Rujin Huang

Radiocarbon-Based Source Apportionment of Carbonaceous Aerosols at a Regional Background Site on Hainan Island, South China

To assign fossil and nonfossil contributions to carbonaceous particles, radiocarbon ((14)C) measurements were performed on organic carbon (OC), elemental carbon (EC), and water-insoluble OC (WINSOC) of aerosol samples from a regional background site in South China under different seasonal conditions. The average contributions of fossil sources to EC, OC and WINSOC were 38 ± 11%, 19 ± 10%, and 17 ± 10%, respectively, indicating generally a dominance of nonfossil emissions. A higher contribution from fossil sources to EC (∼51%) and OC (∼30%) was observed for air-masses transported from Southeast China in fall, associated with large fossil-fuel combustion and vehicle emissions in highly urbanized regions of China. In contrast, an increase of the nonfossil contribution by 5-10% was observed during the periods with enhanced open biomass-burning activities in Southeast Asia or Southeast China. A modified EC tracer method was used to estimate the secondary organic carbon from fossil emissions by determining (14)C-derived fossil WINSOC and fossil EC. This approach indicates a dominating secondary component (70 ± 7%) of fossil OC. Furthermore, contributions of biogenic and biomass-burning emissions to contemporary OC were estimated to be 56 ± 16% and 44 ± 14%, respectively.

Development of a Coupled Diffusion Denuder System Combined with Gas Chromatography/Mass Spectrometry for the Separation and Quantification of Molecular Iodine and the Activated Iodine Compounds Iodine Monochloride and Hypoiodous Acid in the Marine Atmosphere

This study concerns the development of a coupled diffusion denuder system capable of separating and quantifying gaseous molecular iodine (I(2)) and two other highly reactive iodine species, ICl and HOI, which are collectively named activated iodine compounds (AIC). Both I(2) and AIC are key species in the atmospheric chemistry of iodine. 1,3,5-Trimethoxybenzene (1,3,5-TMB)- and alpha-cyclodextrin/(129)I(-) (alpha-CD/(129)I(-))-coated denuders proved to be suitable for the collection of gaseous AIC and I(2), respectively. The experimental collection efficiencies for AIC (tested as ICl) and I(2) agreed well with the theoretical values for gas flow rates in the range between 300 and 1800 mL min(-1). The coupled denuder system (1,3,5-TMB-coated denuder as front-denuder coupled upstream of an alpha-CD/(129)I(-)-coated denuder) was applied successfully to separate test gas mixtures of ICl and I(2) at various mixing ratios in the laboratory. The operation of both denuder systems was demonstrated to be independent of relative humidity (0-100%) and storage period (at least 2 weeks prior to and after sampling). Detection limits were achieved at sub-parts-per-trillion-by-volume (sub-pptv) level. The presented method provides a reliable and practical approach for the speciation of gaseous iodine compounds. In addition, we report for the first time ambient air measurements of AIC mixing ratios, carried out at the atmospheric research station in Mace Head, Ireland. A maximum concentration of AIC of 30.2 pptv was observed for nighttime measurements and 6.0 pptv for daytime measurements. A similar diurnal pattern was found for I(2) with an average concentration level of 23.2 pptv during daytime and 85.1 pptv during nighttime, indicating a strong correlation with AIC.

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.

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.

Black carbon aerosol characterization in a remote area of Qinghai-Tibetan Plateau, western China.

