scholarly journals Dicarboxylic acids, ketocarboxylic acids, α-dicarbonyls, fatty acids and benzoic acid in PM<sub>2.5</sub> aerosol collected during CAREBeijing-2007: an effect of traffic restriction on air quality

2015 ◽  
Vol 15 (6) ◽  
pp. 3111-3123 ◽  
Author(s):  
K. F. Ho ◽  
R.-J. Huang ◽  
K. Kawamura ◽  
E. Tachibana ◽  
S. C. Lee ◽  
...  

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.

2014 ◽  
Vol 14 (10) ◽  
pp. 14855-14887 ◽  
Author(s):  
K. F. Ho ◽  
R.-J. Huang ◽  
K. Kawamura ◽  
E. Tachibana ◽  
S. C. Lee ◽  
...  

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 measure on air pollution reduction. The average concentrations of the total quantified bifunctional organic compounds (TQBOC), total fatty acids and benzoic acid during the entire sampling period were 1184 ± 241 ng m−3, 597 ± 159 ng m−3 and 1496 ± 511ng m−3 in PKU, and 1050 ± 303 ng m−3, 475 ± 114 ng m−3 and 1278 ± 372 ng m−3 in Yufa. 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 palmitic acid (C16:0), followed by stearic acid (C18:0) was found for fatty acids. According to the back trajectories modeling results, the air masses were found to originate mainly from northeast, passing over southeast or south of Beijing (heavily populated, urbanized and industrialized areas), during heavier pollution events, whereas they are mainly from north or northwest sector (mountain areas without serious anthropogenic pollution sources) during cleaner 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 measure on the reduction of local air pollution in Beijing. The results suggested that the "traffic restriction" measure can reduce the air pollutants, but the decrease of pollutants is generally smaller in Yufa compared to that in PKU. Moreover, an enhancement of elemental carbon (EC) value indicates elevated primary emissions in Yufa during restriction period than non-restriction period. 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.


2010 ◽  
Vol 10 (11) ◽  
pp. 26677-26703 ◽  
Author(s):  
K. F. Ho ◽  
S. S. H. Ho ◽  
S. C. Lee ◽  
K. Kawamura ◽  
S. C. Zou ◽  
...  

Abstract. Ground-based PM2.5 samples collected in Pearl River Delta (PRD) region during winter and summer (from 14 December 2006 to 28 January 2007 in winter and from 4 July 2007 to 9 August 2007 in summer) were analyzed for 30 water-soluble organic species, including dicarboxylic acids, ketocarboxylic acids and dicarbonyls, nine fatty acids, and benzoic acid. Molecular distributions of dicarboxylic acids demonstrated that oxalic acid (C2) was the most abundant species followed by phthalic acid (Ph) in PRD region. The concentrations of total dicarboxylic acids ranged from 99 to 1340 ng m−3, with an average of 438 ± 267 ng m−3 in PRD. The concentrations of total ketocarboxylic acids ranged from 0.6 to 207 ng m−3 (43 ± 48 ng m−3 on average) while the concentrations of total α-dicarbonyls, including glyoxal and methylglyoxal, ranged from 0.2 to 89 ng m−3, with an average of 11 ± 18 ng m−3 in PRD. The total quantified water-soluble organic carbon (TQWOC) accounted for 3.4 ± 2.2% of OC and 14.3 ± 10.3% of water-soluble OC (WSOC). Hexadecanoic acid (C16:0), octadecanoic acid (C18:0) and oleic acid (C18:1) are the three most abundant fatty acids in PRD. The distributions of fatty acids are characterized by a strong even carbon number predominance with a maximum (Cmax) at hexadecanoic acid (C16:0). Ratio of C18:1 to C18:0 acts as an indicator for aerosol aging. In PRD, an average of C18:1/C18:0 ratio was 0.53 ± 0.39, suggesting an enhanced photochemical degradation of unsaturated fatty acid. Seasonal variations of the pollutant concentrations were found in the four sampling cities. Higher concentrations of TQWOC were observed in winter (544 ng m−3) than in summer (318 ng m−3). However, the abundances of TQWOC in OC mass were higher in summer (1.8–12.4%, 5.4% on average) than in winter (1.1–5.7, 2.6% on average), being consistent with enhanced secondary production of dicarboxylic acids in warmer weather. Spatial variations of water-soluble dicarboxylic acids were characterized by higher concentrations in Hong Kong and lower concentrations Guangzhou (GZ)/Zhaoqing (ZQ) during winter whereas highest concentrations were observed in GZ/ZQ during summer. These spatial and seasonal distributions are consistent with photochemical production and the subsequent accumulation under different meteorological conditions.


