中国大气颗粒物中金属元素环境地球化学行为研究

大气颗粒物金属污染已成为目前大气污染的研究热点之一。文章梳理、分析归纳了中国近年来大气颗粒中金属元素的环境地球化学方面的研究。目前研究较多的是Fe、Ca、Mg、Si等地壳元素和Cu、Pb、Cd、Zn、Hg等污染元素;大气颗粒物中对人体有害的Cu、Pb、Cd、As、Zn等污染较严重,而Cr、Mn、Co、Ni等污染较轻。大气颗粒物中金属含量随时间分布变化显著,总体上呈现冬季〉秋季〉春季〉夏季的特点,空间分布上一般北方燃煤城市大于南方一般城市;城市内部一般工业区〉交通区〉居民区〉郊区;金属元素在细粒径颗粒（〈2μm）中高,粗颗粒（〉2μm）中低,尤其以污染元素明显。污染元素与地壳元素的垂直分布规律差异较大。大气颗粒物中金属元素的富集程度与元素种类、区域类型、季节变化、粒径大小等有关。最后,提出应加强大气颗粒物中金属元素空间分布差异、时间分布的尺度及差异性研究;同时加强超细颗粒物的研究,以便建立大气颗粒物金属元素与人类健康关系的风险模型。     

超细颗粒物PM25控制技术综述

PM2.5由于其较小的粒径、巨大的比表面积、较大的危害等特点受到世界各国的广泛研究。对此从亚微米粒子的来源、性质、危害等方面进行阐述,对比和总结国内外目前常用的控制技术,详细叙述了静电和其他除尘器相结合以及交流凝并技术脱出超细颗粒物的原理。交流凝并是一种适合收集亚微米粒子的有效方法,这种方法收集效果好,经济实用,适用于去除炼钢、焊接、煤炭燃烧后产生的悬浮性粉尘粒子等方面。研究粒子的荷电、凝并对继续完善荷电凝并理论,提高亚微米粒子的收集效果是十分必要的。     

乌鲁木齐市可吸入颗粒物污染水平及其与气象因素的相关性分析

为了解可吸入颗粒物污染水平与气象因素之间的关系,从2008年9月—2010年2月采集乌鲁木齐市可吸入颗粒物样品,并对其随时间的变化特征及其与气象因素之间的相关性进行了统计分析。结果表明,采样时间内可吸入颗粒物中PM2.5和PM2.5-10的质量浓度的范围分别为38.2~468.7μg/m3和20.8~243.1μg/m3,平均浓度分别为134.2μg/m3和69.2μg/m3。可吸入颗粒物同时受几种气象因素的影响,其浓度与温度、能见度、风速呈负相关,与湿度呈正相关。     

基于TEM-EDS对四川盆地大气单颗粒气溶胶的研究

为了解四川盆地大气中单颗粒气溶胶理化特征,分别在该区域典型城市（成都市）和背景地区（峨眉山）进行了大气单颗粒样品采集.基于带能谱的透射电子显微镜（TEM-EDS）对两地累计3923个单颗粒的化学组成、形貌特征及混合状态等进行了全面观测和分析,并对两地颗粒物差异性进行了对比分析.结果发现：两地气溶胶颗粒主要包括有机物、富硫、矿物、烟尘和飞灰/金属颗粒,除了以单独的外混形式存在外,大多数颗粒以两种及两种以上颗粒类型混合（即内混）形式存在.通过对成都市不同污染状况下单颗粒特征对比发现,"污染天"的内混颗粒占比高于"清洁天",分别为74.2%和68.6%;相比"清洁天","污染天"颗粒物粒径分布范围更广且峰值区间更大,表明污染过程中颗粒物的大气混合趋于更强.对比成都市与峨眉山分析结果得知,成都市以内混的有机物-硫颗粒为主导（占比为50.2%）,而峨眉山以外混的有机物颗粒为主导（占比为50.5%）;成都市含硫类颗粒物（如有机物-硫颗粒）贡献高于峨眉山,而峨眉山两种含碳类颗粒（如烟尘和有机物-烟尘颗粒）占比高于成都市;此外,成都市与峨眉山两地大气颗粒物粒径分布范围及峰值区间均存在一定差异,进一步体现了两地颗粒物来源和老化混合的差异.在峨眉山,与非降雨天相比,一些易溶于水的颗粒物（如含硫类颗粒）在降雨天占比明显降低,而源自当地燃烧过程、粒径较小且疏水性强的颗粒物（如烟尘和有机物-烟尘颗粒）占比相应升高.     

