成都市夏季大气挥发性有机物污染及其对二次有机气溶胶生成的贡献

于2014年7月8日至8月13日在成都市城区和工业区选取两个点位开展挥发性有机物(VOCs)样品采集工作,分析结果显示,成都市夏季城区大气中VOCs质量浓度在34.1~458.8μg/m3,平均值为(137.3±91.8)μg/m3;工业区大气中VOCs质量浓度在26.7~474.9μg/m3,平均值为(135.9±103.5)μg/m3。早高峰时段(7:00~10:00)两个点位VOCs的浓度水平均高于其他时段,说明VOCs浓度受机动车排放的影响较为明显。用·OH消耗速率和臭氧生成潜势评估VOCs大气化学反应活性,结果显示,芳香烃和烯烃是影响大气化学反应活性的关键组分。城区和工业区的二次有机气溶胶(SOA)的生成潜势分别为4.859、4.559μg/m3,芳香烃不仅是臭氧生成潜势的关键活性组分,同时也是SOA的重要前体物。     

Interaction of bisphenol A with dissolved organic matter in extractive and adsorptive removal processes

The fate of endocrine disrupting chemicals (EDCs) in natural and engineered systems is complicated due to their interactions with various water constituents. This study investigated the interaction of bisphenol A (BPA) with dissolved organic matter (DOM) and colloids present in surface water and secondary effluent as well as its adsorptive removal by powdered activated carbons. The solid phase micro-extraction (SPME) method followed by thermal desorption and gas chromatography-mass spectrometry (GC-MS) was utilized for determining the distribution of BPA molecules in water. The BPA removal by SPME decreased with the increased DOM content, where the formation of BPA-DOM complexes in an aqueous matrix was responsible for the reduced extraction of BPA. Colloidal particles in water samples sorbed BPA leading to the marked reduction of liquid phase BPA. BPA-DOM complexes had a negative impact on the adsorptive removal of BPA by powered activated carbons. The complex formation was characterized based on Fourier transform infrared (FTIR) and ultraviolet-visible (UV-Vis) spectroscopy, along with the calculation of molecular interactions between BPA and functional groups in DOM. It was found that the hydrogen bonding between DOM and BPA would be preferred over aromatic interactions. A pseudo-equilibrium molecular coordination model for the complexation between a BPA molecule and a hydroxyl group of the DOM was developed, which enabled estimation of the maximum sorption site and complex formation constant as well as prediction of organic complexes at various DOM levels.     

芳香类有机物氯化生成消毒副产物的特性研究

选择有代表性的芳香类有机物,在含有腐殖酸的水溶液中进行氯化试验.测定三卤甲烷和卤乙酸的生成特性.并分析有机物的化学结构对生成消毒副产物的影响.结果表明.各受试物氯化生成消毒副产物的活性和反应速率排序为间苯二酚>对苯二酚>邻苯二酚>苯酚>苯胺>苯甲酸>硝基苯;芳香类有机物苯环上官能团的性质、数量和位置等影响消毒副产物的生成;间苯二酚的氯化反应可分为快速反应阶段和慢速反应阶段.     

Role of organic and black carbon in the chemical composition of atmospheric aerosol at European background sites

The mass concentrations of inorganic ions, water-soluble organic carbon, water-insoluble organic carbon and black carbon were determined in atmospheric aerosol collected at three European background sites: (i) the Jungfraujoch, Switzerland (high-alpine, PM_2.5 aerosol); (ii) K-puszta, Hungary (rural, PM_1.0 aerosol); (iii) Mace Head, Ireland (marine, total particulate matter). At the Jungfraujoch and K-puszta the contribution of carbonaceous compounds to the aerosol mass was higher than that of inorganic ions by 33% and 94%, respectively. At these continental sites about 60% of the organic carbon was water soluble, 55–75% of the total carbon proved to be refractory and a considerable portion of the water soluble, refractory organic matter was composed of humic-like substances. At Mace Head the mass concentration of organic matter was found to be about twice than that of nonsea-salt ions, 40% of the organic carbon was water soluble and the amount of highly refractory carbon was low. Humic-like substances were not detected but instead low molecular weight carboxylic acids were responsible for about one-fifth of the water-soluble organic mass. These results imply that the influence of carbonaceous compounds on aerosol properties (e.g. hygroscopic, optical) might be significant.     

Reverse quantitative structure-activity relationship for modelling the sorption of esfenvalerate to dissolved organic matter. A multivariate approach

The sorption of the pyrethroid, esfenvalerate, to the dissolved and/or dispersed fraction of eight different natural humic compounds has been investigated. The dissolved organic matters (DOMs) included in this study originate from ground water, soil pore water, and surface waters. Sorption was modelled at DOM concentration levels where equilibrium partitioning of esfenvalerate between DOM and the aqueous bulk phase prevails. The inherent characteristics of the eight different humic materials, quantified in the preceding paper by Thomsen et al. (2002, this issue (PII: S0045-6535(02)00335-1)), have been used as explanatory variables for modelling this equilibrium partitioning. Using a reverse QSAR approach based on by projection-into-latent-structure regression (PLS-R) inherent sorbent properties determining for the sorption affinity of esfenvalerate to DOM were analysed. For all humic substances a decrease in the DOM-normalised equilibrium-partitioning coefficient, K_DOM, with increasing concentration of DOM was observed. Significant variations in K_DOM values, as function of the inherent characteristics of the individual humic substances, were found at DOM concentrations of 75 and 100 ppm, respectively. The latter is a strong indication of variations in sorption mechanisms of esfenvalerate to DOM of varying inherent properties. Groupings in the principal property space quantifying DOMs may indicate that separate models are needed for quantifying the equilibrium partitioning to different classes of DOM.     

