Intermediate-scale horizontal isoprene concentrations in the near-canopy forest atmosphere and implications for emission heterogeneity

The emissions, deposition, and chemistry of volatile organic compounds (VOCs) are thought to be influenced by underlying landscape heterogeneity at intermediate horizontal scales of several hundred meters across different forest subtypes within a tropical forest. Quantitative observations and scientific understanding at these scales, however, remain lacking, in large part due to a historical absence of canopy access and suitable observational approaches. Herein, horizontal heterogeneity in VOC concentrations in the nearcanopy atmosphere was examined by sampling from an unmanned aerial vehicle (UAV) flown horizontally several hundred meters over the plateau and slope forests in central Amazonia during the morning and early afternoon periods of the wet season of 2018. Unlike terpene concentrations, the isoprene concentrations in the near-canopy atmosphere over the plateau forest were 60% greater than those over the slope forest. A gradient transport model constrained by the data suggests that isoprene emissions differed by 220 to 330%from these forest subtypes, which is in contrast to a 0% difference implemented in most present-day biosphere emissions models (i.e., homogeneous emissions). Quantifying VOC concentrations, emissions, and other processes at intermediate horizontal scales is essential for understanding the ecological and Earth system roles of VOCs and representing them in climate and air quality models. © 2019 National Academy of Sciences. All rights reserved

Biogenic-Anthropogenic Interactions in Secondary Organic Aerosol Formation and Health Effects of Atmospheric Organic Aerosol

Secondary organic aerosol (SOA) formed from oxidation of volatile organic compounds (VOCs), comprises a major fraction of atmospheric submicron particulate matter, which is crucial for global climate change and human health. While biogenic VOCs are naturally emitted and cannot be directly controlled, field measurements and satellite observations have shown that biogenic SOA (BSOA) formation correlates well with anthropogenic pollutants and may be anthropogenically controlled. In this work, the formation of the “anthropogenically controllable BSOA” was examined. BSOA from α-pinene ozonolysis was investigated in the presence of laboratory-generated or ambient organic aerosol such as Toronto ambient particles. It is shown that SOA was not equally miscible with all organic species. Aerosol mixing thermodynamics in the atmosphere is composition dependent. Based on laboratory observations, an empirical framework using bulk elemental ratios was developed to predict atmospheric organic miscibility and SOA yield enhancements. Besides organic aerosol, interactions between BSOA formation and SO2 was also examined. Synergistic effects were observed between BSOA formation and SO2 oxidation through Criegee and peroxide chemistry under atmospherically relevant RH conditions. In addition to the physicochemical properties of SOA, health impacts of SOA were examined. An atmospheric simulation reactor (ASR) was developed to investigate the health effects of air pollutants by permitting controlled chronic in vivo exposure of mice to combine particulate and gaseous pollutants at ‘real-life’ concentrations. Results show that daily exposure to SOA from naphthalene photooxidation led to increased airway hyperresponsiveness (AHR) to methacholine in a dose-dependent manner. Multi-pollutant exposures with ozone and/or NO2 in conjunction with a sub-toxic concentration of SOA resulted in additive effects on AHR to methacholine. Inflammatory cell recruitment to the airways was not observed in any of the exposure conditions, indicating the increased AHR was not associated with airway inflammation and may occur through other mechanisms.Ph.D

Substituent effect on the energy barrier for σ-bond formation from π-single-bonded species, singlet 2,2-dialkoxycyclopentane-1,3-diyls

