Junji Cao

Black soot and the survival of Tibetan glaciers

We find evidence that black soot aerosols deposited on Tibetan glaciers have been a significant contributing factor to observed rapid glacier retreat. Reduced black soot emissions, in addition to reduced greenhouse gases, may be required to avoid demise of Himalayan glaciers and retain the benefits of glaciers for seasonal fresh water supplies.

Persistent sulfate formation from London Fog to Chinese haze

Significance Exceedingly high levels of fine particulate matter (PM) occur frequently in China, but the mechanism of severe haze formation remains unclear. From atmospheric measurements in two Chinese megacities and laboratory experiments, we show that the oxidation of SO2 by NO2 occurs efficiently in aqueous media under two polluted conditions: first, during the formation of the 1952 London Fog via in-cloud oxidation; and second, on fine PM with NH3 neutralization during severe haze in China. We suggest that effective haze mitigation is achievable by intervening in the sulfate formation process with NH3 and NO2 emission control measures. Hence, our results explain the outstanding sulfur problem during the historic London Fog formation and elucidate the chemical mechanism of severe haze in China. Sulfate aerosols exert profound impacts on human and ecosystem health, weather, and climate, but their formation mechanism remains uncertain. Atmospheric models consistently underpredict sulfate levels under diverse environmental conditions. From atmospheric measurements in two Chinese megacities and complementary laboratory experiments, we show that the aqueous oxidation of SO2 by NO2 is key to efficient sulfate formation but is only feasible under two atmospheric conditions: on fine aerosols with high relative humidity and NH3 neutralization or under cloud conditions. Under polluted environments, this SO2 oxidation process leads to large sulfate production rates and promotes formation of nitrate and organic matter on aqueous particles, exacerbating severe haze development. Effective haze mitigation is achievable by intervening in the sulfate formation process with enforced NH3 and NO2 control measures. In addition to explaining the polluted episodes currently occurring in China and during the 1952 London Fog, this sulfate production mechanism is widespread, and our results suggest a way to tackle this growing problem in China and much of the developing world.

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.

Mixing State of Black Carbon Aerosol in a Heavily Polluted Urban Area of China: Implications for Light Absorption Enhancement

Black carbon (BC) is important for climate forcing, and its effects on the Earths radiative balance remain a major uncertainty in climate models. In this study, we investigated the mixing state of refractory black carbon (rBC) and aerosol optical properties in a polluted atmosphere at Xi’an, western China. The average rBC mass concentration was 9.9 μg m−3 during polluted periods, 7.6 times higher than that in clean periods. About 48.6% of the rBC was internally-mixed or coated with nonrefractory materials during polluted periods; this was 27% higher than in clean periods. Correlation analysis between the number fraction of thickly-coated rBC particles (fBC) and the major particulate species indicate that organics may be the primary contributor to rBC coatings during polluted periods. The average mass absorption cross section of rBC (MACBC) particles at λ = 870 nm was 7.6 ± 0.02 m2 g−1 for the entire campaign. The MACBC showed a positive correlation with fBC, and the enhancement of MACBC due to internal mixing was 1.8 times. These observations suggest that an enhancement of BC absorption by a factor of ∼2 could be appropriate for climate models associated with high PM2.5 levels. Copyright 2014 American Association for Aerosol Research

Removal of Indoor Volatile Organic Compounds via Photocatalytic Oxidation: A Short Review and Prospect

Volatile organic compounds (VOCs) are ubiquitous in indoor environments. Inhalation of VOCs can cause irritation, difficulty breathing, and nausea, and damage the central nervous system as well as other organs. Formaldehyde is a particularly important VOC as it is even a carcinogen. Removal of VOCs is thus critical to control indoor air quality (IAQ). Photocatalytic oxidation has demonstrated feasibility to remove toxic VOCs and formaldehyde from indoor environments. The technique is highly-chemical stable, inexpensive, non-toxic, and capable of removing a wide variety of organics under light irradiation. In this paper, we review and summarize the traditional air cleaning methods and current photocatalytic oxidation approaches in both of VOCs and formaldehyde degradation in indoor environments. Influencing factors such as temperature, relative humidity, deactivation and reactivations of the photocatalyst are discussed. Aspects of the application of the photocatalytic technique to improve the IAQ are suggested.

Characteristics of indoor/outdoor PM2.5 and elemental components in generic urban, roadside and industrial plant areas of Guangzhou city, China

Quantitative information on mass concentrations and other characteristics, such as spatial distribution, seasonal variation, indoor/outdoor (I/O) ratio, correlations and sources, of indoor and outdoor PM2.5 and elemental components in Guangzhou City were provided. Mass concentration of PM2.5 and elemental components were determined by standard weight method and proton-induced X-ray emission (PIXE) method. 18 elements were detected, the results showed positive results. Average indoor and outdoor PM2.5 concentrations in nine sites were in the range of 67.7-74.5 microg/m3 for summer period, and 109.9-123.7 microg/m3 for winter period, respectively. The sum of 18 elements average concentrations were 5362.6-5533.4 ng/m3 for summer period, and 8416.8-8900.6 ng/m3 for winter period, respectively. Average concentrations of PM2.5 and element components showed obvious spatial characteristic, that the concentrations in roadside area and in industrial plant area were higher than those in generic urban area. An obvious seasonal variation characteristic was found for PM2.5 and elemental components, that the concentrations in winter were higher than that in summer. The I/O ratio of PM2.5 and some elemental components presented larger than 1 sometimes. According to indoor/outdoor correlation of PM2.5 and element concentrations, it was found that there were often good relationships between indoor and outdoor concentrations. Enrichment factors were calculated to evaluate anthropogenic versus natural elements sources.

