2-methylglyceric Acid Research Articles

Novel Method to Quantify Trace Amounts of Isoprene and Monoterpene Secondary Organic Aerosol-Markers in Antarctic Ice.

Biogenic volatile organic compounds (BVOCs) contribute to the formation of secondary organic aerosol (SOA) through atmospheric oxidation. Previously detected SOA-markers in northern hemisphere ice cores from Alaska, Greenland, Russia, and Switzerland indicate the transportation of isoprene and monoterpene oxidation products from their forestry sources to these glacial regions. Antarctica is geographically further removed from the BVOC's source, indicating significantly lower SOA-marker concentrations are likely in southern hemisphere ice cores. The aim of this study was to develop a sensitive mass-spectrometric method to detect and quantify low-abundance SOA-markers of isoprene and monoterpenes in ice core samples. Employment of a triple quadrupole HPLC-MS method enabled limit of detections in the range of 0.4-10 ppt for nine terrestrial SOA-markers and a marker of biomass burning, levoglucosan. Quantification was conducted in the multiple reaction monitoring mode with two specific transitions monitored for each target compound. Application of the developed method onto a section of a Jurassic ice core from Antarctica revealed the presence of seven of the target compounds: 2-methylerythritol, 2-methylglyceric acid, cis-pinonic acid, 3-methyl-1,2,3-butanetricarboxylic acid, pinolic acid, cis-norpinonic acid, and pinic acid. Repeatability ranged between 2.2% and 6.2%. This is the first time that such SOA-markers have been discovered and quantified in Antarctic ice.

New formation and fate of Isoprene SOA markers revealed by field data-constrained modeling

Particulate 2-methyltetrols (2-MT) and 2-methylglyceric acid (2-MG) are typically used to indicate the abundance of isoprene-derived secondary organic aerosols (SOA). However, their formation and fate are not fully understood. In this study, we showed that particulate 2-MT and 2-MG collected at multiple monitoring sites under a wide range of atmospheric and emission conditions, with concentrations spanning six orders of magnitudes, are well reproduced with an expanded isoprene-SOA scheme implemented into the Community Multiscale Air Quality (CMAQ) model. The scheme considers their three-phase (gas-aqueous-organic phase) partitioning, formation from acid-driven multiphase reactions, and degradation by OH radicals in the gas and aqueous phases. The model results reveal that a non-aqueous formation pathway or direct biogenic emission is needed to supplement the commonly assumed acid-driven multiphase reaction process to explain the observed 2-MT concentrations. This missing pathway contributes to 20–40% of 2-MT in areas with aerosol pH<2 and more than 70% under less acidic conditions (pH~2–5), such as those encountered in the western US and China. The typical summertime gas-phase photochemical lifetimes of 2-MT and 2-MG are estimated to be 4–6 and 20–30 h, respectively, and their aqueous lifetimes are approximately 20–40 h. Our simulations show that predicted 2-MT is mainly influenced by its aqueous phase loss to OH, but 2-MG is more sensitive to gas phase OH loss due to the preferential partitioning of the two tracers in the aqueous and gas phases, respectively.

In Situ Observation of Multiphase Oxidation-Driven Secondary Organic Aerosol Formation during Cloud Processing at a Mountain Site in Southern China

Secondary organic aerosols (SOAs) account for a large fraction of atmospheric fine particles, but the mechanisms of their formation and evolution processes remain unclear. In this study, a ground-based counterflow virtual impactor was used in combination with an online time-of-flight aerosol chemical speciation monitor to investigate the multiphase (gaseous and aqueous) oxidation processes and the SOA influencing factors during cloud events at a mountain site in southern China. Our results showed that the clouds promoted the formation of low-oxidized oxygenated organic aerosol (LO-OOA) and more-oxidized oxygenated organic aerosol (MO-OOA). At night, ozone (O3) and nitrate radicals (NO3•) oxidized volatile organic compounds (VOCs, mostly biogenic VOCs) to the precursors of LO-OOA and were absorbed in the cloud droplets to form LO-OOA, while the hydroxyl radical (•OH) was the main oxidant for LO-OOA during daytime. In the cloud droplets, LO-OOA was further oxidized by •OH to form MO-OOA. We propose that isoprene can be oxidized to form products in the gas phase and then absorbed by acidic cloud droplets to form 2-methylglyceric acid (2-MG), 2-MG-organosulfate, and 2-MG-organonitrate. This study improves our understanding of SOA formation, driven by multiphase oxidation during cloud events.

