机动车尾气碳质气溶胶排放因子及其稳定碳同位素特征

机动车尾气是大气碳质气溶胶的重要人为来源,其排放因子与稳定碳同位素组成是重要的基础数据.选取多辆不同类型在用机动车,进行多种工况、冷/热条件下启动的台架试验,收集各测试阶段尾气分析其碳质组分含量与稳定碳同位素比值,并探讨其影响因素.结果表明,总碳排放因子大小为：重型柴油车>轻型柴油车>轻型汽油车,轻型天然气车虽然在低速与中速阶段排放因子极低,但高速行驶阶段可达到重型柴油车的排放水平.各型车冷启动的排放因子均高于热启动,NEDC工况的排放因子整体低于WLTC工况,应与其测试车速有关.汽油车和天然气车各测试阶段排放有机碳(OC)均远高于元素碳(EC),柴油车OC与EC排放因子相近,各类车辆OC/EC都随测试车速的提高而上升.稳定碳同位素EC重于OC,同位素比值大小关系均呈现：汽油车<天然气车<轻型柴油车<重型柴油车,现有源解析的稳定碳同位素源谱较难反映汽油车与天然气车特征.在排放治理与源解析工作中,应注意替代燃料的使用与机动车老化过程所造成的排放因子与同位素特征值的变化影响.     

宁波市PM2.5中碳组分的时空分布特征和二次有机碳估算

为了研究PM2.5中碳质组分的时空分布特征,于2012年12月至2013年10月4个季度典型时段在宁波市5个采样点采集环境大气中的PM2.5,分析了样品中有机碳(OC)和元素碳(EC)的质量浓度,并估算二次有机碳(SOC)对OC的贡献.结果表明:1宁波市PM2.5年均质量浓度为51.6μg·m-3,其中OC和EC的比例分别为17%和6%.反向轨迹模型的分析结果表明,来自内陆地区的区域传输可能是冬季和春季PM2.5浓度较高的主要原因.2OC/EC比值和OC与EC的相关性分析结果表明,夏季有大量SOC生成,而冬季则可能受华北地区燃煤供暖的显著影响.3用EC示踪法对宁波市的SOC进行了估算,结果表明宁波冬季和春季受到区域传输的显著影响,污染源较不稳定,不宜使用该估算方法.夏季和秋季的SOC质量浓度分别为2.5μg·m-3和2.3μg·m-3,占OC的42%和28%.     

太原市PM2.5中有机碳和元素碳的污染特征

采集了太原市4个点位冬季和夏季PM2.5样品,利用元素分析仪测定了PM2.5中有机碳(OC)和元素碳(EC)的质量浓度,并对碳气溶胶污染水平、时空分布、二次有机碳(SOC)以及OC和EC相关性等特征进行了分析.结果表明,太原市冬季有机碳(OC)、元素碳(EC)平均质量浓度为22.3μg·m-3和18.3μg·m-3,夏季OC、EC平均质量浓度为13.1μg·m-3和9.8μg·m-3,冬季和夏季总碳气溶胶(TCA)占PM2.5的比例分别为56.6%和36.5%;各点位OC和EC质量浓度均呈现冬季夏季的季节特征,冬季OC、EC浓度呈现出较好的均一性,夏季OC、EC质量浓度存在较明显的空间分布差异;太原市SOC污染较轻;冬季OC、EC相关性较强,夏季OC、EC相关性差.     

