Zhenxing Shen

Characterization and Temporal Variation of Asian Dust Aerosol from a Site in the Northern Chinese Deserts

Time series for total aerosol mass and the concentrations of nineteen elements, and the mass particle-size distributions of the elements, were determined for samples collected from a site in the northern deserts of China -Zhenbeitai, one of ground sites of the Asia-Pacific Regional Aerosol Characterization Experiment (ACE-Asia). Nine dust storm (DS) events were observed during the spring of 2001, lasting a combined total of twenty-six days. Peak mass loadings greatly exceeded the average (260 μg m−3), and higher than average dust-element concentrations and wind speeds were also observed during the three-month study. Material balance calculations showed that ∼82% mass of the total aerosol particles could be ascribed to Asian dust, of which Al, Ca, Fe, K, Mn, Si and Ti accounted for 7%, 6%, 4%, 2%, 0.1%, 32% and 1% by weight, respectively. Modelcalculated dry deposition velocities for 7 dust-elements during dust storm periods averaged 17 cm s−1 and ranged from 14 to 21 cm s−1. The estimated dry depositiona of Asian dust for the spring of 2001 was 189 g m−2, of which 85% was due to dust storms. Factor analysis indicated that ∼89% of the dust loading during this period was due to remote or regional transport; ∼11% to local or background dust.

Seasonal Variations and Evidence for the Effectiveness of Pollution Controls on Water-Soluble Inorganic Species in Total Suspended Particulates and Fine Particulate Matter from Xi'an, China

Abstract Total suspended particulate (TSP) and particulate matter less than 2.5 μm in aerodynamic diameter (PM2.5) sam ples were collected over Xi’an for a 1-yr period to characterize the seasonal variations of water-soluble inorganic ions and to evaluate the effectiveness of the pollution policies and controls during the past 10 yr. Mass concentrations of five cations (sodium [Na+], potassium [K+], ammonium [NH4 +]], calcium [Ca2+], and magnesium [Mg2+) and four anions (fluoride [F−], chloride [Cl−], nitrate [NO3 −], and sulfate [SO4 2−]) were determined by ion chromatography. The yearly arithmetic-mean mass concentrations of the total measured water-soluble ions in TSP and PM2.5 were 83.9 ± 58.4 and 45 ± 34.3 μg∙m-3. The most abundant ions in TSP were SO4 2−, NO3 −, Ca2+, and NH4 +; whereas in PM2.5 the dominant ions were SO4 2−, NH4 +, and NO3 −. Most of the ions were more concentrated in the PM2.5 than in TSP, but two exceptions were Ca2+ and Mg2+. Comparisons of the molar ratios of Mg2+/Ca2+ in TSP indicated that fugitive dust was the main source for these two ions, and the influence of soil dust from outside of the city was most evident during dust storms. The mass concentrations of SO4 2−, NO3 −, NH4 +, and K+ in TSP were highest in winter and lowest in spring, but Ca2+ was much higher in spring than other seasons because of suspended mineral dust. In PM2.5, NO3 − and K+ also showed winter maxima, but SO4 2− and NH4 + were highest in summer. Calculations of ion equivalents showed that TSP samples were more alkaline than PM2.5, the latter being weakly acidic in winter and autumn. High sulfur and nitrogen oxidation ratios occurred in summer and autumn, and there was evidence for the formation of ammonium bisulfate in TSP, ammonium sulfate in PM2.5, and ammonium nitrate in both fractions. Comparisons with the results of prior studies indicate that pollution controls in Xi’an have reduced the levels of air pollution over the past 10 yr. The SO4 2− concentration during the heating season in 2006 was only about one-eighth of that in 1996, and NH4 + decreased to one-ninth of that in 1996. Seasonal variations in the NO3 −/SO4 2− ratio are different than the patterns observed 10 yr ago, suggesting that emission sources have changed, with those from motor vehicles becoming increasingly important.