2011 ◽  
Vol 11 (5) ◽  
pp. 2197-2208 ◽  
Author(s):  
K. F. Ho ◽  
S. S. H. Ho ◽  
S. C. Lee ◽  
K. Kawamura ◽  
S. C. Zou ◽  
...  

Abstract. Ground-based PM2.5 samples collected at four different sites in Pearl River Delta region (PRD) during winter and summer (from 14 December 2006 to 28 January 2007 in winter and from 4 July to 9 August 2007 in summer) were analyzed for 30 water-soluble organic species, including dicarboxylic acids, ketocarboxylic acids and dicarbonyls, nine fatty acids, and benzoic acid. Molecular distributions of dicarboxylic acids demonstrated that oxalic acid (C2) was the most abundant species followed by phthalic acid (Ph) in PRD region. The concentrations of total dicarboxylic acids ranged from 99 to 1340 ng m−3, with an average of 438 ± 267 ng m−3 in PRD. The concentrations of total ketocarboxylic acids ranged from 0.6 to 207 ng m−3 (43 ± 48 ng m−3 on average) while the concentrations of total α-dicarbonyls, including glyoxal and methylglyoxal, ranged from 0.2 to 89 ng m−3, with an average of 11 ± 18 ng m−3 in PRD. The total quantified water-soluble compounds (TQWOC) (organic carbon) accounted for 3.4 ± 2.2% of OC and 14.3 ± 10.3% of water-soluble OC (WSOC). Hexadecanoic acid (C16:0), octadecanoic acid (C18:0) and oleic acid (C18:1) were the three most abundant fatty acids in PRD. The distributions of fatty acids were characterized by a strong even carbon number predominance with a maximum (Cmax) at hexadecanoic acid (C16:0). Ratio of C18:1 to C18:0 acts as an indicator for aerosol aging. In PRD, an average of C18:1/C18:0 ratio was 0.53 ± 0.39, suggesting an enhanced photochemical degradation of unsaturated fatty acid. Moreover, the concentrations of benzoic acid ranged from 84 to 306 ng m−3, (165 ± 48 ng m−3 on average), which can be emitted as primary pollutant from motor vehicles exhaust, or formed from photochemical degradation of aromatic hydrocarbons. Seasonal variations of the organic specie concentrations were found in the four sampling cities. Higher concentrations of TQWOC were observed in winter (598 ± 321 ng m−3) than in summer (372 ± 215 ng m−3). However, the abundances of TQWOC in OC mass were higher in summer (0.9–12.4%, 4.5 ± 2.7% on average) than in winter (1.1–5.7, 2.5 ± 1.2% on average), being consistent with enhanced secondary production of dicarboxylic acids in warmer weather. Spatial variations of water-soluble dicarboxylic acids were characterized by higher concentrations in Hong Kong and lower concentrations in Guangzhou (GZ)/Zhaoqing (ZQ) during winter whereas the highest concentrations were observed in GZ/ZQ during summer. These spatial and seasonal distributions are consistent with photochemical production and the subsequent accumulation under different meteorological conditions.


2018 ◽  
Author(s):  
Anna Katinka Petersen ◽  
Guy P. Brasseur ◽  
Idir Bouarar ◽  
Johannes Flemming ◽  
Michael Gauss ◽  
...  

Abstract. An operational multi-model forecasting system for air quality has been developed to provide air quality services for urban areas of China. The initial forecasting system included seven state-of-the-art computational models developed and executed in Europe and China (CHIMERE, IFS, EMEP MSC-W, WRF-Chem-MPIM, WRF-Chem-SMS, LOTOS-EUROS and SILAMtest). Several other models joined the prediction system recently, but are not considered in the present analysis. In addition to the individual models, a simple multi-model ensemble was constructed by deriving statistical quantities such as the median and the mean of the predicted concentrations. The prediction system provides daily forecasts and observational data of surface ozone, nitrogen dioxides and particulate matter for the 37 largest urban agglomerations in China (population higher than 3 million in 2010). These individual forecasts as well as the multi-model ensemble predictions for the next 72 hours are displayed as hourly outputs on a publicly accessible web site (www.marcopolo-panda.eu). In this paper, the performance of the predictions system (individual models and the multi-model ensemble) for the first operational year (April 2016 until June 2017) has been analysed through statistical indicators using the surface observational data reported at Chinese national monitoring stations. This evaluation aims to investigate a) the seasonal behavior, b) the geographical distribution and c) diurnal variations of the ensemble and model skills. Statistical indicators show that the ensemble product usually provides the best performance compared to the individual model forecasts. The ensemble product is robust even if occasionally some individual model results are missing. Overall and in spite of some discrepancies, the air quality forecasting system is well suited for the prediction of air pollution events and has the ability to provide alert warning (binary prediction) of air pollution events if bias corrections are applied to improve the ozone predictions.