柴油车排气微粒后处理器的研究

通过同种典型微粒过滤器的比选试验,表明高效袋式消烟器微粒捕集效率最高.其结构简单,成本低,耐热性好,因此具有很好的推广价值.如果应用在公路隧道中,能降低隧道内能见度的影响,具有较大的开发前景.      

Determination of 10 particle-associated multiclass polar and semi-polar pesticides from small streams using accelerated solvent extraction

A new analytical method using accelerated solvent extraction was developed for the determination of 10 particle-associated polar and semipolar pesticides. In addition, six deuterated analogues of the target compounds were evaluated as internal standards. The method yielded acceptable accuracy (73–103% recovery) and precision (<25% relative standard deviation) for eight compounds. Using size exclusion chromatography (SEC) as cleanup step resulted in higher recoveries compared to solid phase extraction (SPE) cleanup.

Deuterated standards with 10 or more deuterium atoms performed well as internal standards concerning similar recovery and correlation with the target analytes.

The method was employed to extract particle-associated pesticides from 16 streams located in an area with intense agriculture in France. Acetochlor, pirimicarb, tebuconazole, fenpropidin, -endosulfan and chlorfenvinphos were detected at concentrations up to 1 mg kg⁻¹ dry weight. A comparison with aquatic toxicity data indicated potential risk to the benthic fauna exposed to these concentrations of pirimicarb, -endosulfan and chlorfenvinphos.

We suggest that the method presented here be used for the extraction and quantitation of particle-associated polar pesticides.     

Spatial & temporal variations of PM10 and particle number concentrations in urban air

The size of particles in urban air varies over four orders of magnitude (from 0.001 μm to 10 μm in diameter). In many cities only particle mass concentrations (PM10, i.e. particles <10 μm diameter) is measured. In this paper we analyze how differences in emissions, background concentrations and meteorology affect the temporal and spatial distribution of PM10 and total particle number concentrations (PNC) based on measurements and dispersion modeling in Stockholm, Sweden. PNC at densely trafficked kerbside locations are dominated by ultrafine particles (<0.1 μm diameter) due to vehicle exhaust emissions as verified by high correlation with NOx. But PNC contribute only marginally to PM10, due to the small size of exhaust particles. Instead wear of the road surface is an important factor for the highest PM10 concentrations observed. In Stockholm, road wear increases drastically due to the use of studded tires and traction sand on streets during winter; up to 90% of the locally emitted PM10 may be due to road abrasion. PM10 emissions and concentrations, but not PNC, at kerbside are controlled by road moisture. Annual mean urban background PM10 levels are relatively uniformly distributed over the city, due to the importance of long range transport. For PNC local sources often dominate the concentrations resulting in large temporal and spatial gradients in the concentrations. Despite these differences in the origin of PM10 and PNC, the spatial gradients of annual mean concentrations due to local sources are of equal magnitude due to the common source, namely traffic. Thus, people in different areas experiencing a factor of 2 different annual PM10 exposure due to local sources will also experience a factor of 2 different exposure in terms of PNC. This implies that health impact studies based solely on spatial differences in annual exposure to PM10 may not separate differences in health effects due to ultrafine and coarse particles. On the other hand, health effect assessments based on time series exposure analysis of PM10 and PNC, should be able to observe differences in health effects of ultrafine particles versus coarse particles.     

