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A copy of Guangbo jiemu bao [Broadcast Program Report] was being passed from hand to hand among a group of young people eager to be the first to read the article introducing the program "What Is Revolutionary Love?" It said: "… Young friends, you are certainly very concerned about this problem'. So, we would like you to meet the young women workers Meng Xiaoyu and Meng Yamei and the older cadre Miss Feng. They are the three leading characters in the short story ‘The Place of Love.’ Through the description of the love lives of these three, the story induces us to think deeply about two questions that merit further examination.

This is How the Discussion Started

. Progress has been made over the past decade in predicting secondary organic aerosol (SOA) mass in the atmosphere using vapor pressure-driven partitioning, which implies that SOA compounds are formed in the gas phase and then partition to an organic phase (gasSOA). However, discrepancies in predicting organic aerosol oxidation state, size and product (molecular mass) distribution, relative humidity (RH) dependence, color, and vertical profile suggest that additional SOA sources and aging processes may be important. The formation of SOA in cloud and aerosol water (aqSOA) is not considered in these models even though water is an abundant medium for atmospheric chemistry and such chemistry can form dicarboxylic acids and "humic-like substances" (oligomers, high-molecular-weight compounds), i.e. compounds that do not have any gas phase sources but comprise a significant fraction of the total SOA mass. There is direct evidence from field observations and laboratory studies that organic aerosol is formed in cloud and aerosol water, contributing substantial mass to the droplet mode. This review summarizes the current knowledge on aqueous phase organic reactions and combines evidence that points to a significant role of aqSOA formation in the atmosphere. Model studies are discussed that explore the importance of aqSOA formation and suggestions for model improvements are made based on the comprehensive set of laboratory data presented here. A first comparison is made between aqSOA and gasSOA yields and mass predictions for selected conditions. These simulations suggest that aqSOA might contribute almost as much mass as gasSOA to the SOA budget, with highest contributions from biogenic emissions of volatile organic compounds (VOC) in the presence of anthropogenic pollutants (i.e. NOx) at high relative humidity and cloudiness. Gaps in the current understanding of aqSOA processes are discussed and further studies (laboratory, field, model) are outlined to complement current data sets.

/pdf/secondary-organic-aerosol-formation-in-cloud-droplets-and-2eke8pinlz.pdf

Secondary organic aerosol formation in cloud droplets and aqueous particles (aqSOA): a review of laboratory, field and model studies

[1] The atmospheric chemistry of volatile organic compounds (VOCs) in urban areas results in the formation of ‘photochemical smog’, including secondary organic aerosol (SOA). State-of-the-art SOA models parameterize the results of simulation chamber experiments that bracket the conditions found in the polluted urban atmosphere. Here we show that in the real urban atmosphere reactive anthropogenic VOCs (AVOCs) produce much larger amounts of SOA than these models predict, even shortly after sunrise. Contrary to current belief, a significant fraction of the excess SOA is formed from first-generation AVOC oxidation products. Global models deem AVOCs a very minor contributor to SOA compared to biogenic VOCs (BVOCs). If our results are extrapolated to other urban areas, AVOCs could be responsible for additional 3–25 Tg yr−1 SOA production globally, and cause up to −0.1 W m−2 additional top-of-the-atmosphere radiative cooling.

Secondary Organic Aerosol Formation from Anthropogenic Air Pollution: Rapid and Higher than Expected

Tropospheric aqueous-phase chemistry: kinetics, mechanisms, and its coupling to a changing gas phase.

