Ketocarboxylic Acids Research Articles

Lactonization of α-Ferrocenyl Ketocarboxylic Acids via Nucleophilic Attack of Carbonyl Oxygen

The effects of the ferrocenyl moiety to enhance the nucleophilicity of the carbonyl group, situated at its adjacent position, have been explored in a series of α-ferrocenyl ketocarboxylic acids. In the presence of trifluoroacetic anhydride, 3-ferrocenoylpropionic acid and 4-ferrocenoylbutyric acid gave 5-ferrocenyl-4-trifluoroacetyl-2(3H)-furanone and 6-ferrocenyl-5-trifluoroacetyl-3,4-dihydropyran-2-one, respectively. Under similar reaction conditions, 2-ferrocenylcarbonylbenzoic acid, a keto carboxylic acid without a β-hydrogen, gave a dimerized lactone, 3,3′-diferrocenyl-3,3′-diphthalide, possibly due to radical coupling. The nucleophilic attack of carbonyl oxygen, activated by the ferrocenyl moiety, on the carboxylic carbon is assumed to be the crucial mechanistic step in forming these lactones. When the carbonyl group was reduced to an alcohol to break its conjugation with the ferrocenyl moiety, saturated lactones were isolated after the acidic workup. These results indicate that the α-ferrocenyl carbinols readily undergo solvolysis under acidic conditions, giving ferrocenylcarbenium ions, which are attacked by the carboxy oxygen to give lactones.

Exceptionally Mild and High-Yielding Synthesis of Vinyl Esters of Alpha-Ketocarboxylic Acids, Including Vinyl Pyruvate, for Parahydrogen-Enhanced Metabolic Spectroscopy and Imaging.

Metabolic changes often occur long before pathologies manifest and treatment becomes challenging. As key elements of energy metabolism, α-ketocarboxylic acids (α-KCA) are particularly interesting, e.g., as the upregulation of pyruvate to lactate conversion is a hallmark of cancer (Warburg effect). Magnetic resonance imaging with hyperpolarized metabolites has enabled imaging of this effect non-invasively and in vivo, allowing the early detection of cancerous tissue and its treatment. Hyperpolarization by means of dynamic nuclear polarization, however, is complex, slow, and expensive, while available precursors often limit parahydrogen-based alternatives. Here, we report the synthesis for novel 13C, deuterated ketocarboxylic acids, and a much-improved synthesis of 1-13C-vinyl pruvate-d6, arguably the most promising tracer for hyperpolarizing pyruvate using parahydrogen-induced hyperpolarization by side arm hydrogenation. The new synthesis is scalable and provides a high yield of 52%. We elucidated the mechanism of our Pd-catalyzed trans-vinylation reaction. Hydrogenation with parahydrogen allowed us to monitor the addition, which was found to depend on the electron demand of the vinyl ester. Electron-poor α-keto vinyl esters react slower than "normal" alkyl vinyl esters. This synthesis of 13C, deuterated α-ketocarboxylic acids opens up an entirely new class of biomolecules for fast and cost-efficient hyperpolarization with parahydrogen and their use for metabolic imaging.

Visible-light-mediated β-acylative divergent alkene difunctionalization with Katritzky salt/CO2

Photoredox-catalyzed, divergent acylative-benzylation and acylative-carboxylation of alkenes are achievedviathe radical–radical/radical–polar crossover pathway respectively with benzyl radicals and CO2following decarboxylation from ketocarboxylic acids.

The β-carotene–oxygen copolymer: its relationship to apocarotenoids and β-carotene function

β-carotene spontaneously copolymerizes with molecular oxygen to form a β-carotene–oxygen copolymer compound (“copolymer”) as the main product, together with small amounts of many apocarotenoids. Both the addition and scission products are interpreted as being formed during progression through successive free radical β-carotene–oxygen adduct intermediates. The product mixture from full oxidation of β-carotene, lacking both vitamin A and β-carotene, has immunological activities, some of which are derived from the copolymer. However, the copolymer’s chemical makeup is unknown. A chemical breakdown study shows the compound to be moderately stable but nevertheless the latent source of many small apocarotenoids. GC–MS analysis with mass-spectral library matching identified a minimum of 45 structures, while more than 90 others remain unassigned. Newly identified products include various small keto carboxylic acids and dicarboxylic acids, several of which are central metabolic intermediates. Also present are glyoxal and methyl glyoxal dialdehydes, recently reported as β-carotene metabolites in plants. Although both compounds at higher concentrations are known to be toxic, at low concentration, methyl glyoxal has been reported to be potentially capable of activating an immune response against microbial infection. In plants, advantage is taken of the electrophilic reactivity of specific apocarotenoids derived from β-carotene oxidation to activate protective defenses. Given the copolymer occurs naturally and is a major product of non-enzymatic β-carotene oxidation in stored plants, by partially sequestering apocarotenoid metabolites, the copolymer may serve to limit potential toxicity and maintain low cellular apocarotenoid concentrations for signaling purposes. In animals, the copolymer may serve as a systemic source of apocarotenoids.