Background: Localized singlet diradicals are in general quite short-lived intermediates in processes involving homolytic bond-cleavage and formation reactions. In the past decade, long-lived singlet diradicals have been reported in cyclic systems such as cyclobutane-1,3-diyls and cyclopentane-1,3-diyls. Experimental investigation of the chemistry of singlet diradicals has become possible. The present study explores the substituents and the effect of their substitution pattern at the C(1)–C(3) positions on the lifetime of singlet octahydropentalene-1,3-diyls to understand the role of the substituents on the reactivity of the localized singlet diradicals.Results: A series of singlet 2,2-dialkoxy-1,3-diaryloctahydropentalene-1,3-diyls DR were generated in the photochemical denitrogenation of the corresponding azoalkanes AZ. The ring-closed products CP, i.e., 3,3-dialkoxy-2,4-diphenyltricyclo[3.3.0.02,4]octanes, were quantitatively obtained in the denitrogenation reaction. The first-order decay process (k = 1/τ) was observed for the fate of the singlet diradicals DR (λmax ≈ 580–590 nm). The activation parameters, ΔH‡ and ΔS‡, for the ring-closing reaction (σ-bond formation process) were determined by the temperature-dependent change of the lifetime. The energy barrier was found to be largely dependent upon the substituents Ar and Ar’. The singlet diradical DRf (Ar = 3,5-dimethoxyphenyl, OCH2Ar’ = OCH2(3,5-dimethoxyphenyl)) was the longest-lived, τ293 = 5394 ± 59 ns, among the diradicals studied here. The lifetime of the parent diradical DR (Ar = Ph, OCH2Ar’ = OCH3) was 299 ± 2 ns at 293 K.Conclusion: The lifetimes of the singlet 1,3-diyls are found to be largely dependent on the substituent pattern of Ar and Ar’ at the C(1)–C(3) positions. Both the enthalpy and entropy effect were found to play crucial roles in increasing the lifetime

Enhancement in Secondary Organic Aerosol Formation in the Presence of Preexisting Organic Particle

Atmospheric models of secondary organic aerosol (SOA) typically assume organic species form a well-mixed phase. As a result, partitioning of semivolatile oxidation products into the particle phase to form SOA is thought to be enhanced by preexisting organic particles. In this work, the physicochemical properties that govern such enhancement in SOA yield were examined. SOA yields from α-pinene ozonolysis were measured in the presence of a variety of organic seeds which were chosen based on polarity and phase state at room temperature. Yield enhancement was only observed with seeds of medium polarities (tetraethylene glycol and citric acid). Solid hexadecanol seed was observed to enhance SOA yields only in chamber experiments with longer mixing time scales, suggesting that the mixing process for SOA and hexadecanol may be kinetically limited at shorter time scales. Our observations indicate that, in addition to kinetic limitations, intermolecular interactions also play a significant role in determining SOA yields. Here we propose for the first time to use the Hansen solubility framework to determine aerosol miscibility and predict SOA yield enhancement. These results highlight that current models may overestimate SOA formation, and parametrization of intermolecular forces is needed for accurate predictions of SOA formation

Quantifying the Role of the Relative Humidity-Dependent Physical State of Organic Particulate Matter in the Uptake of Semivolatile Organic Molecules

The uptake of gas-phase dicarboxylic acids to organic particulate matter (PM) was investigated to probe the role of the PM physical state in exchange processes between gas-phase semivolatile organic molecules and organic PM. A homologous series of probe molecules, specifically isotopically labeled C-13-dicarboxylic acids, was used in conjunction with aerosol mass spectrometry to obtain a quantitative characterization of the uptake to organic PM for different relative humidities (RHs). The PM was produced by the dark ozonolysis of unlabeled alpha-pinene. The uptake of C-13-labeled oxalic, malonic, and alpha-ketoglutaric acids increased stepwise by 5 to 15 times with increases in RH from 15 to 80%. The enhanced uptake with increasing RH was explained primarily by the higher molecular diffusivity in the particle phase, as associated with changes in the physical state of the organic PM from a nonliquid state to a progressively less-viscous liquid state. At high RH, the partitioning of the probe molecules to the particle phase was more associated with physicochemical interactions with the organic PM than that with the co-absorbed liquid water. Uptake of the probe molecules also increased with a decrease in volatility along the homologous series. This study quantitatively shows the key roles of the particle physical state in governing the interactions of organic PM with semivolatile organic molecules

A Review of Aerosol Chemical Composition and Sources in Representative Regions of China during Wintertime