2010 ◽  
Vol 10 (13) ◽  
pp. 6087-6096 ◽  
Author(s):  
G. Wang ◽  
M. Xie ◽  
S. Hu ◽  
S. Gao ◽  
E. Tachibana ◽  
...  

Abstract. Dicarboxylic acids (C2–C10), metals, elemental carbon (EC), organic carbon (OC), and stable isotopic compositions of total carbon (TC) and total nitrogen (TN) were determined for PM10 samples collected at three urban and one suburban sites of Baoji, an inland city of China, during winter and spring 2008. Oxalic acid (C2) was the dominant diacid, followed by succinic (C4) and malonic (C3) acids. Total diacids in the urban and suburban areas were 1546±203 and 1728±495 ng m−3 during winter and 1236±335 and 1028±193 ng m−3 during spring. EC in the urban and the suburban atmospheres were 17±3.8 and 8.0±2.1 μg m−3 during winter and 20±5.9 and 7.1±2.7 μg m−3 during spring, while OC at the urban and suburban sites were 74±14 and 51±7.9 μg m−3 in winter and 51±20 and 23±6.1 μg m−3 in spring. Secondary organic carbon (SOC) accounted for 38±16% of OC in winter and 28±18% of OC in spring, suggesting an enhanced photochemical production of secondary organic aerosols in winter under an inversion layer development. Total metal elements in winter and spring were 34±10 and 61±27 μg m−3 in the urban air and 18±7 and 32±23 μg m−3 in the suburban air. A linear correlation (r2>0.8 in winter and r2>0.6 in spring) was found between primary organic carbon (POC) and Ca2+/Fe, together with a strong dependence of pH value of sample extracts on water-soluble inorganic carbon, suggesting fugitive dust as an important source of the airborne particles. Polycyclic aromatic hydrocarbons (PAHs), sulfate, and Pb in the samples well correlated each other (r2>0.6) in winter, indicating an importance of emissions from coal burning for house heating. Stable carbon isotope compositions of TC (δ13C) became higher with an increase in the concentration ratios of C2/OC due to aerosol aging. In contrast, nitrogen isotope compositions of TN (δ15N) became lower with an increases in the mass ratios of NH4+/PM10 and NO3−/PM10, which is possibly caused by an enhanced adsorption and/or condensation of gaseous NH3 and HNO3 onto particles.


2016 ◽  
Vol 16 (8) ◽  
pp. 5263-5282 ◽  
Author(s):  
Dhananjay K. Deshmukh ◽  
Kimitaka Kawamura ◽  
Manuel Lazaar ◽  
Bhagawati Kunwar ◽  
Suresh K. R. Boreddy

Abstract. Size-segregated aerosols (nine stages from < 0.43 to > 11.3 µm in diameter) were collected at Cape Hedo, Okinawa, in spring 2008 and analyzed for water-soluble diacids (C2–C12), ω-oxoacids (ωC2–ωC9), pyruvic acid, benzoic acid, and α-dicarbonyls (C2–C3) as well as water-soluble organic carbon (WSOC), organic carbon (OC), and major ions (Na+, NH4+, K+, Mg2+, Ca2+, Cl−, NO3−, SO42−, and MSA−). In all the size-segregated aerosols, oxalic acid (C2) was found to be the most abundant species, followed by malonic and succinic acids, whereas glyoxylic acid (ωC2) was the dominant oxoacid and glyoxal (Gly) was more abundant than methylglyoxal. Diacids (C2–C5), ωC2, and Gly as well as WSOC and OC peaked at fine mode (0.65–1.1 µm) whereas azelaic (C9) and 9-oxononanoic (ωC9) acids peaked at coarse mode (3.3–4.7 µm). Sulfate and ammonium were enriched in fine mode, whereas sodium and chloride were in coarse mode. Strong correlations of C2–C5 diacids, ωC2 and Gly with sulfate were observed in fine mode (r =  0.86–0.99), indicating a commonality in their secondary formation. Their significant correlations with liquid water content in fine mode (r =  0.82–0.95) further suggest an importance of the aqueous-phase production in Okinawa aerosols. They may also have been directly emitted from biomass burning in fine mode as supported by strong correlations with potassium (r =  0.85–0.96), which is a tracer of biomass burning. Bimodal size distributions of longer-chain diacid (C9) and oxoacid (ωC9) with a major peak in the coarse mode suggest that they were emitted from the sea surface microlayers and/or produced by heterogeneous oxidation of biogenic unsaturated fatty acids on sea salt particles.


2021 ◽  
Author(s):  
Connor Stahl ◽  
Ewan Crosbie ◽  
Paola Angela Bañaga ◽  
Grace Betito ◽  
Rachel A. Braun ◽  
...  