Heterogeneous reactions of volatile organic compounds in the atmosphere

Recent studies have shown that heterogeneous reactions of hydrogen peroxide (H2O2) on aerosol surfaces may play an important role in tropospheric chemistry. The data concerning the kinetics and mechanisms of these reactions, however, are quite scarce so far. Here, we investigated, for the first time, the heterogeneous reactions of gaseous H2O2 on SiO2 and α-Al2O3 particles, two major components of mineral dust aerosol, using transmission-Fourier Transform Infrared (T-FTIR) spectroscopy, and high-performance liquid chromatography (HPLC). It is found that H2O2 molecularly adsorbs on SiO2, and a small amount of molecularly adsorbed H2O2 decomposes due to its thermal instability. For α-Al2O3, catalytic decomposition of H2O2 evidently occurs, but there is also a small amount of H2O2 molecularly adsorbed on the particle surface. The BET uptake coefficients of H2O2 on both particles appear to be independent of gaseous H2O2 concentration (1.27−13.8 ppmv) and particle sample mass (2.8−6.5 mg for SiO2 and 8.6−18.9 ...

Kinetics and Mechanisms of Heterogeneous Reaction of Gaseous Hydrogen Peroxide on Mineral Oxide Particles

. Chemical composition, size distributions, and degree of
oligomerization of secondary organic aerosol (SOA) from α -pinene
(C 10 H 16) ozonolysis were investigated for low-temperature
conditions (223 K). Two types of experiments were performed using two
simulation chambers at the Karlsruhe Institute of Technology: the Aerosol
Preparation and Characterization (APC) chamber, and the Aerosol Interaction
and Dynamics in the Atmosphere (AIDA) chamber. Experiment type 1 simulated
SOA formation at upper tropospheric conditions: SOA was generated in the AIDA
chamber directly at 223 K at 61 % relative humidity (RH; experiment
termed “cold humid”, CH) and for comparison at 6 % RH (experiment
termed “cold dry”, CD) conditions. Experiment type 2 simulated SOA
uplifting: SOA was formed in the APC chamber at room temperature (296 K) and
< 1 % RH (experiment termed “warm dry”, WD) or 21 % RH
(experiment termed “warm humid”, WH) conditions, and then partially
transferred to the AIDA chamber kept at 223 K, and 61 % RH (WDtoCH) or
30 % RH (WHtoCH), respectively. Precursor concentrations varied between
0.7 and 2.2 ppm α -pinene, and between 2.3 and 1.8 ppm ozone for type 1 and
type 2 experiments, respectively. Among other instrumentation, a chemical
ionization mass spectrometer (CIMS) coupled to a filter inlet for gases and
aerosols (FIGAERO), deploying I − as reagent ion, was used for SOA
chemical composition analysis. For type 1 experiments with lower α -pinene concentrations and cold SOA
formation temperature (223 K), smaller particles of 100–300 nm vacuum
aerodynamic diameter ( dva) and higher mass fractions
(> 40 %) of adducts (molecules with more than 10 carbon
atoms) of α -pinene oxidation products were observed. For type 2
experiments with higher α -pinene concentrations and warm SOA formation
temperature (296 K), larger particles ( ∼  500 nm dva) with
smaller mass fractions of adducts ( We also observed differences (up to 20  ∘ C) in maximum desorption
temperature ( Tmax) of individual compounds desorbing from the
particles deposited on the FIGAERO Teflon filter for different experiments,
indicating that Tmax is not purely a function of a compound's
vapor pressure or volatility, but is also influenced by diffusion limitations
within the particles (particle viscosity), interactions between particles
deposited on the filter (particle matrix), and/or particle mass on the
filter. Highest Tmax were observed for SOA under dry conditions
and with higher adduct mass fraction; lowest Tmax were observed for SOA under
humid conditions and with lower adduct mass fraction. The observations
indicate that particle viscosity may be influenced by intra- and
inter-molecular hydrogen bonding between oligomers, and particle water
uptake, even under such low-temperature conditions. Our results suggest that particle physicochemical properties such as
viscosity and oligomer content mutually influence each other, and that
variation in Tmax of particle desorptions may have
implications for particle viscosity and particle matrix effects. The
differences in particle physicochemical properties observed between our
different experiments demonstrate the importance of taking experimental
conditions into consideration when interpreting data from laboratory studies
or using them as input in climate models.