Theoretical Study on the Gas-Phase and Aqueous Interface Reaction Mechanism of Criegee Intermediates with 2-Methylglyceric Acid and the Nucleation of Products.

Criegee intermediates (CIs) are important in the sink of many atmospheric substances, including alcohols, organic acids, amines, etc. In this work, the density functional theory (DFT) method was used to calculate the energy barriers for the reactions of CH3CHOO with 2-methyl glyceric acid (MGA) and to evaluate the interaction of the three functional groups of MGA. The results show that the reactions involving the COOH group of MGA are negligibly affected, and that hydrogen bonding can affect the reactions involving α-OH and β-OH groups. The water molecule has a negative effect on the reactions of the COOH group. It decreases the energy barriers of reactions involving the α-OH and β-OH groups as a catalyst. The Born-Oppenheimer molecular dynamic (BOMD) was applied to simulate the reactions of CH3CHOO with MGA at the gas-liquid interface. Water molecule plays the role of proton transfer in the reaction. Gas-phase calculations and gas-liquid interface simulations demonstrate that the reaction of CH3CHOO with the COOH group is the main pathway in the atmosphere. The molecular dynamic (MD) simulations suggest that the reaction products can form clusters in the atmosphere to participate in the formation of particles.

Diurnal variations in primary and secondary organic aerosols in an eastern China coastal city: The impact of land-sea breezes

The land-sea breeze circulation significantly impacts the atmospheric transport of organic aerosols in coastal regions. However, the links between organic aerosols and land-sea breezes remain poorly understood. In this study, organic marker compounds for biomass burning, primary biological aerosols, biogenic and anthropogenic secondary organic aerosols (SOA) in fine particles from a coastal city in East China were analysed using gas chromatography–mass spectrometry. Land-sea breeze circulations were identified to explore their potential influence on organic molecular compositions. Organic marker compounds showed obvious diurnal/seasonal patterns. Surprisingly, due to the combined influence of weakened East Asian monsoons and land-sea breezes, all detected organic markers decreased except α/β-pinene SOA markers during land-sea breeze periods in early autumn; whereas, all the organic markers increased except α/β-pinene SOA markers, pollen and plant debris markers during land-sea breeze periods in early spring. Furthermore, the reaction pathway and aging of biogenic SOA were also related to land-sea breezes. During the land-sea breeze periods, the ratios of 2-methylglyceric acid (2-MGA) to 2-methyltetrols increased in early autumn, indicating that more isoprene-derived SOA generated from the high-NOx (nitrogen oxides) pathway when the land-sea breezes occurred; while the ratios decreased in early spring, this may be related to the chemical transformation of 2-MGA to 2-MGA sulfates. Changes in the ratio of monoterpene SOA markers demonstrate that monoterpene SOA was relatively aged during sea breeze periods, while it was fresher when the land breeze occurred. Although boundary layer height, emissions, gas/particle partitioning, etc. are important reasons for the diurnal variations of organic aerosols, night/day ratios of molecular markers increased obviously when land-sea breezes occurred in both early autumn and early spring. Our results provide new insights into the shift in the chemical composition of organic aerosols over coastal areas that are influenced by land-sea breezes.

Second-Order Kinetic Rate Coefficients for the Aqueous-Phase Sulfate Radical (SO4•-) Oxidation of Some Atmospherically Relevant Organic Compounds.

The sulfate anion radical (SO4•–) is a reactive oxidant formed in the autoxidation chain of sulfur dioxide, among other sources. Recently, new formation pathways toward SO4•– and other reactive sulfur species have been reported. This work investigated the second-order rate coefficients for the aqueous SO4•– oxidation of the following important organic aerosol compounds (kSO4): 2-methyltetrol, 2-methyl-1,2,3-trihydroxy-4-sulfate, 2-methyl-1,2-dihydroxy-3-sulfate, 1,2-dihydroxyisoprene, 2-methyl-2,3-dihydroxy-1,4-dinitrate, 2-methyl-1,2,4-trihydroxy-3-nitrate, 2-methylglyceric acid, 2-methylglycerate, lactic acid, lactate, pyruvic acid, pyruvate. The rate coefficients of the unknowns were determined against that of a reference in pure water in a temperature range of 298–322 K. The decays of each reagent were measured with nuclear magnetic resonance (NMR) and high-performance liquid chromatography–high-resolution mass spectrometry (HPLC-HRMS). Incorporating additional SO4•– reactions into models may aid in the understanding of organosulfate formation, radical propagation, and aerosol mass sinks.