Ultrasound-assisted synthesis and in vitro antimicrobial activity of novel 5-oxo-2-pyrrolidinecarboxamides and 7-oxo-2-azepanecarboxamides

A facile one-pot reaction has been set up for the synthesis of novel 5-oxo-2-pyrrolidinecarboxamides and 7-oxo-2-azepanecarboxamides 4a-j from three-component reaction of keto carboxylic acids 1a-d, various primary amines 2a-b and isocyanides 3a-b under ultrasound irradiation. The present protocol offers attractive characteristics such as easy handling methodology, good-to-excellent yields, environmental friendliness, clean reaction, higher atom economy, convenient operation, and shorter reaction time. The newly synthesized 5-oxo-2-pyrrolidinecarboxamides and 7-oxo-2-azepanecarboxamides 4a-j have been screened for their antimicrobial activity and the majority of these cyclic amides exhibited weak antimicrobial activity.

Synthesis of Spiro[cycloalkane-pyridazinones] with High Fsp3 Character

Background: owadays, in course of the drug design and discovery much attention is paid to the physicochemical parameters of a drug candidate, in addition to their biological activity. Disadvantageous physicochemical parameters can hinder the success of a drug candidate. Objective: Lovering et al. introduced the Fsp3 character as a measure of carbon bond saturation, which is related to the physicochemical paramethers of the drug. The pharmaceutical research focuses on the synthesis of compounds with high Fsp3 character. Methods: To improve the physicochemical properties (clogP, solubility, more advantageous ADME profile, etc.) of drug-candidate molecules one possibility is the replacement of all-carbon aromatic systems with bioisoster heteroaromatic moieties, e.g. with one or two nitrogen atom containing systems, such as pyridines and pyridazines, etc. The other option is to increase the Fsp3 character of the drug candidates. Both of these aspects were considered in the design the new spiro[cycloalkanepyridazinones], the synthesis of which is described in the present study. Results: Starting from 2-oxaspiro[4.5]decane-1,3-dione or 2-oxaspiro[4.4]nonane-1,3-dione, the corresponding ketocarboxylic acids were obtained by Friedel-Crafts reaction with anisole or veratrole. The ketocarboxylic acids were treated by hydrazine, methylhydrazine or phenylhydrazine to form the pyridazinone ring. N-Alkylation reaction of the pyridazinones resulted in the formation of further derivatives with high Fsp3 character. Conclusion: A small compound library was obtained incorporating compounds with high Fsp3 characters, which predicts advantageous physico-chemical parameters (LogP, ClogP and TPSA) for potential applications in medicinal chemistry.

Molecular characteristics and stable carbon isotope compositions of dicarboxylic acids and related compounds in the urban atmosphere of the North China Plain: Implications for aqueous phase formation of SOA during the haze periods