Sorption of polycyclic aromatic hydrocarbons (PAHs) to carbonaceous materials in a river floodplain soil

We report on sorption isotherm of phenanthrene (Phe) for river floodplain soil associated with carbonaceous materials, with particular attention being devoted to the natural loading of Phe. Our sorption experiments with original soil samples, size, and density sub-fractions showed that the light fraction had the highest sorption capacity comparable to low rank coals. In addition, the light fraction contributed most for the sorption of Phe in total soil samples. K_oc values for all fractions were in the same range, thus indicating that coal and coal-derived particles in all samples are responsible for the enhanced sorption for Phe. Sorption was strongly nonlinear and the combined partitioning and pore-filling model gave a better fit than the Freundlich sorption model. In addition, the spiked PAHs did not show the same behavior as the naturally aged ones, therefore the accessibility of indigenous background organic contaminants was reduced when coal and coal-derived particles are associated with the soils.     

Improvement of an efficient separation method for chemicals in diesel exhaust particles: analysis for nitrophenols

GOAL, SCOPE, AND BACKGROUND: Diesel exhaust is believed to consist of thousands of organic constituents and is a major cause of urban pollution. We recently reported that a systematic separation procedure involving successive solvent extractions, followed by repeated column chromatography, resulted in the isolation of vasodilatory active nitrophenols. These findings indicated that the estimation of the amount of nitrophenols in the environment is important to evaluate their effect on human health. The isolation procedure, however, involved successive solvent extractions followed by tedious, repeated chromatography, resulting in poor fractionation and in a significant loss of accuracy and reliability. Therefore, it was crucial to develop an alternative, efficient, and reliable analytical method. Here, we describe a facile and efficient acid-base extraction procedure for the analysis of nitrophenols. MATERIALS AND METHODS: Diesel exhaust particles (DEP) were collected from the exhaust of a 4JB1-type engine (ISUZU Automobile Co., Tokyo, Japan). Gas chromatography-mass spectrometry (GC-MS) analysis was performed with a GCMS-QP2010 instrument (Shimadzu, Kyoto, Japan). RESULTS: A solution of DEP in 1-butanol was extracted with aqueous NaOH to afford a nitrophenol-rich oily extract. The resulting oil was methylated with trimethylsilyldiazomethane and subsequently subjected to GC-MS analysis, revealing that 4-nitrophenol, 3-methyl-4-nitrophenol, 2-methyl-4-nitrophenol, and 4-nitro-3-phenylphenol were present in significantly higher concentrations than those reported previously. DISCUSSION: Simple acid-base extraction followed by the direct analysis of the resulting extract by GC-MS gave only broad peaks of nitrophenols with a poor detection limit, while the GC-MS analysis of the sample pretreated with (trimethylsilyl)diazomethane gave satisfactorily clear chromatograms with sharp peaks and with a significantly lowered detection limit (0.5 ng/ml, approximately 100 times). CONCLUSION: The present method involving an acid-base extraction, in situ derivatization, and GC-MS analysis has shown to be a simple, efficient, and reliable method for the isolation and identification of the chemical substances in DEP.     

新版《环境空气质量标准》热点污染物PM2.5监控策略的思考与建议

随着工业化和城市化进程的加速,大气气溶胶污染日趋严重,由气溶胶细粒子PM2.5污染造成的能见度恶化事件越来越多,中国东部地区灰霾天气迅速增加.灰霾天气的本质是细粒子气溶胶污染,与光化学污染相关联,形成灰霾天气的气溶胶组成非常复杂.近年来由于灰霾天气日趋严重引发的环境效应问题,以及气溶胶辐射强迫引发的气候效应问题,已引起科学界、政府部门和社会公众的广泛关注,成为热门话题.在此背景下,国家出台了新版《环境空气质量标准》(GB 3095-2012),增设PM2.5浓度限值,对环境监测、环境管理和环境评价提出了新的要求.通过分析中国大气污染背景、国际组织和其他国家的PM2.5标准,及近期热点问题,提出在环境监测、环境管理和环境评价过程中实施新标准,监控PM2.5的策略.