Spatial and seasonal variations of primary and secondary organic aerosols at urban areas and continental background site of China: Ambient levels, size distribution, and sources

Organic aerosols are important constituents of particulate matter (PM) in the atmosphere, however, the studies on their size distribution, particularly for special primary and secondary organic aerosols (POA, SOA), are relatively limited. In this work, the size-segregated PM was collected from five megacities (Shanghai, Guangzhou, Xi’an, Chengdu, Urumqi) and a continental background site (Qinghai Lake, Tibetan Plateau) of China during 2012–2014. Special POA (plant wax n-alkanes, fossil fuel n-alkanes, PAHs, levoglucosan, and trehalose) and biogenic SOA (BSOA, i.e. isoprene oxidants, monoterpene oxidants, and β-caryophyllenic acid) in PM were measured using gas chromatography/mass spectrometry. n-Alkanes were highest in autumn in the Southeast of China and highest in summer in the Northwest of China during the four seasons. PAHs and levoglucosan were higher in the cold season, mainly influenced by residential heating. Isoprene and monoterpene oxidants were higher in the warm season, while β-caryophyllenic acid was found to be much higher in cold seasons. n-Alkanes showed a monomodal distribution, with a peak at the fine mode (<1.1 µm). PAHs and levoglucosan were characterized by an accumulation mode, revealing the peak at <1.1 µm. However, only trehalosedisplayed coarse mode at the six sites, peaking at a size of 3.3–9.0 µm, because it was mostly derived frombiota in desert regions. Isoprene oxidants including 2-methylglyceric acid, 2-methyltetrols, and C5-alkene triols exhibited a unimodal size distribution pattern with a peak in the fine mode. Monoterpene oxidants such as cis-pinic acid, pinonic acid, 3-hydroxyglutaric acid, and 3-methyl-1,2,3-butanetricarboxylic acid exhibited a bimodal size distribution pattern in the whole sampling time, peaking at the size range of <1.1 µm and 3.3–9.0 µm, respectively. Only β-caryophyllenic acid displayed a fine mode at the six sites during the whole sampling time. These findings can be used to support research into the origin and formation mechanisms of POA and BSOA.

Organosulfates in atmospheric aerosols in Shanghai, China: seasonal and interannual variability, origin, and formation mechanisms

Abstract. Organosulfates (OSs) are ubiquitous in the atmosphere and serve as important tracers for secondary organic aerosols (SOAs). Despite intense research over the years, the abundance, origin, and formation mechanisms of OSs in ambient aerosols, particularly in regions with severe anthropogenic pollution, are still not well understood. In this study, we collected filter samples of ambient fine particulate matter (PM2.5) over four seasons in both 2015–2016 and 2018–2019 at an urban site in Shanghai, China, and comprehensively characterized the OS species in these PM2.5 samples using an ultra-performance liquid chromatography quadrupole time-of-flight mass spectrometer equipped with an electrospray ionization (ESI) source (UPLC-ESI-QToFMS). Overall, we find that while the concentration of organic aerosols (OAs) decreased by 29 % in 2018–2019 compared to that in 2015–2016, mainly as a result of the reduction of anthropogenic pollutant emissions in eastern China, the annually averaged concentrations of 35 quantified OSs were similar in both years (65.5 ± 77.5 ng m−3, 0.57 % ± 0.56 % of OA in 2015–2016 vs. 59.4 ± 79.7 ng m−3, 0.66 % ± 0.56 % of OA in 2018–2019), suggesting an increased contribution of SOAs to OAs in 2018–2019 compared to 2015–2016. Isoprene- and monoterpene-derived OSs were the two most abundant OS families, on average, accounting for 36.3 % and 31.0 % of the quantified OS concentrations, respectively, during both sampling years, suggesting an important contribution of biogenic emissions to the production of OSs and SOAs in Shanghai. The abundance of biogenic OSs, particularly those arising from isoprene, exhibited strong seasonality (peaked in summer) but no significant interannual variability. In contrast, the quantified anthropogenic OSs had little seasonal variability and declined in 2018–2019 compared with those in 2015–2016. The C2 and C3 OS species that have both biogenic and anthropogenic origins contributed, on average, 19.0 % of the quantified OSs, with C2H3O6S−, C3H5O5S−, and C3H5O6S− being the most abundant species, together accounting for 76 % of the C2 and C3 OS concentrations in 2015–2016 and 2018–2019. 2-Methyltetrol sulfate (2-MTS, C5H11O7S−) and monoterpene-derived C10H16NO7S− were the most abundant OSs and nitrooxy OSs in summer, on average, contributing 31 % and 5 % of the quantified OSs, respectively, during the summertime of the sampling years. The substantially larger concentration ratio of 2-MTS to 2-methylglyceric acid sulfate (2-MAS, C4H7O7S−) in summer (6.8–7.8) compared to the other seasons (0.31–0.78) implies that low-NOx oxidation pathways played a dominant role in isoprene-derived SOA formation in summer, while high-NOx reaction pathways were more important in other seasons. We further find that the production of OSs was largely controlled by the level of Ox (Ox= O3+ NO2), namely the photochemistry of OS precursors, particularly in summer, though sulfate concentration, aerosol acidity, and aerosol liquid water content (ALWC) that could affect the heterogeneous chemistry of reactive intermediates leading to OS formation also played a role. Our study provides valuable insights into the characteristics and mechanisms of OS formation in a typical Chinese megacity and implies that the mitigation of Ox pollution can effectively reduce the production of OSs and SOAs in eastern China.