In the past five years, Chinese government has promulgated stringent measures to mitigate air pollution. However, PM2.5 levels in the China North Plain (NCP), which is one of the regions with the heaviest air pollution in the world, are still far beyond the World Health Organization (WHO) standard. To improve our understanding on the sources and formation mechanisms of haze in the NCP, PM2.5 samples were collected during the winter of 2017 on a day/night basis at the urban site of Liaocheng, which is one of the most polluted cities in the NCP. The samples were determined for molecular distributions and stable carbon isotope compositions of dicarboxylic acids and their precursors (ketocarboxylic acids and α-dicarbonyls), levoglucosan, elemental carbon (EC), organic carbon (OC) and water-soluble organic carbon (WSOC). Our results showed that oxalic acid (C2) is the dominant dicarboxylic acid, followed by succinic acid (C4) and malonic acid (C3), and glyoxylic acid (ωC2) is the most abundant ketocarboxylic acids. Concentrations of C2, glyoxal (Gly) and methylglyoxal (mGly) presented robust correlations with levoglucosan, suggesting that biomass burning is a significant source of PM2.5 in the NCP. Moreover, C2 and Gly and mGly linearly correlated with SO42-, relative humidity (RH), aerosol liquid water content (LWC) as well as particle in-situ pH (pHis), indicating that aqueous-phase oxidation is the major formation pathway of these SOA, and is driven by acid-catalyzed oxidation. Concentrations and relative abundances of secondary species including SNA (SO42−, NO3− and NH4+), dicarboxylic acids, and aerosol LWC in PM2.5 are much higher in the haze periods than in the clean periods, suggesting that aqueous reaction is a vital role in the haze formation. In comparison with those in the clean periods, stable carbon isotopic compositions (δ13C) of major dicarboxylic acids and related SOA and the mass ratios of C2/diacids, C2/Gly and C2/mGly are higher in the haze periods, indicating that haze particles were more aged and enriched in secondary species.

Diurnal Variation of Dicarboxylic Acids and Related SOA in PM2.5 from Heze City in Winter

To identify the diurnal variation and formation mechanism of dicarboxylic acids and related compounds in PM2.5 from Heze City, PM2.5 samples were collected in the winter (December) of 2017, which were subsequently analyzed for dicarboxylic acids, ketocarboxylic acids, α-dicarbonyls, and levoglucosan (Levo). The results showed that the total concentrations of dicarboxylic and ketocarboxylic acids were higher during daytime than those during nighttime. In contrast to the diurnal variation of dicarboxylic and ketocarboxylic acids, the total concentrations of α-dicarbonyls exhibited higher concentrations in nighttime than in daytime. Because α-dicarbonyls are the major precursors of dicarboxylic acids, the opposing patterns suggest that the photochemical oxidation in daytime is stronger than that in nighttime. Oxalic acid (C2) is the dominant species during both day-and nighttime, followed by phahalic acid (Ph), succinic acid (C4), and malonic acid (C3), which is consistent with that in other urban regions. The mass ratios of C3/C4 (R2>0.7) correlated strongly with temperature, indicating that organic compounds in the atmosphere of Heze City are mainly derived from the photochemical oxidation of local emissions rather than long-range transport in winter. C2 correlated with in-situ pH and SO42-, suggesting that aqueous-phase oxidation was the major formation pathway of C2, which is driven by acid-catalyzed oxidation. Since the major SOA (C2, glyoxal, and methyglyoxal, secondary organic aerosol) correlated with Levo and the average mass rations of K+/organic carbon was 0.06 (ranging from 0.03 to 0.13), it can be concluded that the dicarboxylic acids and related SOA and K+ in Heze City were significantly influenced by biomass burning in winter.

Seasonal Variation and Sources of Dicarboxylic Acids and Related Compounds in PM10 from Mt. Huangshan

To identify the seasonal variation of dicarboxylic acids and related compounds in PM10 from Mt. Huangshan. PM10samples were collected during the summer and winter of 2015, which were then analyzed for dicarboxylic acids, ketocarboxylic acids, and α-dicarbonyls. The results showed that oxalic acid(HOOC-COOH, C2) was the dominant species in the summer and winter months, followed by malonic acid(HOOC-CH2-COOH, C3), and succinic acid[HOOC-(CH2)2-COOH, C4], being consistent with that in other high-altitude regions. Most of the diacids were more abundant in the summer months than in the winter months, while adipic acid(C6) and phahalic acid(Ph) were twice lower in the summer months, suggesting significant impact of anthropogenic pollution on the wintertime alpine atmosphere. Moreover, as major precursors of C2, glyoxal(Gly) and methylglyoxal(mGly) were also lower in the summer months than in the winter months, which were opposite to those of the diacids, indicating that the mountain troposphere was more oxidative in the summer months than in the winter months. Principal component analysis(PCA) further revealed that the wintertime SOA in the Mt. Huangshan troposphere mostly originated from the anthropogenic pollutants from long-distance transport. Conversely, the summertime SOA mostly originated from the further oxidation of the mountainous biogenic sources. The AIM(Aerosol Inorganic Model) calculation results showed that the aqueous-phase C2 production was the primary mechanism of C2 formation in ambient aerosol and was driven by acid-catalyzed oxidation in summer.