A comparative evaluation of passive and active samplers for measurements of gaseous semi-volatile organic compounds in the tropical atmosphere

The polyurethane foam (PUF) disk-based passive air samplers (PAS), mounted inside two aluminium bowls to buffer the air flow to the disk and to shield it from precipitation and sunlight, were used for the collection of atmospheric SVOCs in Singapore during April 2008–June 2008. Data obtained from PAS measurements are compared to those from active high-volume air sampling (AAS). Single factor ANOVA tests show that there were no significant differences in chemical distribution profiles between actively and passively collected samples (PAHs, F = 3.38 × 10^?8 < F_critical = 4.17 with p > 0.05; OCPs, F = 2.71 × 10^?8 < F_critical = 4.75 with p > 0.05). The average air-side mass transfer coefficient (k_A) for PAS, determined from the loss of depuration compounds such as 13C₆ – HCB (1000 ng), 13C₁₂ – 4,4′ DDT (1000 ng) and 13C₁₂ – PCB 101 (1000 ng)spiked on the disks prior to deployment, was 0.12 ± 0.04 m s^?1. These values are comparable to those reported previously in the literature. The average sampling rate was 3.78 ± 1.83 m³ d^?1 for the 365 cm² PUF disk. Throughout the entire sampling period (～68 d), most of the PAHs and all OCPs exhibited a linear uptake trend on PAS, while naphthalene, acenaphthylene, acenaphthene and fluorene reached the curvilinear phase after the first ～30 d exposure. Theoretically estimated times to equilibrium (t_eq) ranged from around one month for Acy to hundreds of years for DB(ah)A. Sampling rates, based on the time integrated active sampling-derived concentrations and masses collected by PUF disks during the linear uptake phase, were determined for all target compounds with the average values of 2.50 m³ d^?1 and 3.43 m³ d^?1 for PAHs and OCPs, respectively. More variations were observed as compared to those from the depuration study. These variation were most likely due to the difference of physicochemical properties of individual species. Lastly, multiple linear regression models were developed to estimate the log-transformed gaseous concentration of an individual compound in air based on the mass collection rate of the gaseous SVOCs measured using the PAS and the molecular weight (MW) of the particular compound for both PAHs and OCPs, respectively.     

Contribution of motor vehicle emissions to organic carbon and fine particle mass in Pittsburgh, Pennsylvania: Effects of varying source profiles and seasonal trends in ambient marker concentrations

We present estimates of the vehicular contribution to ambient organic carbon (OC) and fine particle mass (PM) in Pittsburgh, PA using the chemical mass balance (CMB) model and a large dataset of ambient molecular marker concentrations. Source profiles for CMB analysis are selected using a method of comparing the ambient ratios of marker species with published profiles for gasoline and diesel vehicle emissions. The ambient wintertime data cluster on a hopanes/EC ratio–ratio plot, and therefore can be explained by a large number of different source profile combinations. In contrast, the widely varying summer ambient ratios can be explained by a more limited number of source profile combinations. We present results for a number of different CMB scenarios, all of which perform well on the different statistical tests used to establish the quality of a CMB solution. The results illustrate how CMB estimates depend critically on the marker-to-OC and marker-to-PM ratios of the source profiles. The vehicular contribution in the winter is bounded between 13% and 20% of the ambient OC (274±56–416±72 ng-C m⁻³). However, variability in the diesel profiles creates uncertainty in the gasoline–diesel split. On an OC basis, one set of scenarios suggests gasoline dominance, while a second set indicates a more even split. On a PM basis, all solutions indicate a diesel-dominated split. The summer CMB solutions do not present a consistent picture given the seasonal shift and wide variation in the ambient hopanes-to-EC ratios relative to the source profiles. If one set of source profiles is applied to the entire dataset, gasoline vehicles dominate vehicular OC in the winter but diesel dominates in the summer. The seasonal pattern in the ambient hopanes-to-EC ratios may be caused by photochemical decay of hopanes in the summer or by seasonal changes in vehicle emission profiles.     

A simple model for estimating emissions of volatile organic compounds from grass and cut grass in urban airsheds and its application to two Australian cities

Grass, and particularly cut grass, recently has been shown to emit significant amounts of volatile organic compounds (VOCs) into the atmosphere. Some components of these emissions are highly reactive and may contribute to photochemical smog in urban areas. A simple model for estimating the VOC emissions from grass and for grass cutting that allows these processes to be included in urban/regional emissions inventories is presented here. Using previous work and recent literature values, estimates are made of these biogenic volatile organic compound (BVOC) emissions for two typical urban airsheds, those including the cities of Sydney and Melbourne in Australia. Grass and cut grass could contribute approximately 2% for Sydney and 3% for Melbourne of the total VOCs emitted into these urban atmospheres annually. These contributions could rise to 4 and 5%, respectively, during the weekends of the summer growing season and, thus, could contribute to weekday/weekend ozone differences. It is recommended that the emissions of BVOCs from grass and cut grass be included in urban and global emissions inventories so that more accurate predictions of smog chemistry can be determined.     

MBBR与A/O法对污水中有机物及氮处理效果的研究

实验在不同水力停留时间（HRT）、进水COD浓度和不同COD容积负荷条件下考察了移动床生物膜反应器（MBBR）和活性污泥A/O工艺对污水中有机物及氮的处理效果。结果表明,MBBR工艺去除有机物和脱氮效果均优于A/O工艺。在进水COD和NH₃－N浓度分别为1000和25 mg/L,HRT为8 h时,MBBR的COD和TN去除率分别为92％和94％,而A/O工艺分别为78％和82％。造成这种结果的原因是MBBR的生物活性高,并且在生物膜内发生了同时硝化反硝化。MBBR脱氮能力受COD冲击明显小于A/O,但在较低进水COD浓度下,两者TN去除率均较低。