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.     

空气中总悬浮颗粒物的X射线衍射定性分析研究

以天津市环境监测中心采集的空气中总悬浮颗粒物（ＴＳＰ）膜（９７１０１２号）为样品,使用日本理学Ｄ／ｍａｘＲＡＸ射线衍射仪对其进行化合物定性分析,并介绍样品的采集与制样方法、仪器测试条件。最后通过ＪＣＰＤＳＩＣＤＤ（国际粉末衍射数据中心）标准数据库检索出该样品所含的全部化合物     

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.     

铝合金微电偶腐蚀机理与数值模拟研究进展

综述了铝合金微电偶腐蚀在机理研究和数值模拟两方面的研究进展,针对独立微电偶的腐蚀机理表征、多元微电偶空间随机分布相互作用规律、结构/载荷因素与铝合金微电偶腐蚀驱动力间的竞争机制等3个方面进行了展望,期望为铝合金微电偶腐蚀研究提供方向参考。     

CHARACTERIZATION OF INORGANIC PARTICLES IN SELECTED RESERVOIRS AND TRIBUTARIES OF THE NEW YORK CITY WATER SUPPLY1

ABSTRACT: Individual particle analysis (IPA) by scanning electron microscopy interfaced with automated image and X‐ray analyses was used to characterize inorganic particles in five reservoirs and four tributaries located within the Catskill and Delaware systems of the New York City water supply. Individual particle analysis provides combined elemental and morphologic characterizations. Results are presented in terms of particle projected area per unit volume (PAV), consistent with optical impacts, and partitioned into seven generic particle types according to composition. Minerals of terrigenous origins, particularly clay minerals, dominated the inorganic particle populations of all the study systems except one downstream reservoir. Higher PAV levels were observed in the Catskill system. Particle dynamics represented by PAV were driven primarily by runoff, while the reservoirs were also greatly influenced by the timing of sediment resuspension promoted by drawdown of the surface and fall mixing. The benefit of the serial configuration of the reservoirs in decreasing inorganic particles with progression downstream towards the city is demonstrated. The patterns in PAV levels among the study systems generally tracked those of more common metrics of impacts of suspensoids, including mass concentrations of suspended solids, turbidity, and Secchi disc transparency.     

上海市大气颗粒物中水溶性离子的粒径分布特征

分析了上海市嘉定区不同粒径的大气颗粒物中9种水溶性离子(SO42-、NO3-、NH4+、K+、Na+、Cl-、Ca2+、Mg2+、F-)的分布特征.结果显示,SO42-、NO3-和NH4+含量很高,占9种离子总和的65%～81%.颗粒物的C/A值平均为1.08,说明颗粒物呈中性,略偏碱,这可能与缺少碳酸根等的测定有关.1.5μm颗粒物中的离子占所有粒径段离子的52%～87%,表明离子主要集中在细颗粒物中.NH4+、K+呈单峰分布,峰值出现在0.95μm的颗粒段;SO42-、NO3-、Ca2+、Cl-呈双峰分布,峰值分别出现在0.95μm和3.0～7.2μm的粒径段,其中SO42-、NO3-的较高峰出现在0.95μm的细颗粒段,Ca2+的较高峰出现在3.0μm的颗粒段,Cl-则两峰高度相当;既有双峰分布又有单峰分布的离子是Na+、Mg2+和F-,3种离子的较高峰出现在3.0μm的颗粒段.离子粒径分布与采样期间的气象条件、离子的形成机制和来源有关.     

青岛大气气溶胶水溶性无机离子的粒径分布特征

为了解大气颗粒物中水溶性离子的来源及环境效应,利用安德森采样器连续采集青岛近海2008年1~12月大气颗粒物分级样品,用离子色谱法分析其中主要的水溶性离子,并讨论其粒径分布特征.结果表明, NH4+、K+、Cl-、NO3-、PO43-、SO42-主要存在于粒径小于2.1μm的细粒子中,Na+、Mg2+、Ca2+、F-则主要存在于粒径大于2.1μm的粗粒子中.各离子的粒径分布存在明显的季节变化.NH4+、K+和SO42-四季均主要分布于细粒子中,而Mg2+和Ca2+则主要分布在粗粒子中,两者均在3.3~4.7μm出现峰值;Na+在春、夏、秋3个季节主要存在于粗粒子中,集中分布在3.3~7.0μm粒径范围内,而在冬季则集中分布于0.43~1.1μm且细粒子含量高于粗粒子;春季Cl-在粗粒子中分布较多,尤以2.1~3.3μm范围内的最为突出,而其他3个季节均是细粒子比例明显偏高;NO3-春、夏两季在粗、细粒子中的含量各占50%,秋、冬季节均为细粒子占多数;PO43-夏季只出现在0.65~1.1μm以及>11μm的粒径范围内,粗粒子占95%,其他3个季节则是细粒子含量较高;春季F-在3.3~4.7μm出现峰值,夏季各粒径均未检出,而秋、冬两季粗、细粒子各占50%.K+、NH4+、F-、Cl-、NO3-、SO42-和PO43-受供暖期燃煤取暖的影响较大.K+和NH4+在供暖期和非供暖期峰值均出现在0.43~0.65μm粒径范围;F-供暖期在0.43~0.65μm和3.3~4.7μm粒径段出现峰值;供暖期Cl-的峰值出现在0.43~0.65μm粒径段,而在非供暖期,则出现在2.1~3.3μm的粗粒径段;SO42-和NO3-在供暖期和非供暖期的峰值均出现在0.43~0.65μm和3.3~4.7μm粒径段;供暖期PO43-的最大峰值出现在0.43~0.65μm粒径段,而在非供暖期其最大峰值出现在3.3~4.7μm粒径段.     

电动增压补气消除柴油机瞬态加速冒烟的试验

将自行开发的、适用车载24V电源的电动增压补气系统在一台490QDI柴油机上进行了实验研究.实验工况包括起始负荷分别为0和40N.m的加载加速的瞬态工况以及1400r·min-1、60N·m,1600 r·min-1、90N-m和1800 r.min-1、120N·m 3种低转速、大扭矩稳态工况,针对以上工况分别进行了有无电动增压补气的实验.试验结果表明,有电动增压补气的柴油机同原机相比,零负荷加载加速时的微粒排放降低达70%以上,瞬间输出功率最大可提高54.5%;在稳态工况时,HC、CO排放都随着电机转速的升高而降低,最大减少量分别达到66.7%和75.O%;波许烟度平均减小50%以上.此外,加速补气对提高燃油经济性也有一定效果,比油耗最大能降低7.46%.