Field observation on secondary organic aerosols during Asian dust storm periods: Formation mechanism of oxalic acid and related compounds on dust surface

Chemical evolution of East Asian dust during transpacific transport has been given much attention for inorganic species such as sulfate, nitrate and ammonium. However, the role of organic species during the transport has almost entirely been ignored. To understand the formation mechanism of secondary organic aerosols (SOA) on dust surfaces, this study investigated the concentrations and compositions of dicarboxylic acids, keto-carboxylic acids, α-dicarbonyls and inorganic ions in size-segregated aerosols (9-stages) collected in Xi'an, central China during the two dust storm episodes in the springs of 2009 and 2011 and compared with those in nondust storm periods. During the events the ambient particulate dicarboxylic acids were 932–2240 ng m−3, which are comparable and even higher than those in nondust periods. Molecular compositions of the above SOA are similar to those in nondust periods with oxalic acid being the leading species. In the presence of the dust storms, all the above mentioned SOA species in Xi'an were predominantly enriched on the coarse particles (>2.1 μm), and oxalic acid well correlated with NO3− (R2 = 0.72, p < 0.001) rather than SO42−. This phenomenon differs greatly from the SOA in any other nondust period that is usually characterized by an enrichment of oxalic acid in fine mode and a strong correlation of oxalic acid with SO42−. We propose a formation pathway to explain these observations, in which nitric acid and/or nitrogen oxides react with dust to produce Ca(NO3)2 and form a liquid phase on the surface of dust aerosols via water vapor-absorption of Ca(NO3)2, followed by a partitioning of the gas-phase water-soluble organic precursors (e.g.,glyoxal and methylglyoxal) into the aqueous-phase and a subsequent oxidation into oxalic acid. To the best of our knowledge, we found for the first time the enrichment of glyoxal and methylglyoxal on dust surface. Our data suggest an important role of nitrate in the heterogeneous formation process of SOA on the surface of dust.

Size-resolved airborne particulate oxalic and related secondary organic aerosol species in the urban atmosphere of Chengdu, China

Size-segregated (9-stages) airborne particles during winter in Chengdu city of China were collected on a day/night basis and determined for dicarboxylic acids (diacids), ketocarboxylic acids (ketoacids), α-dicarbonyls, inorganic ions, and water-soluble organic carbon and nitrogen (WSOC and WSON). Diacid concentration was higher in nighttime (1831±607ngm−3) than in daytime (1532±196ngm−3), whereas ketoacids and dicarbonyls showed little diurnal difference. Most of the organic compounds were enriched in the fine mode (<2.1μm) with a peak at the size range of 0.7–2.1μm. In contrast, phthalic acid (Ph) and glyoxal (Gly) presented two equivalent peaks in the fine and coarse modes, which is at least in part due to the gas-phase oxidation of precursors and a subsequent partitioning into pre-existing particles. Liquid water content (LWC) of the fine mode particles was three times higher in nighttime than in daytime. The calculated in-situ pH (pHis) indicated that all the fine mode aerosols were acidic during the sampling period and more acidic in daytime than in nighttime. Robust correlations of the ratios of glyoxal/oxalic acid (Gly/C2) and glyoxylic acid/oxalic acid (ωC2/C2) with LWC in the samples suggest that the enhancement of LWC is favorable for oxidation of Gly and ωC2 to produce C2. Abundant K+ and Cl− in the fine mode particles and the strong correlations of K+ with WSOC, WSON and C2 indicate that secondary organic aerosols in the city are significantly affected by biomass burning emission.

Dicarboxylic acids, ketocarboxylic acids, α-dicarbonyls, fatty acids and benzoic acid in PM&amp;lt;sub&amp;gt;2.5&amp;lt;/sub&amp;gt; aerosol collected during CAREBeijing-2007: an effect of traffic restriction on air quality