Strong anthropogenic control of secondary organic aerosol formation from isoprene in Beijing

Abstract. Isoprene-derived secondary organic aerosol (iSOA) is a significant contributor to organic carbon (OC) in some forested regions, such as tropical rainforests and the Southeastern US. However, its contribution to organic aerosol in urban areas that have high levels of anthropogenic pollutants is poorly understood. In this study, we examined the formation of anthropogenically influenced iSOA during summer in Beijing, China. Local isoprene emissions and high levels of anthropogenic pollutants, in particular NOx and particulate SO42-, led to the formation of iSOA under both high- and low-NO oxidation conditions, with significant heterogeneous transformations of isoprene-derived oxidation products to particulate organosulfates (OSs) and nitrooxy-organosulfates (NOSs). Ultra-high-performance liquid chromatography coupled to high-resolution mass spectrometry was combined with a rapid automated data processing technique to quantify 31 proposed iSOA tracers in offline PM2.5 filter extracts. The co-elution of the inorganic ions in the extracts caused matrix effects that impacted two authentic standards differently. The average concentration of iSOA OSs and NOSs was 82.5 ng m−3, which was around 3 times higher than the observed concentrations of their oxygenated precursors (2-methyltetrols and 2-methylglyceric acid). OS formation was dependant on both photochemistry and the sulfate available for reactive uptake, as shown by a strong correlation with the product of ozone (O3) and particulate sulfate (SO42-). A greater proportion of high-NO OS products were observed in Beijing compared with previous studies in less polluted environments. The iSOA-derived OSs and NOSs represented 0.62 % of the oxidized organic aerosol measured by aerosol mass spectrometry on average, but this increased to ∼3 % on certain days. These results indicate for the first time that iSOA formation in urban Beijing is strongly controlled by anthropogenic emissions and results in extensive conversion to OS products from heterogenous reactions.

Molecular composition and source apportionment of fine organic aerosols in Northeast China

Abstract We examined the characteristics and source apportionment of organic aerosols in ambient PM2.5 samples collected during the late autumn in Changchun, Northeast China. 8 compound classes (>90 individual species) were detected in the aerosol samples, including biomass burning tracers, aliphatic lipids (fatty acids and fatty alcohols), secondary oxidation products, polycyclic aromatic hydrocarbons (PAHs), sugar compounds, hopanes and biogenic secondary organic aerosol (SOA) tracers. The concentrations of total quantified organic species ranged from 138.2 to 6.8 × 103 ng m−3, among which levoglucosan was the most abundant compound. Biomass burning tracers (anhydrosugars, lignin and resin acids) were the most abundant compounds, followed by fatty acids, secondary oxidation products, PAHs, sugar compounds and fatty alcohols. Biogenic SOA tracers and hopanes were less abundant. The homohopane index [defined as 31abS/(31abS + 31abR)] was 0.5, indicating a potential contribution of traffic emission. PAHs showed a dominance of benzo(b)fluoranthene (BbF), and the diagnostic ratios implicated a substantial contribution of petroleum combustion as well as coal combustion. 2-methylglyceric acid to 2-methyltetrols ratio (2.2) indicated that NOx influence isoprene oxidation products formation. Furthermore, the average ratio of cis-pinonic acid plus pinic acid to 3-hydroxyglutaric acid (31.4) revealed the much fresher α/β-pinene oxidation products to some extent. A good correlation was found between β-caryophyllinic acid and levoglucosan (r = 0.61), suggesting that β-caryophyllene can mainly be generated by biomass burning. The biogenic secondary organic carbon (SOC) was underestimated by the tracer-based method, which only occupied 0.4% of the organic carbon (OC). In contrast, PMF model indicated that emissions from fossil fuel combustion and biomass burning were most important, accounting for 42.4% and 33.6%, respectively, followed by biogenic SOA emission (17.0%) and fungal spore derived source (7.0%), suggesting biogenic aerosol is a nonnegative contributor. Capsule Fossil fuel combustion (42.4%) as well as biomass burning (33.6%) were most important contributors of organic aerosols in a typical city in Northeast China.