北京秋冬季有机碳和元素碳(黑碳)测试结果的细节研究

长期以来,对碳气溶胶的定量研究主要关注OC（有机碳）、EC（元素碳）或BC（黑碳）的整体测定结果,很少有对测定结果细节特征的深入解读.为全面掌握和利用仪器分析结果包含的科学信息,使用热光法IMPROVE_A协议（model 2001A）测定了2015年10月（秋季）和2016年1月（冬季）北京市PM_2.5中的ρ（OC）和ρ（EC）,使用光学法（黑碳仪AE31）测定了相应的ρ（BC）.结果表明:① ρ（OC）和ρ（EC）的秋季平均值分别为8.59、3.89 μg/m3,冬季分别为16.45和6.19 μg/m3,冬季明显高于秋季;② 热光法测定结果显示,秋季样品中ρ（OC₁）/ρ（OC）的平均值为0.08±0.04,而冬季则升至0.22±0.05,这可能与冬季较高的挥发性有机物（VOCs）排放及低温带来的冷凝效应有关;③ 七波长黑碳仪测定结果显示,在秋季,紫外波段（370 nm）测定的BC当量[ρ（BC370）]与红外波段（880 nm）测定的BC标准量[ρ（BC880）]的比值[ρ（BC370）/ρ（BC880）]为1.05±0.11,说明棕色碳（BrC）的吸光影响非常弱,而冬季该比值升至1.47±0.11,升幅达40%;④ 结合两种方法对强吸光碳的测定结果,发现ρ（BC）/ρ（EC）与ρ（PM_2.5）的变化趋势一致,证明污染程度加重会带来EC内混合比例上升,因而提高其吸光能力,使黑碳仪测得的ρ（BC）上升.然而,进一步考察表明,这种上升是有限度的,当ρ（PM_2.5）达到50~70 μg/m3时,ρ（BC）/ρ（EC）进入"平台状态",秋季"平台值"约为1.05,冬季约为0.55.研究显示,仪器的测定结果包含大量被忽略的信息,对其细节的深入解读有利于更好地了解碳气溶胶的综合特征.      

PM2.5 chemical composition and health risks by inhalation near a chemical complex

Particulate matter (PM_2.5) samples were collected in the vicinity of an industrial chemical pole and analysed for organic and elemental carbon (OC and EC), 47 trace elements and around 150 organic constituents. On average, OC and EC accounted for 25.2% and 11.4% of the PM_2.5 mass, respectively. Organic compounds comprised polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs, anhydrosugars, phenolics, aromatic ketones, glycerol derivatives, aliphatic alcohols, sterols, and carboxyl groups, including aromatic, carboxylic and dicarboxylic acids. Enrichment factors > 100 were obtained for Pb, Cd, Zn, Cu, Sn, B, Se, Bi, Sb and Mo, showing the contribution of industrial emissions and nearby major roads. Principal component analysis revealed that vehicle, industrial and biomass burning emissions accounted for 66%, 11% and 9%, respectively, of the total PM_2.5-bound PAHs. Some of the detected organic constituents are likely associated with plasticiser ingredients and thermal stabilisers used in the manufacture of PVC and other plastics in the industrial complex. Photooxidation products of both anthropogenic (e.g., toluene) and biogenic (e.g., isoprene and pinenes) precursors were also observed. It was estimated that biomass burning accounted for 13.8% of the PM_2.5 concentrations and that secondary OC represented 37.6% of the total OC. The lifetime cancer risk from inhalation exposure to PM_2.5-bound PAHs was found to be negligible, but it exceeded the threshold of 10⁻⁶ for metal(loi)s, mainly due to Cr and As.     

模拟酸雨对不同土层酸度和K+淋失规律的影响

在江西表土施用KCl肥料后,用室内模拟酸雨的土柱实验,研究酸雨对不同土层酸度及K⁺淋失的影响.其结果表明,不同土层淋出液pH值的变化先下降后上升,但起始pH值存在明显差异,pH2.5酸雨在A层和AB层淋溶的中后期又下降;淋出液电导变化有一个峰值,其出现在淋溶的起始阶段,表明土壤中养分迅速向下迁移.K+的淋失与降雨的酸度有关,pH2.5酸雨会加速K⁺在土体内向下迁移,在A层土壤中K⁺的释放可分为2个阶段:快速释放过程和中速释放过程;至于pH4.5酸雨淋溶下,K⁺淋失分为快速释放过程和慢速释放过程.     

应用元素碳示踪物法解析复杂排放源地区有机碳来源的局限性

元素碳示踪物法(The EC tracer method)因其简单易行被广泛应用于区分有机气溶胶的一次和二次来源.本文以源排放复杂的北京城区(冬夏两季)和山东长岛作为城市和偏远地区的代表,利用气溶胶质谱仪(AMS)和碳黑测定仪等多种仪器的观测结果,基于元素碳示踪物法估算了在这些地区二次源对有机碳的贡献,并将该结果和同观测受体模型正定矩阵因子分析(PMF)的结果进行比较.探讨了北京地区餐饮源和生物质燃烧源对元素碳示踪物法估算二次有机碳的影响.本研究指明了元素碳示踪物法基本假设在源复杂地区应用的局限性,利用该方法对二次有机气溶胶估算会因存在具有较高OC/EC比值的一次排放源,而有一定偏差(例如本论文10%~40%).该研究对其他的元素示踪物法的估算工作具有一定的借鉴意义.     