The concentrations, size distributions, and mixing states of refractory black carbon (rBC) aerosols were measured with a ground-based Single Particle Soot Photometer (SP2), and aerosol absorption was measured with an Aethalometer at Qinghai Lake (QHL), a rural area in the Northeastern Tibetan Plateau of China in October 2011. The area was not pristine, with an average rBC mass concentration of 0.36 μg STP-m(-3) during the two-week campaign period. The rBC concentration peaked at night and reached the minimal in the afternoon. This diurnal cycle of concentration is negatively correlated with the mixed layer depth and ventilation. When air masses from the west of QHL were sampled in late afternoon to early evening, the average rBC concentration of 0.21 μg STP-m(-3) was observed, representing the rBC level in a larger Tibetan Plateau region because of the highest mixed layer depth. A lognormal primary mode with mass median diameter (MMD) of ~175 nm, and a small secondary lognormal mode with MMD of 470-500 nm of rBC were observed. Relative reduction in the secondary mode during a snow event supports recent work that suggested size dependent removal of rBC by precipitation. About 50% of the observed rBC cores were identified as thickly coated by non-BC material. A comparison of the Aethalometer and SP2 measurements suggests that non-BC species significantly affect the Aethalometer measurements in this region. A scaling factor for the Aethalometer data at a wavelength of 880 nm is therefore calculated based on the measurements, which may be used to correct other Aethalometer datasets collected in this region for a more accurate estimate of the rBC loading. The results present here significantly improve our understanding of the characteristics of rBC aerosol in the less studied Tibetan Plateau region and further highlight the size dependent removal of BC via precipitation.

In situ Fabrication of α-Bi2O3/(BiO)2CO3 Nanoplate Heterojunctions with Tunable Optical Property and Photocatalytic Activity

Exploring the full potential use of heterojunction photocatalysts containing bismuth has attracted considerable interest in recent years. Fabrication of well-defined heterojunction photocatalysts with precise modulation of their chemical composition is crucial for tuning their optical properties and photocatalytic activity. In this study, we fabricated nanoplate α-Bi2O3/(BiO)2CO3 heterojunctions through in situ thermal treatment of (BiO)2CO3 nanoplates synthesized using a facile hydrothermal process. Characterization results showed that the as-prepared Bi2O3/(BiO)2CO3 heterojunctions possessed distinct crystal interface and exhibited pronounced structural and optical modulation, resulting in significant improvement of their photocatalytic activity for NO removal under simulated solar light irradiation compared with pristine (BiO)2CO3. Electron spin resonance spectroscopy showed that ⋅OH radicals were the major reactive species involved in NO degradation, which is consistent with the theoretical analysis. The heterojunction formation can not only broaden the light absorption range but also improve the charge separation of photo-induced electron–hole pairs. This study is an important advancement in the development of semiconductor heterojunctions towards achieving functional photocatalysts.

Chemical profiles of urban fugitive dust PM2.5 samples in Northern Chinese cities

Urban fugitive dust PM2.5 samples were collected in 11 selected cities in North China, and 9 ions (SO4(2-), NO3(-), Cl(-), F(-), Na(+), NH4(+), K(+), Mg(2+), and Ca(2+)) and 22 elements (Si, Al, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Br, Rb, Sr, Sn, Sb, Ba, and Pb) were determined to investigate chemical profiles of PM2.5. The coefficient of divergence (CD) was used to compare the similarities of the chemical profiles for fugitive dust among three regions in North China, and the results showed that their composition are quite similar. Total water soluble ions occupied 9.3% and 10.0% on average of road dust and construction dust, respectively, indicating that most of the materials in urban fugitive dust samples were insoluble. Ca(2+) was the most abundant cation and SO4(2-) dominated in anions. Soil dust loading was calculated to occupy 70.8% and 83.6% in road dust and construction dust, respectively. Ca, Si, Fe, and Al were the most abundant elements in all the samples, and Ca was absolutely the most abundant specie among the 22 detected elements in construction dust samples. Chemical species ratios were used to highlight the characteristics of urban fugitive dust by comparing with other types of aerosols. High Ca/Al ratio was a good marker to distinguish urban fugitive dust from Asian dust and Chinese loess. In addition, low K(+)/K and NO3(-)/SO4(2-), and high Zn/Al and Pb/Al ratios were good indicators to separate urban fugitive dust from desert dust, Chinese loess, or urban PM2.5 samples.

Effect of heavy haze and aerosol pollution on rice and wheat productions in China.