Molecular characteristics of organic compositions in fresh and aged biomass burning aerosols

Biomass burning (BB) is the most important source of primary organic aerosols (OA) in the atmosphere that has significant impact on local/regional air quality and human health. However, few studies paid attention to the evolution of molecular characteristics of BB OA in the atmospheric aging processes. In this study, both fresh and aged PM2.5 aerosols from burning of rice, maize, and wheat straws were collected from a combined system of combustion chamber and oxidation flow reactor, and were analyzed for >100 organic species. The emission factors (EFs) of anhydrosugars and some fatty acids showed slight variations between fresh and aged samples, indicating that these compounds are relatively stable. However, the EFs of n-alkanes, fatty alcohols, and parent-PAHs decreased 8–57% from fresh to aged samples, suggesting that they can undergo further oxidation to form other organic materials in the atmosphere. Phthalic acids, nitrophenols and isoprene-derived products were mainly secondarily formed by aging processes. Thus their EFs increased by 2–23 times from fresh to aged samples. Levoglucosan was the most abundant individual organic tracer, and its EF varied slightly between fresh and aged samples, proving its indicative role on BB emission. Moreover, the ratio of vanillic acid to levoglucosan and p-hydroxybenzoic acid to levoglucosan increased 2–13 times from fresh to aged samples. Therefore they can be used to investigate the impact of aging processes on BB aerosols in the atmosphere. RO2 + HO2 pathway derived 2-methyltetrols (2-MTs) predominated the EFs of isoprene-derived products (SOAi) in the fresh samples. However, RO2 + NO pathway derived 2-methylglyceric acid (2-MGA) increased by >30 times and became comparable with 2-MTs in aged particles. The ratio of 2-MGA/2-MTs increased from 0.06–0.27 in fresh samples to 0.94–1.18 in aged samples, because the high loading of NOx in BB smoke enhanced the formation of SOAi through RO2 + NO reactions.

Natural and Anthropogenically Influenced Isoprene Oxidation in Southeastern United States and Central Amazon.

Anthropogenic emissions alter secondary organic aerosol (SOA) formation chemistry from naturally emitted isoprene. We use correlations of tracers and tracer ratios to provide new perspectives on sulfate, NOx, and particle acidity influencing isoprene-derived SOA in two isoprene-rich forested environments representing clean to polluted conditions-wet and dry seasons in central Amazonia and Southeastern U.S. summer. We used a semivolatile thermal desorption aerosol gas chromatograph (SV-TAG) and filter samplers to measure SOA tracers indicative of isoprene/HO2 (2-methyltetrols, C5-alkene triols, 2-methyltetrol organosulfates) and isoprene/NOx (2-methylglyceric acid, 2-methylglyceric acid organosulfate) pathways. Summed concentrations of these tracers correlated with particulate sulfate spanning three orders of magnitude, suggesting that 1 μg m-3 reduction in sulfate corresponds with at least ∼0.5 μg m-3 reduction in isoprene-derived SOA. We also find that isoprene/NOx pathway SOA mass primarily comprises organosulfates, ∼97% in the Amazon and ∼55% in Southeastern United States. We infer under natural conditions in high isoprene emission regions that preindustrial aerosol sulfate was almost exclusively isoprene-derived organosulfates, which are traditionally thought of as representative of an anthropogenic influence. We further report the first field observations showing that particle acidity correlates positively with 2-methylglyceric acid partitioning to the gas phase and negatively with the ratio of 2-methyltetrols to C5-alkene triols.

Impact of anthropogenic emissions on biogenic secondary organic aerosol: observation in the Pearl River Delta, southern China