Abstract. Thirty water-soluble organic species, including dicarboxylic acids, ketocarboxylic acids, α-dicarbonyls, fatty acids and benzoic acid were determined as well as organic carbon (OC), elemental carbon (EC) and water-soluble organic carbon (WSOC) in PM2.5 samples collected during the Campaign of Air Quality Research in Beijing 2007 (CAREBeijing-2007) in the urban and suburban areas of Beijing. The objective of this study is to identify the influence of traffic emissions and regional transport to the atmosphere in Beijing during summer. PM2.5 samples collected with or without traffic restriction in Beijing are selected to evaluate the effectiveness of local traffic restriction measures on air pollution reduction. The average concentrations of the total quantified bifunctional organic compounds (TQBOCs), total fatty acids and benzoic acid during the entire sampling period were 1184±241, 597±159 and 1496±511 ng m−3 in Peking University (PKU), and 1050±303, 475±114 and 1278±372 ng m−3 in Yufa, Beijing. Oxalic acid (C2) was found as the most abundant dicarboxylic acid at PKU and Yufa followed by phthalic acid (Ph). A strong even carbon number predominance with the highest level at stearic acid (C18:0), followed by palmitic acid (C16:0) was found for fatty acids. According to the back trajectories modeling results, the air masses were found to originate mainly from the northeast, passing over the southeast or south of Beijing (heavily populated, urbanized and industrialized areas), during heavier pollution events, whereas they are mainly from the north or northwest sector (mountain areas without serious anthropogenic pollution sources) during less pollution events. The data with wind only from the same sector (minimizing the difference from regional contribution) but with and without traffic restriction in Beijing were analyzed to evaluate the effectiveness of local traffic restriction measures on the reduction of local air pollution in Beijing. The results suggested that the traffic restriction measures can reduce the air pollutants, but the decrease of pollutants is generally smaller in Yufa compared to that in PKU. Moreover, an enhancement of EC value indicates more elevated primary emissions in Yufa during restriction periods than in non-restriction periods. This study demonstrates that even when primary exhaust was controlled by traffic restriction, the contribution of secondary organic species formed from photochemical processes was critical with long-range atmospheric transport of pollutants.

Efficient production of hyperpolarized bicarbonate by chemical reaction on a DNP precursor to measure pH.

To produce hyperpolarized bicarbonate indirectly via chemical reaction from a hyperpolarized precursor and utilize it for the simultaneous regional measurement of metabolism and pH. Alpha keto carboxylic acids are first hyperpolarized by dissolution dynamic nuclear polarization (DNP). These precursor molecules are rapidly reacted with hydrogen peroxide (H2O2) to decarboxylate the species, resulting in new target molecules. Unreacted H2O2 is removed from the system by reaction with sulfite. Interrogation of the ratio of dissolved carbon dioxide (CO2) to bicarbonate can be used to determine pH. Conversion of hyperpolarized alpha keto acids to bicarbonate and CO2 results in a minimal loss of the spin order. The reaction can be conducted to completion within seconds and preserves the nuclear spin polarization. Through a rapid chemical reaction, we can conserve the nuclear spin order of a DNP precursor to generate multiple hyperpolarized bioprobes otherwise unamenable to polarization. This indirect technique for the production of hyperpolarized agents can be applied to different precursor compounds to generate additional novel probes.

Seasonal characteristics of oxalic acid and related SOA in the free troposphere of Mt. Hua, central China: Implications for sources and formation mechanisms

PM10 aerosols from the summit of Mt. Hua (2060ma.s.l) in central China during the winter and summer of 2009 were analyzed for dicarboxylic acids, ketocarboxylic acids and α-dicarbonyls. Molecular composition of dicarboxylic acids (C2–C11) in the free tropospheric aerosols reveals that oxalic acid (C2, 399±261ngm−3 in winter and 522±261ngm−3 in summer) is the most abundant species in both seasons, followed by malonic (C3) and succinic (C4) acids, being consistent with that on ground levels. Most of the diacids are more abundant in summer than in winter, but adipic (C6) and phthalic (Ph) acids are twice lower in summer, suggesting more significant impact of anthropogenic pollution on the wintertime alpine atmosphere. Moreover, glyoxal (Gly) and methylglyoxal (mGly) are also lower in summer (12±6.1ngm−3) than in winter (22±13ngm−3). As both dicarbonyls are a major precursor of C2, their seasonal variation patterns, which are opposite to those of the diacids, indicate that the mountain troposphere is more oxidative in summer.C2 showed strong linear correlations with levoglucosan in winter and oxidation products of isoprene and monoterpene in summer. PCA analysis further suggested that the wintertime C2 and related SOA in the Mt. Hua troposphere mostly originate from photochemical oxidations of anthropogenic pollutants emitted from biofuel and coal combustion in lowland regions. On contrast, the summertime C2 and related SOA mostly originate from further oxidation of the mountainous isoprene and monoterpene oxidation products. The AIM model calculation results showed that oxalic acid concentration well correlated with particle acidity (R2=0.60) but not correlated with particle liquid water content, indicating that particle acidity favors the organic acid formation because aqueous-phase C2 production is the primary mechanism of C2 formation in ambient aerosols and is driven by acid-catalyzed oxidation.