In China, regional haze pollution is a serious environmental problem. The impact on ecosystem, however, is not clearly understood. This study investigates the effect of regional haze pollution on the yields of rice and wheat in China. The spatial and temporal distributions of aerosol optical depth (AOD) show high particulate pollution in the North China Plain region, Yangtze River Delta region, the central eastern China, and the Si Chuan Basin, coexisted largely with crop growth in time and space. The solar irradiance reaching these regions is estimated to reduce by up to 28–49%, calculated using the AOD distributions and tropospheric ultraviolet-visible (TUV) model. Reduction of solar irradiance in these regions can depress optimal yields of about 45% of rice and 75% of wheat growth in China, leading to 2% reduction in total rice production and 8% reduction in total wheat production in China. However, there are large uncertainties of the estimate related to the diffuse solar radiation. For high diffuse radiation case, the estimate reductions of rice and wheat decrease to 1% and 4.5%, respectively. A further detailed study is needed to clearly understand this effect to meet the growing food demand in the nation in the coming decades.

Seasonal variations of monocarbonyl and dicarbonyl in urban and sub-urban sites of Xi’an, China

Seventeen airborne carbonyls including monocarbonyls and dicarbonyls were determined in urban and sub-urban sites of Xi’an, China in three seasons in 2010. In winter, acetone was the most abundant carbonyl in the urban site due to usage of organic solvents in constructions and laboratories and its slower atmospheric removal mechanisms by photolysis and reaction with hydroxyl radical than those of formaldehyde and acetaldehyde. In the sub-urban site, acetaldehyde was the most abundant carbonyl, followed by formaldehyde and acetone. During summer, however, formaldehyde was the most dominant carbonyl in both sites. The photooxidations of a wide range of volatile organic compounds (VOCs) yielded much more formaldehyde than other carbonyls under high solar radiation and temperature. In the urban site, the average concentrations of dicarbonyls (i.e., glyoxal and methyglyoxal) in spring and summer were higher than that in winter. Transformation of aromatic VOCs emitted from fuel evaporation leads to the formation of 1,2-dicarbonyls. A reverse trend was observed in sub-urban sites, as explained by the relatively low abundances and accumulations of VOC precursors in the rural atmosphere during warm seasons. Moreover, cumulative cancer risk based on measured outdoor carbonyls (formaldehyde and acetaldehyde) in Xi’an Jiaotong University and Heihe was estimated (8.82 × 10−5 and 4.96 × 10−5, respectively). This study provides a clear map on the abundances of carbonyls and their source interpretation in the largest and the most economic city in Northwestern China.

Extensive evaluation of a diffusion denuder technique for the quantification of atmospheric stable and radioactive molecular iodine.

In this paper we present the evaluation and optimization of a new approach for the quantification of gaseous molecular iodine (I(2)) for laboratory- and field-based studies and its novel application for the measurement of radioactive molecular iodine. alpha-Cyclodextrin (alpha-CD) in combination with (129)I(-) is shown to be an effective denuder coating for the sampling of gaseous I(2) by the formation of an inclusion complex. The entrapped (127)I(2) together with the (129)I(-) spike in the coating is then released and derivatized to 4-iodo-N,N-dimethylaniline (4-I-DMA) for gas chromatography-mass spectrometry (GC-MS) analysis. The (127)I(2) collected can be differentiated from the (129)I(-) spike by MS. A set of parameters affecting the analytical performances of this approach, including amount of alpha-CD and (129)I(-) applied, denuder length, sampling gas flow rate and sampling duration, relative humidity, sample storage period, and condition of release and derivatization of iodine, is extensively evaluated and optimized. The collection efficiency is larger than 98% and the limit of detection (LOD) obtained is 0.17 parts-per-trillion-by-volume (pptv) for a sampling duration of 30 min at 500 mL min(-1). Furthermore, the potential use of this protocol for the determination of radioactive I(2) at ultra trace level is also demonstrated when (129)I(-) used in the coating is replaced by (127)I(-) and a multiple denuder system is used. Using the present method we observed 25.7-108.6 pptv (127)I(2) at Mweenish Bay, Ireland and 10(8) molecule m(-3 129)I(2) at Mainz, Germany.