Abstract. Secondary organic aerosol (SOA) formation from biogenic precursors is affected by anthropogenic emissions, which are not well understood in polluted areas. In this study, we accomplished a year-round campaign at nine sites in polluted areas located in the Pearl River Delta (PRD) region during 2015. We measured typical biogenic SOA (BSOA) tracers from isoprene, monoterpenes, and β-caryophyllene, as well as major gaseous and particulate pollutants and investigated the impact of anthropogenic pollutants on BSOA formation. The concentrations of BSOA tracers were in the range of 45.4 to 109 ng m−3 with the majority composed of products from monoterpenes (SOAM, 47.2±9.29 ng m−3), isoprene (SOAI, 23.1±10.8 ng m−3), and β-caryophyllene (SOAC, 3.85±1.75 ng m−3). We found that atmospheric oxidants, Ox (O3 plus NO2), and sulfate correlated well with later-generation SOAM tracers, but this was not the case for first-generation SOAM products. This suggested that high Ox and sulfate levels could promote the formation of later-generation SOAM products, which probably led to the relatively aged SOAM that we observed in the PRD. For the SOAI tracers, both 2-methylglyceric acid (NO/NO2-channel product) and the ratio of 2-methylglyceric acid to 2-methyltetrols (HO2-channel products) exhibit NOx dependence, indicating the significant impact of NOx on SOAI formation pathways. The SOAC tracer was elevated in winter at all sites and was positively correlated with levoglucosan, Ox, and sulfate. Thus, the unexpected increase in SOAC in wintertime might be highly associated with the enhancement of biomass burning, O3 chemistry, and the sulfate component in the PRD. The BSOAs that were estimated using the SOA tracer approach showed the highest concentration in fall and the lowest concentration in spring with an annual average concentration of 1.68±0.40 µg m−3. SOAM dominated the BSOA mass all year round. We also found that BSOA correlated well with sulfate and Ox. This implied a significant effect from anthropogenic pollutants on BSOA formation and highlighted that we could reduce BSOA by controlling the anthropogenic emissions of sulfate and Ox precursors in polluted regions.

Organic Hydroxy Acids as Highly Oxygenated Molecular (HOM) Tracers for Aged Isoprene Aerosol.

Highly oxygenated molecules (HOMs) are a class of compounds associated with secondary organic aerosols exhibiting high oxygen to carbon (O:C) ratios and often originating from the oxidation of biogenic compounds. Here, the photooxidation and ozonolysis of isoprene were examined under a range of conditions to identify HOM tracers for aged isoprene aerosol. The HOM tracers were identified as silylated derivatives by gas chromatography-mass spectrometry and by detecting their parent compounds by liquid chromatography-high resolution mass spectrometry. In addition to the previously observed methyltetrols and 2-methylglyceric acid, seven tracer compounds were identified, including 2-methyltartronic acid (MTtA), 2-methylerythronic acid (2MeTrA), 3-methylerythronic acid (3MeTrA), 2-methylthreonic acid (2MTrA), 3-methylthreonic acid (3MTrA), erythro-methyltartaric acid (e-MTA), and threo-methyltartaric acid (t-MTA). The molecular structures were confirmed with authentic standards synthesized in the laboratory. The presence of some of these HOMs in the gas and particle phases simultaneously provides evidence of their gas/particle partitioning. To determine the contributions of aged isoprene products to ambient aerosols, we analyzed ambient PM2.5 samples collected in the southeastern United States in summer 2003 and at two European monitoring stations located in Zielonka and Godów (Poland). Our findings show that methyltartaric acids (MTA) and 2- and 3-methylthreonic acids (and their stereoisomers) are representative of aged isoprene aerosol because they occur both in the laboratory chamber aerosol obtained and in ambient PM2.5. On the basis of gas chromatography-mass spectrometry (GC-MS) analysis, their concentrations were found to range from 0.04 ng for 3-methylthreonic acid to 6.3 ng m-3 for methyltartaric acid at the southeast site in Duke Forest, NC, USA.

Enhancement of Atmospheric Nucleation by Highly Oxygenated Organic Molecules: A Density Functional Theory Study.

New particle formation (NPF) by gas-particle conversion is the main source of atmospheric aerosols. Highly oxygenated organic molecules (HOMs) and sulfuric acid (SA) are important NPF participants. 2-Methylglyceric acid (MGA), a kind of HOMs, is a tracer of isoprene-derived secondary organic aerosols. The nucleation mechanisms of MGA with SA were studied using density functional theory and atmospheric cluster dynamics simulation in this study, along with that of MGA with methanesulfonic acid (MSA) as a comparison. Our theoretical works indicate that the (MGA)(SA) and (MGA)(MSA) clusters are the most stable ones in the (MGA) i(SA) j ( i = 1-2, j = 1-2) and (MGA) i(MSA) j ( i = 1-2, j = 1-2) clusters, respectively. Both the formation rates of (MGA)(SA) and (MGA)(MSA) clusters are quite large and could have significant contributions to NPF. The results imply that the homomolecular nucleation of MGA is unlikely to occur in the atmosphere, and MGA and SA can effectively contribute to heteromolecular nucleation mainly in the form of heterodimers. MSA exhibits properties similar to SA in its ability to form clusters with MGA but is slightly weaker than SA.