Comparison of dicarboxylic acids and related compounds in aerosol samples collected in Xi'an, China during haze and clean periods

PM10 aerosols from Xi'an, a mega city of China in winter and summer, 2009 were measured for secondary organic aerosols (SOA) (i.e., dicarboxylic acids (DCA), keto-carboxylic acids, and α-dicarbonyls), water-soluble organic (WSOC) and inorganic carbon (WSIC), elemental carbon (EC) and organic carbon (OC). Molecular compositions of SOA on haze and clean days in both seasons were compared to investigate their sources and formation mechanisms. DCA in the samples were 1843 ± 810 ng m−3 in winter and 1259 ± 781 ng m−3 in summer, respectively, which is similar and even higher than those measured in 2003. Oxalic acid (C2, 1162 ± 570 ng m−3 in winter and 1907 ± 707 ng m−3 in summer) is the predominant species of DCA, followed by t-phthalic (tPh) in winter and phthalic (Ph) in summer. Such a molecular composition is different from those in other Asian cities where succinic acid (C4) or malonic acid (C3) is the second highest species, which is mostly due to significant emissions from household combustion of coal and open burning of waste material in Xi'an. Mass ratios of C2/diacids, diacids/WSOC, WSOC/OC and individual diacid-C/WSOC are higher on the haze days than on the clean days in both seasons, suggesting an enhanced SOA production under the haze condition. We also found that the haze samples are acidic while the clean samples are almost neutral. Such a difference in particle acidity is consistent with the enhanced SOA production, because acid-catalysis is an important aqueous-phase formation pathway of SOA. Gly/mGly mass ratio showed higher values on haze days than on clean day in both seasons. We comprehensively investigated the ratio in literature and found a consistent pattern. Based on our observation results and those documented data we proposed for the first time that concentration ratio of Gly/mGly can be taken as an indicator of aerosol ageing.

High abundances of water-soluble dicarboxylic acids, ketocarboxylic acids and α-dicarbonyls in the mountaintop aerosols over the North China Plain during wheat burning season

Abstract. Aerosol (TSP) samples were collected at the summit of Mount Tai (elevation: 1534 m a.s.l., 36.25° N, 117.10° E) located in the North China Plain using a high-volume air sampler and pre-combusted quartz filters. Sampling was conducted on day/night or 3 h basis in the period from 29 May to 28 June 2006 during the field burning of wheat straw residue and the post-burning season. The filter samples were analyzed for low-molecular-weight dicarboxylic acids, ketoacids and α-dicarbonyls using capillary gas chromatography (GC) and GC-MS employing water extraction and butyl ester derivatization. Molecular distributions of dicarboxylic acids (C2-C11, 220–6070 ng m−3) were characterized by a predominance of oxalic (C2) acid (105–3920 ng m−3) followed by succinic (C4) or malonic (C3) acid. Unsaturated aliphatic diacids, including maleic (M), isomaleic (iM) and fumaric (F) acids, were also detected together with aromatic diacids (phthalic, isophthalic and terephthalic acids). ω-oxocarboxylic acids (C2-C9, 24–610 ng m−3) were detected as the second most abundant compound class with the predominance of glyoxylic acid (11–360 ng m−3), followed by α-ketoacid (pyruvic acid, 3–140 ng m−3) and α-dicarbonyls (glyoxal, 1–230 ng m−3 and methylglyoxal, 2–120 ng m−3). We found that these levels (&gt;6000 ng m−3 for diacids) are several times higher than those reported in Chinese megacities at ground levels. The concentrations of diacids increased from late May to early June, showing a maximum on 7 June, and then significantly decreased during the period 8–11 June, when the wind direction shifted from southerly to northerly. Similar temporal trends were found for ketocarboxylic acids and α-dicarbonyls as well as total carbon (TC) and water-soluble organic carbon (WSOC). The temporal variations of water-soluble organics were interpreted by the direct emission from the field burning of agricultural wastes (wheat straw) in the North China Plain and the subsequent photochemical oxidation of volatile and semi-volatile organic precursors emitted from field burning as well as dark ozonolysis of volatile organic compounds and other organics, accretion reactions and oxidation of nonvolatile organics such as unsaturated fatty acids. This study demonstrates that the field burning of agricultural wastes in early summer strongly influenced the air quality of the free troposphere over the North China Plain.