Comparison of Elemental Carbon in Lake Sediments Measured by Three Different Methods and 150-Year Pollution History in Eastern China

Concentrations of elemental carbon (EC) were measured in a 150 yr sediment record collected from Lake Chaohu in Anhui Province, eastern China, using three different thermal analytical methods: IMPROVE_A thermal optical reflectance (TOR), STN_thermal optical transmittance (TOT), and chemothermal oxidation (CTO). Distribution patterns for EC concentrations are different among the three methods, most likely due to the operational definition of EC and different temperature treatments prescribed for each method. However, similar profiles were found for high-temperature EC fractions among different methods. Historical soot(TOR) (high-temperature EC fractions measured by the IMPROVE_A TOR method) from Lake Chaohu exhibited stable low concentrations prior to the late 1970s and a sharp increase thereafter, corresponding well with the rapid industrialization of China in the last three decades. This may suggest that high-temperature thermal protocols are suitable for differentiating between soot and other carbon fractions. A similar soot(TOR) record was also obtained from Lake Taihu (~200 km away), suggesting a regional source of soot. The ratio of char(TOR) (low-temperature EC fraction measured by the IMPROVE_A TOR method, after correction for pyrolysis) to soot(TOR) in Lake Chaohu shows an overall decreasing trend, consistent with gradual changes in fuel use from wood burning to increasing fossil fuel combustions. Average higher char(TOR)/soot(TOR) was observed in Lake Taihu than in Lake Chaohu in the past 150 years, consistent with the longer and more extensive industrialization around the Taihu region.

Exposure to PM2.5 and PAHs from the Tong Liang, China Epidemiological Study

Chemically speciated PM2.5 and particle-bound polycyclic aromatic hydrocarbon (PAH) measurements were made at three sites near urban Tong Liang, Chongqing, a Chinese inland city where coal combustion is used for electricity generation and residential purposes outside of the central city. Ambient sampling was based on 72-hr averages between 3/2/2002 and 2/26/2003. Elevated PM2.5 and PAH concentrations were observed at all three sites, with the highest concentrations found in winter and the lowest in summer. This reflects a coupling effect of source variability and meteorological conditions. The PM2.5 mass estimated from sulfate, nitrate, ammonium, organics, elemental carbon, crustal material, and salt corresponded with the annual average gravimetric mass within ±10%. Carbonaceous aerosol was the dominant species, while positive correlations between organic carbon and trace elements (e.g., As, Se, Br, Pb, and Zn) were consistent with coal-burning and motor vehicle contributions. Ambient particle-bound PAHs of molecular weight 168–266 were enriched by 1.5 to 3.5 times during the coal-fired power plant operational period. However, further investigation is needed to determine the relative contribution from residential and utility coal combustion and vehicular activities.

Visible-Light-Active Plasmonic Ag-SrTiO3 Nanocomposites for the Degradation of NO in Air with High Selectivity.

Harnessing inexhaustible solar energy for photocatalytic disposal of nitrogen oxides is of great significance nowadays. In this study, Ag-SrTiO3 nanocomposites (Ag-STO) were synthesized via one-pot solvothermal method for the first time. The deposition of Ag nanoparticles incurs a broad plasmonic resonance absorption in the visible light range, resulting in enhanced visible light driven activity on NO removal in comparison with pristine SrTiO3. The Ag loading amount has a significant influence on light absorption properties of Ag-STO, which further affects the photocatalytic efficiency. It was shown that 0.5% Ag loading onto SrTiO3 (in mass ratio) could remove 30% of NO in a single reaction path under visible light irradiation, which is twice higher than that achieved on pristine SrTiO3. Most importantly, the generation of harmful intermediate (NO2) is largely inhibited over SrTiO3 and Ag-STO nanocomposites, which can be ascribed to the basic surface property of strontium sites. As identified by electron spin resonance (ESR) spectra,·O2(-) and ·OH radicals are the major reactive species for NO oxidation. Essentially speaking, the abundance of reactive oxygen radicals produced over Ag-STO nanocomposites are responsible for the improved photocatalytic activity. This work provides a facile and controllable route to fabricate plasmonic Ag-SrTiO3 nanocomposite photocatalyst featuring high visible light activity and selectivity for NO abatement.

The Influence of Dust on Quantitative Measurements of Black Carbon in Ice and Snow when Using a Thermal Optical Method

Accurate measurements of black carbon concentrations in snow and ice are essential to quantify its impact on glacial melting and sequential climate forcing via snow albedo. However, snow and ice contain dust that may severely bias the precision of the elemental carbon (EC) and organic carbon (OC) measurements of filters with a thermal/optical method. To evaluate the effects of dust on black carbon analysis and to optimize filtration methods, meltwater from ice core and surface snow samples with variable dust content were filtered with different methods, including filtration of the entire material (including settling) and supernatant liquid, mechanical stirring and sonication, as well as utilization of single and double quartz filters. In this research, it is shown that dust can induce an extra decrease in optical reflectance during the 250°C heating stage in the thermal/optical method and an improper OC and EC split. To address this problem, a correction procedure was suggested and used to revise the OC and EC results. The OC, EC, and TC concentration variations from different filtration methods along the ice core depth and along surface snow elevation were illustrated. These results indicate that black carbon and dust generally mix as agglomerates. The agglomerate structure will contribute to the underestimation of EC and OC in the measurement. However, carbonaceous matter can be efficiently detached from dust particles by ultrasonic agitation of the meltwater samples, which significantly improves carbon volatilization during the thermal/optical analysis. Copyright 2012 American Association for Aerosol Research