Carbonaceous aerosols in PM10 and pollution gases in winter in Beijing

An intensive observation of organic carbon (OC) and elemental carbon (EC) in PM10 and gaseous materials (SO2, CO, and O3) was conducted continuously to assess the characteristics of wintertime carbonaceous aerosols in an urban area of Beijing, China. Results showed that the averaged total carbon (TC) and PM10 concentrations in observation period are 30.2 +/- 120.4 and 172.6 +/- 198.3 microg/m3, respectively. Average OC concentration in nighttime (24.9 +/- 19.6 microg/m3) was 40% higher than that in daytime (17.7 +/- 10.9 microg/m3). Average EC concentrations in daytime (8.8 +/- 15.2 microg/m3) was close to that in nighttime (8.9 +/- 15.1 microg/m3). The OC/EC ratios in nighttime ranging from 2.4 to 2.7 are higher than that in daytime ranging from 1.9 to 2.0. The concentrations of OC, EC, PM10 were low with strong winds and high with weak winds. The OC and EC were well correlated with PM10, CO and SO2, which implies they have similar sources. OC and EC were not well correlated with 03. By considering variation of OC/EC ratios in daytime and night time, correlations between OC and O3, and meteorological condition, we speculated that OC and EC in Beijing PM10 were emitted as the primary particulate form. Emission of motor vehicle with low OC/EC ratio and coal combustion sources with high OC/EC ratio are probably the dominant sources for carbonaceous aerosols in Beijing in winter. A simple ratio method was used to estimate the relative contribution of sources to carbonaceous aerosols in Beijing PM10. Motor vehicle source accounts for 80% and 68%, while coal combustion accounts for 20% and 32% in daytime and nighttime, respectively in Beijing. Averagely, the motor vehicle and coal combustion accounted for 74% and 26%, respectively, for carbonaceous aerosols during the observation period. It points to the motor vehicle is dominant emission for carbonaceous aerosols in Beijing PM10 in winter period, which should be paid attention to control high level of PM10 in Beijing effectively.

Environment-Friendly Carbon Quantum Dots/ZnFe2O4 Photocatalysts: Characterization, Biocompatibility, and Mechanisms for NO Removal

A highly efficient and environmentally-friendly oxidation process is always desirable for air purification. This study reported a novel carbon quantum dots (CQDs)/ZnFe2O4 composite photocatalyst for the first time through a facile hydrothermal process. The CQDs/ZnFe2O4 (15 vol %) composite demonstrates stronger transient photocurrent response, approximately 8 times higher than that of ZnFe2O4, indicating superior transfer efficiency of photogenerated electrons and separation efficiency of photogenerated electron-hole pairs. Compared with pristine ZnFe2O4 nanoparticles, CQDs/ZnFe2O4 displayed enhanced photocatalytic activities on gaseous NOx removal and high selectivity for nitrate formation under visible light (λ > 420 nm) irradiation. Electron spin resonance analysis and a series of radical-trapping experiments showed that the reactive species contributing to NO elimination were ·O2- and ·OH radicals. The possible mechanisms were proposed regarding how CQDs improve the photocatalytic performance of ZnFe2O4. The CQDs are believed to act as an electron reservoir and transporter as well as a powerful energy-transfer component during the photocatalysis processes over CQDs/ZnFe2O4 samples. Furthermore, the toxicity assessment authenticated good biocompatibility and low cytotoxity of CQDs/ZnFe2O4. The results of this study indicate that CQDs/ZnFe2O4 is a promising photocatalyst for air purification.

Characterization and seasonal variations of levoglucosan in fine particulate matter in Xi’an, China