Atmospheric oxalic acid and related secondary organic aerosols in Qinghai Lake, a continental background site in Tibet Plateau

Summertime PM2.5 aerosols collected from Qinghai Lake (3200 m a.s.l.), a remote continental site in the northeastern part of Tibetan Plateau, were analyzed for dicarboxylic acids (C2–C11), ketocarboxylic acids and α-dicarbonyals. Oxalic acid (C2) is the dominant dicarboxylic acid in the samples, followed by malonic, succinic and azelaic acids. Total dicarboxylic acids (231 ± 119 ng m−3), ketocarboxylic acids (8.4 ± 4.3 ng m−3), and α-dicarbonyls (2.7 ± 2.1 ng m−3) at the Tibetan background site are 2–5 times less than those detected in lowland areas such as 14 Chinese megacities. Compared to those in other urban and marine areas enhancements in relative abundances of C2/total diacids and diacids-C/WSOC of the PM2.5 samples suggest that organic aerosols in the region are more oxidized due to strong solar radiation. Molecular compositions and air mass trajectories demonstrate that the above secondary organic aerosols in the Qinghai Lake atmosphere are largely derived from long-range transport. Ratios of oxalic acid, glyoxal and methylglyoxal to levoglucosan in PM2.5 aerosols emitted from household burning of yak dung, a major energy source for Tibetan in the region, are 30–400 times lower than those in the ambient air, which further indicates that primary emission from biomass burning is a negligible source of atmospheric oxalic acid and α-dicarbonyls at this background site.

Molecular composition of dicarboxylic acids, ketocarboxylic acids, α-dicarbonyls and fatty acids in atmospheric aerosols from Tanzania, East Africa during wet and dry seasons

Abstract. Atmospheric aerosol samples of PM2.5 and PM10 were collected during the wet and dry seasons in 2011 from a rural site in Tanzania and analysed for water-soluble dicarboxylic acids, ketocarboxylic acids, α-dicarbonyls, and fatty acids using a gas chromatography/flame ionization detector (GC/FID) and GC/mass spectrometry. Here we report the molecular composition and sources of diacids and related compounds for wet and dry seasons. Oxalic acid (C2) was found as the most abundant diacid species followed by succinic and/or malonic acids whereas glyoxylic acid and glyoxal were the dominant ketoacid and α-dicarbonyl, respectively in both seasons in PM2.5 and PM10. Mean concentration of C2 in PM2.5 (121 ± 47 ng m−3) was lower in wet season than dry season (258 ± 69 ng m−3). Similarly, PM10 samples showed lower concentration of C2 (169 ± 42 ng m−3) in wet season than dry season (292 ± 165 ng m−3). Relative abundances of C2 in total diacids were 65% and 67% in PM2.5 and 65% and 64% in PM10 in the wet and dry seasons, respectively. Total concentrations of diacids (289–362 ng m−3), ketoacids (37.8–53.7 ng m−3), and α-dicarbonyls (5.7–7.8 ng m−3) in Tanzania are higher than those reported at a rural background site in Nylsvley (South Africa) but comparable or lower than those reported from sites in Asia and Europe. Diacids and ketoacids were found to be present mainly in PM2.5 in both seasons (total α-dicarbonyls in the dry season), suggesting a production of organic acids from pyrogenic sources and photochemical oxidations. Averaged contributions of total diacids to aerosol total carbon were 1.4% in PM2.5 and 2.1% in PM10 during wet season and 3.3% in PM2.5 and 3.9% in PM10 during dry season whereas those to water-soluble organic carbon were 2.2% and 4.7% in PM2.5 during wet season and 3.1% and 5.8% in PM10 during dry season. The higher ratios in dry season suggest an enhanced photochemical oxidation of organic precursors probably via heterogeneous reactions on aerosols under strong solar radiation. Strong positive correlations were found among diacids and related compounds as well as good relations to source tracers in both seasons, suggesting a mixed source from natural biogenic emissions, biomass burning, biofuel combustion, and photochemical production.