Comparisons of aerosol composition and sources in different cities or regions are rather limited, yet important for an in-depth understanding of the spatial diversity of aerosol pollution in China. In this study, the data originating from 25 different winter aerosol mass spectrometer (AMS)/aerosol chemical speciation monitor (ACSM) studies were used to provide spatial coverage of the Beijing-Tianjin-Hebei (BTH), Guanzhong (GZ), Yangtze River Delta (YRD), and Pearl River Delta (PRD) regions. The spatial distribution and diurnal variations in aerosol composition and organic sources were analyzed to investigate the aerosol characteristics in the four regions. It was found that there were differences in the compositions of non-refractory particulate matter across the regions, e.g., more sulfate in the PRD versus more nitrate in the YRD, as well as in the organic sources, e.g., more coal combustion in BTH versus more biomass burning in GZ. The characteristics of the composition of NR-PM are similar when the campaigns were classified according to the winter of different years or the cities of different regions. The diurnal variation of the PRD-sulfate indicated its regional nature, whereas the organics from burning sources in two regions of northern China exhibited local characteristics. Based on these findings, we suggest that strict control policies for coal combustion and biomass burning emissions should be enforced in the BTH and GZ regions, respectively

Estimating Absorption Angstrom Exponent of Black Carbon Aerosol by Coupling Multiwavelength Absorption with Chemical Composition

Light absorption by black carbon (BC) and brown carbon (BrC) aerosols determines their impacts on climate warming, and the absorption Angstrom exponent (AAE ) attribution method often is used to distinguish the contributions of the two species to light absorption, but obtaining an accurate value for BC AAE (AAE(BC)) has proven challenging. In this study, a receptor model was coupled with multiwavelength absorption information for light-absorbing aerosols used to retrieve a site-dependent AAE(BC) that reflected the optical properties of the bulk BC aerosol. The results of a positive matrix factorization model showed that AAE(BC )could be separated in contributions from two BC-related factors (pure-BC and BC-rich) during the campaign, and the retrieved average AAE(BC) was 1.19, which is within the range of values obtained through source-related experiments and numerical calculations. The BrC light absorption estimated from AAE(BC) = 1.19 was significantly different from the value (i-e.,AAE(BC) = 1.0) usually assumed in the literature. Our study provides insights that can improve the accuracy in quantifying the light absorption caused by carbonaceous aerosols, especially BrC

Chemical composition and sources of submicron aerosols in winter at a regional site in Beijing-Tianjin-Hebei region: Implications for the Joint Action Plan

The Ministry of Environmental Protection released a joint Action Plan for Control of Air Pollution (Hereafter, joint Action Plan, JAP), to reduce PM2.5 concentrations in the Beijing-Tianjin-Hebei region (13TH) during the winter of 2017. To investigate the effectiveness of the controls, we deployed an aerosol chemical speciation monitor and collected filter samples at Xianghe, a representative site for the BTH, to characterize the aerosol composition during the implementation of the JAP. Those results were compared with earlier data obtained from a literature survey and reanalysis of studies in the BTH. During several pollution episodes in the control period, the major aerosol types changed relative to the earlier studies from sulfate, oxygenated organic aerosol, and coal combustion organic aerosol to nitrate and biomass burning organic aerosol. The dominant secondary inorganic aerosol species during the JAP changed from sulfate to nitrate, and the main source for primary organic aerosol switched from coal combustion to biomass burning. These changes can be explained by the fact that the JAP controls targeted coal combustion and SO2 but not biomass burning or NOx emissions. Our evaluation of the control measures provides a scientific basis for developing new policies in the future. (C) 2020 Elsevier B.V. All rights reserved

Increased secondary aerosol contribution and possible processing on polluted winter days in China

China experiences severe particulate pollution, especially in winter, and determining the characteristics of particulate matter (PM) during pollution events is imperative for understanding the sources and causes of the pollution. However, inconsistencies have been found in the aerosol composition, sources and secondary processing among reported studies. Modern meta-analysis was used to probe the PM chemical characteristics and processing in winter at four representative regions of China, and the first finding was that secondary aerosol formation was the major effect factor for PM pollution. The secondary inorganic species behaved differently in the four regions: sulfate, nitrate, and ammonium increased in the Beijing-Tianjin-Hebei (BTH) and Guanzhong (GZ) areas, but only nitrate increased in the Pearl River Delta (PRD) and Yangtze River Delta (YRD) regions. The increased production of secondary organic aerosol (SOA) was probably caused by aqueous-phase processing in the GZ and BTH regions and by photochemical reactions in the PRD. Finally, we suggest future AMS/ACSM observations should focus on the aerosol characteristics in rural areas in winter in China.</p