemental composition of the particles. Thus, the temperature at which aerosol particle formation is induced seems to be a critical parameter for the particle elemental composition. Comparison of the HR-ToF-AMS-derived estimates of the content of organic acids in the particles based on m/z 44 in the mass spectra show good agreement with results from off-line molecular analysis of particle filter samples collected from the same experiments. Higher temperatures are associated with a decrease in the absolute mass concentrations of organic acids (R-COOH) and organic acid functionalities (-COOH), while the organic acid functionalities account for an increasing fraction of the measured particle mass.Peer reviewe

The Aarhus Chamber Campaign on Highly Oxygenated Organic Molecules and Aerosols (ACCHA) : particle formation, organic acids, and dimer esters from alpha-pinene ozonolysis at different temperatures

Little is known about the effects of subzero temperatures on the formation of secondary organic aerosol (SOA) from alpha-pinene. In the current work, ozone-initiated oxidation of alpha-pinene at initial concentrations of 10 and 50 ppb, respectively, is performed at temperatures of 20, 0, and -15 degrees C in the Aarhus University Research on Aerosol (AURA) smog chamber during the Aarhus Chamber Campaign on Highly Oxygenated Organic Molecules and Aerosols (ACCHA). Herein, we show how temperature influences the formation and chemical composition of alpha-pinene-derived SOA with a specific focus on the formation of organic acids and dimer esters. With respect to particle formation, the results show significant increase in particle-formation rates, particle number concentrations, and particle mass concentrations at low temperatures. In particular, the number concentrations of sub-10 nm particles were significantly increased at the lower 0 and -15 degrees C temperatures. Temperature also affects the chemical composition of formed SOA. Here, detailed offline chemical analyses show that organic acids contribute from 15 % to 30 % by mass, with highest contributions observed at the lowest temperatures, indicative of enhanced condensation of these semivolatile species. In comparison, a total of 30 identified dimer esters were seen to contribute between 4 % and 11 % to the total SOA mass. No significant differences in the chemical composition (i.e. organic acids and dimer esters) of the alpha-pinene-derived SOA particles are observed between experiments performed at 10 and 50 ppb initial alpha-pinene concentrations, thus suggesting a higher influence of reaction temperature compared to that of alpha-pinene loading on the SOA chemical composition. Interestingly, the effect of temperature on the formation of dimer esters differs between the individual species. The formation of less oxidized dimer esters - with oxygento-carbon ratio (O : C) 0.4) is suppressed, consequently resulting in temperature-modulated composition of the a -pinene-derived SOA. Temperature ramping experiments exposing alpha-pinenederived SOA to changing temperatures (heating and cooling) reveal that the chemical composition of the SOA with respect to dimer esters is governed almost solely by the temperature at which oxidization started and is insusceptible to subsequent changes in temperature Similarly, the resulting SOA mass concentrations were found to be more influenced by the initial alpha-pinene oxidation temperatures, thus suggesting that the formation conditions to a large extent govern the type of SOA formed, rather than the conditions to which the SOA is later exposed. For the first time, we discuss the relation between the identified dimer ester and the highly oxygenated organic molecules (HOMs) measured by chemical ionization-atmospheric pressure interface-time-of-flight mass spectrometer (CI-APi-ToF) during the ACCHA experiments. We propose that, although very different in chemical structures and O : C ratios, many dimer esters and HOMs may be linked through similar RO2 reaction pathways and that dimer esters and HOMs merely represent two different fates of the RO2 radicals.Peer reviewe

Maoism in the Cultural Revolution: A Political Religion?”

in Robert Mallett, John Tortorice and Roger Griffin, ed., The Sacred in Twentieth-Century Politics: Essays in Honour of Professor Stanley G. Payne (Basingstoke: Palgrave, 2008)

Effect of temperature on the formation of highly oxygenated organic molecules (HOMs) from alpha-pinene ozonolysis

Highly oxygenated organic molecules (HOMs) are important contributors to secondary organic aerosol (SOA) and new-particle formation (NPF) in the boreal atmosphere. This newly discovered class of molecules is efficiently formed from atmospheric oxidation of biogenic volatile organic compounds (VOCs), such as monoterpenes, through a process called autoxidation. This process, in which peroxy-radical intermediates isomerize to allow addition of molecular oxygen, is expected to be highly temperature-dependent. Here, we studied the dynamics of HOM formation during a -pinene ozonolysis experiments performed at three different temperatures, 20, 0 and - 15 degrees C, in the Aarhus University Research on Aerosol (AURA) chamber. We found that the HOM formation, under our experimental conditions (50 ppb alpha-pinene and 100 ppb ozone), decreased considerably at lower temperature, with molar yields dropping by around a factor of 50 when experiments were performed at 0 degrees C, compared to 20 degrees C. At -15 degrees C, the HOM signals were already close to the detection limit of the nitrate-based chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometer used for measuring gas-phase HOMs. Surprisingly, comparing spectra measured at 0 and 20 degrees C, ratios between HOMs of different oxidation levels, e.g., the typical HOM products C10H14O7, C10H14O9, and C10H14O11, changed considerably less than the total HOM yields. More oxidized species have undergone more isomerization steps; yet, at lower temperature, they did not decrease more than the less oxidized species. One possible explanation is that the primary rate-limiting steps forming these HOMs occur before the products become oxygenated enough to be detected by our CI-APi-TOF (i.e., typically seven or more oxygen atoms). The strong temperature dependence of HOM formation was observed under temperatures highly relevant to the boreal forest, but the exact magnitude of this effect in the atmosphere will be much more complex: the fate of peroxy radicals is a competition between autoxidation (influenced by temperature and VOC type) and bimolecular termination pathways (influenced mainly by concentration of reaction partners). While the temperature influence is likely smaller in the boreal atmosphere than in our chamber, both the magnitude and complexity of this effect clearly deserve more consideration in future studies in order to estimate the ultimate role of HOMs on SOA and NPF under different atmospheric conditions.Peer reviewe

CaV1.3 channel clusters characterized by live-cell and isolated plasma membrane nanoscopy

Abstract A key player of excitable cells in the heart and brain is the L-type calcium channel CaV1.3. In the heart, it is required for voltage-dependent Ca2+-signaling, i.e., for controlling and modulating atrial cardiomyocyte excitation-contraction coupling. The clustering of CaV1.3 in functionally relevant channel multimers has not been addressed due to a lack of stoichiometric labeling combined with high-resolution imaging. Here, we developed a HaloTag-labeling strategy to visualize and quantify CaV1.3 clusters using STED nanoscopy to address the questions of cluster size and intra-cluster channel density. Channel clusters were identified in the plasma membrane of transfected live HEK293 cells as well as in giant plasma membrane vesicles derived from these cells that were spread on modified glass support to obtain supported plasma membrane bilayers (SPMBs). A small fraction of the channel clusters was colocalized with early and recycling endosomes at the membranes. STED nanoscopy in conjunction with live-cell and SPMB imaging enabled us to quantify CaV1.3 cluster sizes and their molecular density revealing significantly lower channel densities than expected for dense channel packing. CaV1.3 channel cluster size and molecular density were increased in SPMBs after treatment of the cells with the sympathomimetic compound isoprenaline, suggesting a regulated channel cluster condensation mechanism