Abstract. This work focuses on total organic carbon (TOC) and contributing species in cloud water over Southeast Asia using a rare airborne dataset collected during NASA’s Cloud, Aerosol and Monsoon Processes Philippines Experiment (CAMP2Ex), in which a wide variety of maritime clouds were studied, including cumulus congestus, altocumulus, altostratus, and cumulus. Knowledge of TOC levels and their contributing species is needed for improved modeling of cloud processing of organics and to understand how aerosols and gases impact and are impacted by clouds. This work relies on 159 samples collected with an Axial Cyclone Cloud water Collector at altitudes of 0.2–6.8 km that had sufficient volume for both TOC and speciated organic composition analysis. Species included monocarboxylic acids (glycolate, acetate, formate, and pyruvate), dicarboxylic acids (glutarate, adipate, succinate, maleate, and oxalate), methanesulfonate (MSA), and dimethylamine (DMA). TOC values range between 0.018–13.660 ppm C with a mean of 0.902 ppm C. The highest TOC values are observed below 2 km with a general reduction aloft. An exception is samples impacted by biomass burning for which TOC remains enhanced as high as 6.5 km (7.048 ppm C). Estimated total organic matter derived from TOC contributes a mean of 30.7 % to total measured mass (inorganics + organics). Speciated organics contribute (on carbon mass basis) an average of 30.0 % to TOC in the study region, and account for an average of 10.3 % to total measured mass. The order of the average contribution of species to TOC, in decreasing contribution of carbon mass, is as follows: acetate (14.7 ± 20.5 %), formate (5.4 ± 9.3 %), oxalate (2.8 ± 4.3 %), DMA (1.7 ± 6.3 %), succinate (1.6 ± 2.4 %), pyruvate (1.3 ± 4.5 %), glycolate (1.3 ± 3.7 %), adipate (1.0 ± 3.6 %), MSA (0.1 ± 0.1 %), glutarate (0.1 ± 0.2 %), maleate (< 0.1 ± 0.1 %). Approximately 70 % of TOC remains unaccounted for, thus highlighting the complex nature of organics in the study region; samples collected in biomass burning plumes have up to 95.6 % of unaccounted TOC mass based on the species detected. Consistent with other regions, monocarboxylic acids dominate the speciated organic mass (~75 %) and are about four times in greater abundance than dicarboxylic acids. Samples are categorized into four cases based on back-trajectory history revealing source-independent similarity between the bulk contributions of monocarboxylic and dicarboxylic acids to TOC (16.03 %–23.66 % and 3.70 %–8.75 %, respectively). Furthermore, acetate, formate, succinate, glutarate, pyruvate, oxalate, and MSA are especially enhanced during biomass burning periods, attributed to peat emissions transported from Sumatra and Borneo. Lastly, dust (Ca2+) and sea salt (Na+/Cl−) tracers exhibit strong correlations with speciated organics, thus supporting how coarse aerosol surfaces interact with these water-soluble organics.


2018 ◽  
Vol 11 (11) ◽  
pp. 5941-5964 ◽  
Author(s):  
Caroline R. Nowlan ◽  
Xiong Liu ◽  
Scott J. Janz ◽  
Matthew G. Kowalewski ◽  
Kelly Chance ◽  
...  

Abstract. The GEOstationary Coastal and Air Pollution Events (GEO-CAPE) Airborne Simulator (GCAS) was developed in support of NASA's decadal survey GEO-CAPE geostationary satellite mission. GCAS is an airborne push-broom remote-sensing instrument, consisting of two channels which make hyperspectral measurements in the ultraviolet/visible (optimized for air quality observations) and the visible–near infrared (optimized for ocean color observations). The GCAS instrument participated in its first intensive field campaign during the Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) campaign in Texas in September 2013. During this campaign, the instrument flew on a King Air B-200 aircraft during 21 flights on 11 days to make air quality observations over Houston, Texas. We present GCAS trace gas retrievals of nitrogen dioxide (NO2) and formaldehyde (CH2O), and compare these results with trace gas columns derived from coincident in situ profile measurements of NO2 and CH2O made by instruments on a P-3B aircraft, and with NO2 observations from ground-based Pandora spectrometers operating in direct-sun and scattered light modes. GCAS tropospheric column measurements correlate well spatially and temporally with columns estimated from the P-3B measurements for both NO2 (r2=0.89) and CH2O (r2=0.54) and with Pandora direct-sun (r2=0.85) and scattered light (r2=0.94) observed NO2 columns. Coincident GCAS columns agree in magnitude with NO2 and CH2O P-3B-observed columns to within 10 % but are larger than scattered light Pandora tropospheric NO2 columns by 33 % and direct-sun Pandora NO2 columns by 50 %.


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