Dicarboxylic acids, ketocarboxylic acids and glyoxal in the marine aerosols collected during a round-the-world cruise

This study investigated spatial distributions of water-soluble dicarboxylic acids and related compounds in the marine aerosols collected at low- to mid-latitudes in the Northern Hemisphere for a better understanding of the photochemical aging of organic aerosols during long-range transport. Their molecular distributions were characterized by the predominance of oxalic acid (C2) followed by malonic (C3) and succinic (C4) acids, except for one sample (QFF114, C2>C4>C3) that was collected in the western North Pacific with a heavy influence of biomass burning. Concentration ranges of diacids, ketoacids (including glyoxylic acid and pyruvic acid), and glyoxal were 17–718ngm−3 (average 218ngm−3), 0.40–72ngm−3 (23ngm−3), and 0.16–19ngm−3 (3.3ngm−3), which account for 3.6–23% (14%), 0.09–2.3% (1.3%), and 0.04–0.45% (0.19%) of organic carbon (OC) in the marine aerosols, respectively. Positive correlations were observed between OC and diacids/ketoacids. Positive correlations were also found between biogenic secondary organic aerosol (SOA) tracers (e.g., 2-methylglyceric acid) and diacids/ketoacids, suggesting a significant contribution of biogenic secondary source. The spatial distributions of diacids exhibited higher loadings over the coastal/tropical regions than the open oceans, which are similar to those of the concentration ratios of malonic/succinic (C3/C4) and adipic/azelaic (C6/C9), indicating a more significant influence of anthropogenic sources over the coastal regions than the remote oceans. However, the concentration ratios of oxalic acid to levoglucosan, a biomass-burning tracer, and to C29n-alkane, a tracer for terrestrial biogenic emission showed higher values over the open oceans than the coastal regions, suggesting a continuous production of oxalic acid during long-range atmospheric transport. This study indicates that the long-range transport of primary and secondary aerosols of continental origin and photo-oxidation/aerosol aging are important factors controlling the organic chemical composition of aerosol particles in the marine atmosphere.

Distributions of low molecular weight dicarboxylic acids, ketoacids and α-dicarbonyls in the marine aerosols collected over the Arctic Ocean during late summer

Abstract. Oxalic and other small dicarboxylic acids have been reported as important water-soluble organic constituents of atmospheric aerosols from different environments. Their molecular distributions are generally characterized by the predominance of oxalic acid (C2) followed by malonic (C3) and/or succinic (C4) acids. In this study, we collected marine aerosols from the Arctic Ocean during late summer in 2009 when sea ice was retreating. The marine aerosols were analyzed for the molecular distributions of dicarboxylic acids as well as ketocarboxylic acids and α-dicarbonyls to better understand the source of water-soluble organics and their photochemical processes in the high Arctic marine atmosphere. We found that diacids are more abundant than ketoacids and α-dicarbonyls, but their concentrations are generally low (&lt; 30 ng m−3), except for one sample (up to 70 ng m−3) that was collected near the mouth of Mackenzie River during clear sky condition. Although the molecular compositions of diacids are in general characterized by the predominance of oxalic acid, a depletion of C2 was found in two samples in which C4 became the most abundant. Similar depletion of oxalic acid has previously been reported in the Arctic aerosols collected at Alert after polar sunrise and in the summer aerosols from the coast of Antarctica. Because the marine aerosols that showed a depletion of C2 were collected under the overcast and/or foggy conditions, we suggest that a photochemical decomposition of oxalic acid may have occurred in aqueous phase of aerosols over the Arctic Ocean via the photo dissociation of oxalate-Fe (III) complex. We also determined stable carbon isotopic compositions (δ13C) of bulk aerosol carbon and individual diacids. The δ13C of bulk aerosols showed −26.5‰ (range: −29.7 to −24.7‰, suggesting that marine aerosol carbon is derived from both terrestrial and marine organic materials. In contrast, oxalic acid showed much larger δ13C values (average: −20.9‰, range: −24.7‰ to −17.0‰) than those of bulk aerosol carbon. Interestingly, δ13C values of oxalic acid were higher than C3 (av. −26.6‰) and C4 (−25.8‰) diacids, suggesting that oxalic acid is enriched with 13C due to its photochemical processing (aging) in the marine atmosphere.