Low-volatility compounds contribute significantly to isoprene secondary organic aerosol (SOA) under high-NO&amp;lt;sub&amp;gt;&amp;lt;i&amp;gt;x&amp;lt;/i&amp;gt;&amp;lt;/sub&amp;gt; conditions

Abstract. Recent advances in our knowledge of the gas-phase oxidation of isoprene, the impact of chamber walls on secondary organic aerosol (SOA) mass yields, and aerosol measurement analysis techniques warrant reevaluating SOA yields from isoprene. In particular, SOA from isoprene oxidation under high-NOx conditions forms via two major pathways: (1) low-volatility nitrates and dinitrates (LV pathway) and (2) hydroxymethyl-methyl-α-lactone (HMML) reaction on a surface or the condensed phase of particles to form 2-methyl glyceric acid and its oligomers (2MGA pathway). These SOA production pathways respond differently to reaction conditions. Past chamber experiments generated SOA with varying contributions from these two unique pathways, leading to results that are difficult to interpret. This study examines the SOA yields from these two pathways independently, which improves the interpretation of previous results and provides further understanding of the relevance of chamber SOA yields to the atmosphere and regional or global modeling. Results suggest that low-volatility nitrates and dinitrates produce significantly more aerosol than previously thought; the experimentally measured SOA mass yield from the LV pathway is ∼0.15. Sufficient seed surface area at the start of the reaction is needed to limit the effects of vapor wall losses of low-volatility compounds and accurately measure the complete SOA mass yield. Under dry conditions, substantial amounts of SOA are formed from HMML ring-opening reactions with inorganic ions and HMML organic oligomerization processes. However, the lactone organic oligomerization reactions are suppressed under more atmospherically relevant humidity levels, where hydration of the lactone is more competitive. This limits the SOA formation potential from the 2MGA pathway to HMML ring-opening reactions with water or inorganic ions under typical atmospheric conditions. The isoprene SOA mass yield from the LV pathway measured in this work is significantly higher than previous studies have reported, suggesting that low-volatility compounds such as organic nitrates and dinitrates may contribute to isoprene SOA under high-NOx conditions significantly more than previously thought and thus deserve continued study.

Analysis of molecular species of phosphatidylcholine hydroperoxide in human native and copper-oxidized triglyceride-rich lipoproteins

The presence of water-soluble dicarboxylic acids in atmospheric aerosols has a significant influence on the regional radiative forcing through direct aerosol effect and cloud formation process. Fine aerosol (PM2.5) samples collected in central Alaska (Fairbanks: 64.51°N and 147.51°W) during summer of 2009 were measured for water-soluble diacids (C2–C12), oxoacids (C2–C9) and α-dicarbonyls (C2–C3) as well as elemental carbon (EC), organic carbon (OC) and water-soluble OC (WSOC) to assess their sources and formation processes. We found the predominance of oxalic acid (C2) followed by malonic (C3) and succinic acid (C4) in Alaskan aerosols. Higher C3/C4 diacid ratios (ave. 1.2) in Alaskan aerosols than those reported for fresh aerosols emitted from fossil fuel combustion (ave. 0.35) and biomass burning (0.51–0.66) suggest that organic aerosols in central Alaska were photochemically processed. The relatively high correlations of major diacids and related compounds with levoglucosan (r = 0.80–0.99) than those with 2-methylglyceric acid (r = 0.59–0.98) suggest that they were significantly produced from biomass burning emission. Strong correlations of C2 with normal-chain saturated diacids (C3-C9: r = 0.80–0.98), glyoxylic acid (ωC2: r = 0.95) and methylglyoxal (MeGly: r = 0.88), together with strong correlations of solar radiation with ratio of C2 to C2–C12 diacids (r = 0.83), ωC2 (r = 0.80) and MeGly (r = 0.82) suggest that oxalic acid in PM2.5 aerosol was produced by the photooxidation of higher homologous diacids, glyoxylic acid and methylglyoxal in the atmosphere of central Alaska. These results reveal that photochemical processing of organic precursors mainly produced from biomass burning control the water-soluble organic chemical composition of fine aerosols in central Alaska.