PM2.5 (particulate matter with an aerodynamic diameter <2.5 μm) samples (n = 58) collected every sixth day in Xi’an, China, from 5 July 2008 to 27 June 2009 are analyzed for levoglucosan (1,6-anhydro-β-d-glucopyranose) to evaluate the impacts of biomass combustion on ambient concentrations. Twenty-four-hour levoglucosan concentrations displayed clear summer minima and winter maxima that ranged from 46 to 1889 ng m−3, with an average of 428 ± 399 ng m−3. Besides agricultural burning, biomass/biofuel combustion for household heating with straws and branches appears to be of regional importance during the heating season in northwestern China. Good correlations (0.70 < R < 0.91) were found between levoglucosan relative to water-soluble K+, Cl−, organic carbon (OC), elemental carbon (EC), and glyoxal. The highest levoglucosan/OC ratio of 2.3% was found in winter, followed by autumn (1.5%). Biomass burning contributed to 5.1–43.8% of OC (with an average of 17.6 ± 8.4%). Implications: PM2.5 levoglucosan concentrations and the correlation between levoglucosan relative to other compounds during four seasons in Xi’an showed that the influence of biomass burning is maximum during the residential heating season (winter), although some important influences may be detected in spring (field preparation burnings) and autumn (corn stalks and wheat straw burning, fallen dead leaves burning) at Xi’an and surrounding areas. Household heating with biomass during winter was quite widespread in Guanzhong Plain. Therefore, the control of biomass/biofuel combustion could be an effective method to reduce pollutant emission on a regional scale.

n-Alkanes and polycyclic aromatic hydrocarbons in total suspended particulates from the southeastern Tibetan Plateau: concentrations, seasonal variations, and sources.

Sixty-two suspended particle (TSP) samples were collected from Lulang on the southeastern Tibetan Plateau from July 2008 and July 2009 to investigate the concentrations, seasonal variations, and sources of n-alkanes and polycyclic aromatic hydrocarbons (PAHs). Samples were analyzed using thermal-deposition gas chromatography mass spectrometry. The concentrations of particulate total n-alkanes ranged from 0.10 to 21.83 ng m(-3), with an annual mean of 1.25 ng m(-3); the PAHs ranged from 0.06 to 2.53, with a mean of 0.59 ng m(-3). Up to 70% of PAHs were 5- and 6-ring compounds. The n-alkanes and PAHs both showed higher concentrations in winter and lower concentrations in summer. Analyses of diagnostic ratios indicate that 6.4% to 58.9% (mean 24.9%) of the n-alkanes were from plant waxes. Source characterization studies, i.e. diagnostic ratio and positive factor matrix analysis, suggest that the PAHs were from biomass burning as well as from fossil fuel combustion. Backward trajectory analysis suggests that the biomass mass burning pollutants could be from South Asia and western China via long distance transport. The study contributes to a more comprehensive understanding of the concentrations, seasonal variations, and sources of n-alkanes and PAHs in a remote background area in Tibetan Plateau.

Long-Term Trends in Visibility and at Chengdu, China

Long-term (1973 to 2010) trends in visibility at Chengdu, China were investigated using meteorological data from the U.S. National Climatic Data Center. The visual range exhibited a declining trend before 1982, a slight increase between 1983 and 1995, a sharp decrease between 1996 and 2005, and some improvements after 2006. The trends in visibility were generally consistent with the economic development and implementation of pollution controls in China. Intensive PM2.5 measurements were conducted from 2009 to 2010 to determine the causes of visibility degradation. An analysis based on a modification of the IMPROVE approach indicated that PM2.5 ammonium bisulfate contributed 27.7% to the light extinction coefficient (bext); this was followed by organic mass (21.7%), moisture (20.6%), and ammonium nitrate (16.3%). Contributions from elemental carbon (9.4%) and soil dust (4.3%) were relatively minor. Anthropogenic aerosol components (sulfate, nitrate, and elemental carbon) and moisture at the surface also were important determinants of the aerosol optical depth (AOD) at 550 nm, and the spatial distributions of both bext and AOD were strongly affected by regional topography. A Positive Matrix Factorization receptor model suggested that coal combustion was the largest contributor to PM2.5 mass (42.3%) and the dry-air light-scattering coefficient (47.7%); this was followed by vehicular emissions (23.4% and 20.5%, respectively), industrial emissions (14.9% and 18.8%), biomass burning (12.8% and 11.9%), and fugitive dust (6.6% and 1.1%). Our observations provide a scientific basis for improving visibility in this area.

Characterization of PM2.5 in Guangzhou, China: uses of organic markers for supporting source apportionment.