厦门市冬季大气PM2.5中有机碳和元素碳的污染特征

为探讨厦门市冬季大气PM_(2.5)含碳组成特征,于2014-12-10至2015-01-09同步采集了城区和郊区的PM_(2.5)样品。采用热光透射法分析了PM_(2.5)中OC、EC的质量浓度。结果表明,近年来厦门市PM_(2.5)、OC、EC的浓度表现出逐年降低的趋势。城区和郊区的OC平均浓度分别为9.77±1.87和9.17±2.42μg/m~3,EC平均浓度分别为1.87±0.73和2.43±1.10μg/m~3,与国内外其他城市相比,厦门市冬季大气PM_(2.5)中的OC、EC浓度均处于较低水平,人为引起的大气含碳成分污染相对较轻。城区和郊区的OC/EC值均大于2,SOC占OC比例分别高达34.96%、39.03%,厦门大气PM_(2.5)中的OC受到二次污染较严重。PM_(2.5)、OC、EC的分布规律表明,OC、EC受到了除天气条件以外的其他因素如OC和EC污染源种类、源强以及二次转化程度的影响。城区(R2=0.107 9)和郊区(R2=0.341 9)的OC与EC相关性不明显,初步判断厦门市冬季PM_(2.5)中OC和EC的来源较复杂,EC可能主要来自化石燃料和生物质不完全燃烧等一次排放源,OC则主要受到化石燃料燃烧和二次污染的影响,城区污染源还包括烹饪源以及生物质燃烧。     

Multivariate Statistics of the Pyrolysis Products of High Molecular Components in Pulping Wastewaters to Explain Their Toxicity (6 pp)

Background, Aim and Scope At present, large-scale paper manufacture involves delignification and bleaching by elemental chlorine free (ECF) or totally chlorine free (TCF) processes. The wastewater is purified by secondary treatment (mechanical, chemical and biological) which removes most of the toxic substances from the discharge. However, we found residual toxicity in the high molecular (> 1000 D) matter (HMWM) of the discharge by test of the RET (reverse electronic transfer) inhibition. This fraction consists mainly of polydisperse lignin (LIG) and carbohydrate (CH) macromolecules. Structural units in these molecules are studied by pyrolysis gas chromatography / mass spectrometry (Pyr-GC/MS). In the present work, our aim was to find out those structural units which could explain the RET toxicity of LIG or CH molecules. We compared statistically RET toxicity values of the HMWM samples from treated wastewaters of pilot pulping experiments and intensity variation of the pyrolysis product gas chromatograms of these samples. This application is a novel study procedure. Methods Pyrolysis products (Py-GC/MS results) and inhibition of RET (reverse electronic transport toxicity) as TU50 and TU20 of HMWM (High Molecular Weight Material; Mw > 1000 D) were compared by multivariate statistics. The samples were from laboratory pilot stages of TCF (Totally Chlorine Free) and ECF (Elemental Chlorine Free) manufacture of softwood pulp. Py-GC/MS was done without and with addition of TMAH (Tetra Methyl Ammonium Hydroxide). The name and structure of each abundant fragment compound was identified from its retention time and mass spectrum compared to authentic reference compounds or literature. Four sets of Toxicity Units (TUs) and GC peak areas of the pyrolysis fragments were obtained. The data were normalized by division with LIG (lignin content of each sample). TU values were dependent and the fragment values independent (explanatory) variables in statistical treatments by SPSS system. Separate analyses of correlations, principal components (PCA) and stepwise multiple linear regression (SMLR) were performed from the four sample sets TCF and ECF with and without TMAH. Results and Discussion From the CH fragments, 2-furfural in TCF, and from the LIG fragments, styrene in ECF showed the highest probabilities to originate from source structures of toxicity. Other possible compounds in concern were indicated to be CH fragment 2-methyl-2-cyclopenten-1-one in ECF and LIG fragments 2-methoxy-4-methylphenol, 4,5-dimethoxy-2-methylphenol and 2-methylphenol in TCF.     

欧盟关于环境空气中几项污染物质量标准制订方法

文章概述了欧盟正在制订的关于空气中砷、镉、汞、镍和多环芳烃质量标准的指令草案的法律及政策基础,制订依据与方法,几种污染物对人体健康的影响,污染物评价阈值和排放减少战略.通过分析欧盟环境空气质量标准的制订过程,为我国环境质量标准的制订提供参考与借鉴.