/pdf/a-pinene-secondary-organic-aerosol-at-low-temperature-22b5ce64w2.pdf

α -Pinene secondary organic aerosol at low temperature: chemical composition and implications for particle viscosity

. Aqueous phase chemical processes of organic compounds in the atmosphere have received increasing attention, partly due to their potential contribution to the formation of secondary organic aerosol (SOA). Here, we analyzed the aqueous OH-initiated oxidation of isoprene and its reaction products including carbonyl compounds and organic acids, regarding the acidity and temperature as in-cloudy conditions. We also performed a laboratory simulation to improve our understanding of the kinetics and mechanisms for the products of aqueous isoprene oxidation that are significant precursors of SOA; these included methacrolein (MACR), methyl vinyl ketone (MVK), methyl glyoxal (MG), and glyoxal (GL). We used a novel chemical titration method to monitor the concentration of isoprene in the aqueous phase. We used a box model to interpret the mechanistic differences between aqueous and gas phase OH radical-initiated isoprene oxidations. Our results were the first demonstration of the rate constant for the reaction between isoprene and OH radical in water, 1.2 ± 0.4) × 1010 M−1 s−1 at 283 K. Molar yields were determined based on consumed isoprene. Of note, the ratio of the yields of MVK (24.1 ± 0.8 %) to MACR (10.9 ± 1.1%) in the aqueous phase isoprene oxidation was approximately double that observed for the corresponding gas phase reaction. We hypothesized that this might be explained by a water-induced enhancement in the self-reaction of a hydroxy isoprene peroxyl radical (HOCH2C(CH3)(O2)CH = CH2) produced in the aqueous reaction. The observed yields for MG and GL were 11.4 ± 0.3 % and 3.8 ± 0.1 %, respectively. Model simulations indicated that several potential pathways may contribute to the formation of MG and GL. Finally, oxalic acid increased steadily throughout the course of the study, even after isoprene was consumed completely. The observed yield of oxalic acid was 26.2 ± 0.8 % at 6 h. The observed carbon balance accounted for ~50 % of the consumed isoprene. The presence of high-molecular-weight compounds may have accounted for a large portion of the missing carbons, but they were not quantified in this study. In summary, our work has provided experimental evidence that the availably abundant water could affect the distribution of oxygenated organic compounds produced in the oxidation of volatile organic compounds.

/pdf/the-kinetics-and-mechanism-of-an-aqueous-phase-isoprene-2f1a7imj9i.pdf

The kinetics and mechanism of an aqueous phase isoprene reaction with hydroxyl radical

Reactions of volatile organic compounds (VOC) with NO3 radicals and of reactive intermediates of oxidized VOC with NOx can lead to the formation of highly functionalized organonitrates (ON). We present quantitative and chemical information on ON contributing to high night-time organic aerosol (OA) mass concentrations measured during July–August 2016 in a rural area in southwest Germany. A filter inlet for gases and aerosols coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (FIGAERO-HR-ToF-CIMS) was used to analyze the molecular composition of ON in both the gas and particle phase. We find larger contributions of ON to OA mass during the night. Identified ON are highly functionalized, with 4 to 12 oxygen atoms. The diel patterns of ON compounds with 5, 7, 10, or 15 carbon atoms per molecule vary, indicating a corresponding behavior of their potential precursor VOC. The temporal behavior of ON after sunset correlates with that of the number concentration of ultrafine particle...

Xiaoli Shen

Papers

Heterogeneous reactions of volatile organic compounds in the atmosphere

Kinetics and Mechanisms of Heterogeneous Reaction of Gaseous Hydrogen Peroxide on Mineral Oxide Particles

α -Pinene secondary organic aerosol at low temperature: chemical composition and implications for particle viscosity

The kinetics and mechanism of an aqueous phase isoprene reaction with hydroxyl radical

Chemical Characterization of Highly Functionalized Organonitrates Contributing to Night-Time Organic Aerosol Mass Loadings and Particle Growth