Organic carbon (OC), elemental carbon (EC), and non-polar organic compounds including n-alkanes (n-C14-n-C40), polycyclic aromatic hydrocarbons (PAHs), phthalate esters (PAEs) and hopanes were quantified in fine particulate (PM2.5), which were collected in urban area of Guangzhou, China in winter and summer in 2012/2013. The pollutants levels were well comparable with the data obtained in previous studies in Pearl River Delta (PRD) region but much lower than most northern Chinese megacities. The contribution of EC to PM2.5 and OC/EC ratio suggest that the pollution sources were relatively consistent in GZ between the two seasons. Benzo[a]pyrene (BaP) was the most abundant PAHs, which were 4.9 and 1.0ng/m(3) on average, accounting for 10.7% and 9.1% to the total quantified PAHs in winter and summer, respectively. The total concentrations of PAEs ranged from 289.1 to 2435ng/m(3) and from 102.4 to 1437ng/m(3), respectively, in winter and summer. Di-n-butyl phthalate (DBP) was the most dominant PAEs. The ambient levels of PAEs could be partly attributed to the widespread uses of the household products, municipal garbage compressing, sewage, and external painting material on the building. Source apportionment for OC with chemical mass balance (CMB) model demonstrated coal combustion, vehicle emission, cooking, and secondary organic compounds (SOC) formation were the four major pollution sources. Both of the indices of n-alkanes and diagnostic PAHs ratios support that anthropogenic sources such as vehicle emission and coal combustion were the significant pollution sources with some extents from epicuticular waxes by terrestrial plants. The ratio of hopanes to EC proved the influences from vehicle emission, and displayed a certain degree of the air aging in the Guangzhou ambient air.

Sphere-Shaped Mn3O4 Catalyst with Remarkable Low-Temperature Activity for Methyl–Ethyl–Ketone Combustion

Mn3O4, FeMnOx, and FeOx catalysts synthesized via a solvothermal method were employed for catalytic oxidation of methyl-ethyl-ketone (MEK) at low temperature. Mn3O4 with sphere-like morphology exhibited the highest activity for MEK oxidation, over which MEK was completely oxidized to CO2 at 200 °C, and this result can be comparable to typical noble metal loaded catalysts. The activation energy of MEK over Mn3O4 (30.8 kJ/mol) was much lower than that of FeMnOx (41.5 kJ/mol) and FeOx (47.8 kJ/mol). The dominant planes, surface manganese species ratio, surface-absorbed oxygen, and redox capability played important roles in the catalytic activities of catalysts, while no significant correlation was found between specific surface area and MEK removal efficiency. Mn3O4 showed the highest activity, accounting for abundant oxygen vacancies, low content of surface Mn4+ and strong reducibility. The oxidation of MEK to CO2 via an intermediate of diacetyl is a reaction pathway on Mn3O4 catalyst. Due to high efficiency and low cost, sphere-shaped Mn3O4 is a promising catalyst for VOCs abatement.

Characteristics and major sources of carbonaceous aerosols in PM2.5 from Sanya, China.

PM2.5 samples were collected in Sanya, China in summer and winter in 2012/2013. Organic carbon (OC), elemental carbon (EC), and non-polar organic compounds including n-alkanes (n-C14-n-C40) and polycyclic aromatic hydrocarbons (PAHs) were quantified. The concentrations of these carbonaceous matters were generally higher in winter than summer. The estimated secondary organic carbon (OCsec) accounted for 38% and 54% of the total organic carbon (TOC) in winter and summer, respectively. The higher value of OCsec in addition to the presences of photochemically-produced PAHs in summer supports that photochemical conversions of organics are much active at the higher air temperatures and with stronger intense solar radiation. Carbon preference index (CPI) and percent contribution of wax n-alkanes suggest that anthropogenic sources were more dominant than derivation from terrestrial plants in Sanya. Diagnostic ratios of atmospheric PAHs further indicate that there was a wide mix of pollution sources in winter while fossil fuel combustion was the most dominant in summer. Positive Matrix Factorization (PMF) analysis with 18 PAHs in the winter samples found that motor vehicle emissions and biomass burning were the two main pollution sources, contributing 37.5% and 24.6% of the total quantified PAHs, respectively.