Dicarboxylic acids, oxocarboxylic acids and α-dicarbonyls in atmospheric aerosols from Mt. Fuji, Japan: Implication for primary emission versus secondary formation

Aerosol samples were collected at the summit of Mt. Fuji in July–August 2009 and analyzed for diacids and related compounds together with major ions to decipher the sources and formation process of organic aerosols in the free troposphere. Molecular distributions of diacids showed the predominance of oxalic acid (C2) followed by succinic (C4) and malonic (C3) acids. The average concentration of total diacids is ten times higher in whole-day samples than night-only samples due to the uplift of planetary boundary layer in daytime, suggesting the daytime formation of diacids in the uplifted ground-level air mass along the mountain slope. A strong correlation is found between C4 and levoglucosan in whole-day and nighttime samples. Liquid water content (LWC) shows strong correlations in nighttime with anthropogenic and biogenic secondary organic aerosol (SOA) tracers (e.g., adipic (0.90, p < 0.05) and phthalic acids (0.93, p < 0.05) and 3-methyl 2,3,4-trihydroxy-1-butene (0.95, p < 0.05), suggesting that aqueous-phase chemistry is important for the formation of water-soluble organic aerosols in the free troposphere. In whole-day samples, LWC is strongly correlated with organic carbon (r = 0.97, p < 0.05), and isoprene-SOA tracers such as methylthreitol (0.96, p < 0.05), methylerythritol (0.97, p < 0.05), 2-methylglyceric acid (0.94, p <0 .05) and glycolic acid (0.98, p < 0.05), suggesting that daytime SOAs are mainly from the oxidation of isoprene emitted from the regional forests on the foothill of Mt. Fuji. A strong correlation between LWC and glycolic acid further suggests that isoprene is the main precursor for the production of oxalic acid via glycolic acid as intermediate. This study supports the heterogeneous formation of diacids in the free troposphere.

Chemical composition of isoprene SOA under acidic and non-acidic conditions: effect of relative humidity.

The effect of acidity and relative humidity on bulk isoprene aerosol parameters has been investigated in several studies; however, few measurements have been conducted on individual aerosol compounds. The focus of this study has been the examination of the effect of acidity and relative humidity on secondary organic aerosol (SOA) chemical composition from isoprene photooxidation in the presence of nitrogen oxide (NOx). A detailed characterization of SOA at the molecular level was also investigated. Experiments were conducted in a 14.5 m3 smog chamber operated in flow mode. Based on a detailed analysis of mass spectra obtained from gas chromatography–mass spectrometry of silylated derivatives in electron impact and chemical ionization modes, ultra-high performance liquid chromatography/electrospray ionization/time-of-flight high-resolution mass spectrometry, and collision-induced dissociation in the negative ionization modes, we characterized not only typical isoprene products but also new oxygenated compounds. A series of nitroxy-organosulfates (NOSs) were tentatively identified on the basis of high-resolution mass spectra. Under acidic conditions, the major identified compounds include 2-methyltetrols (2MT), 2-methylglyceric acid (2mGA), and 2MT-OS. Other products identified include epoxydiols, mono- and dicarboxylic acids, other organic sulfates, and nitroxy- and nitrosoxy-OS. The contribution of SOA products from isoprene oxidation to PM2.5 was investigated by analyzing ambient aerosol collected at rural sites in Poland. Methyltetrols, 2mGA, and several organosulfates and nitroxy-OS were detected in both the field and laboratory samples. The influence of relative humidity on SOA formation was modest in non-acidic-seed experiments and stronger under acidic seed aerosol. Total secondary organic carbon decreased with increasing relative humidity under both acidic and non-acidic conditions. While the yields of some of the specific organic compounds decreased with increasing relative humidity, others varied in an indeterminate manner from changes in the relative humidity.

Typical polar organic aerosol tracers in PM2.5 over the North China Plain: Spatial distribution, seasonal variations, contribution and sources

PM2.5 samples were collected simultaneously at three urban sites including Beijing (BJ), Tianjin (TJ), Shijiazhuang (SJZ) and one background site Xinglong (XL) from June 2014 till April 2015. Typical polar organic aerosol tracers including 2-methylglyceric acid, 2-methyltetrols, 3-hydroxyglutaric acid, anhydrous saccharides and phthalic acid were analyzed by gas chromatography-mass spectrometry. Both Isoprene secondary organic aerosol (SOA) tracers and pinene SOA tracers had higher mass concentrations at background site than those at urban sites. But they showed different seasonal variations. The former had the highest mass concentration in summer while the latter had the highest mass concentration in spring. Anhydrous saccharides and phthalic acids at urban sites had higher mass concentrations than those at background site and showed higher mass concentration in autumn and winter, respectively. Corresponding estimated secondary organic carbons (SOCs) showed similar variation trends with tracers. In general, biogenic sources had more influence on background site while urban sites were more affected by anthropogenic sources.