大气气溶胶含碳物质基本特征综述

准确界定了气溶胶含碳物质,特别是有机碳和元素碳的基本概念,指出了元素碳与黑碳的异同,总结了有机碳和元素碳的排放源,以及二次有机碳的经验公式.阐述了有机碳、元素碳对全球气候、大气化学过程及人体健康带来的危害及机理.归纳了气溶胶中有机碳、元素碳组分的空间分布特征、时间变化特征.概述了国内气溶胶有机碳、元素碳的研究状况,指出国内相关研究重点和趋势.     

大气气溶胶中无机碳和有机碳

一、序言 大气气溶胶中常含有大量的含碳化合物,其中主要是有机碳化物、无素碳(石墨化碳、炭黑等)及碳酸盐.元素碳主要是由于化石燃料不完全燃烧所产生,有机碳则包括污染源直接排放的一次有机磷化物(Cp)和碳氢化合物通过光化学反应等途径生成的二次有机碳化物(Cs),碳酸盐多存在于大粒子中,这些大粒子主要来源于     

含碳气溶胶采样偏差评估方法研究进展

含碳气溶胶采样偏差是影响含碳气溶胶及大气颗粒物精确测定的主要因素之一,进而影响大气颗粒物的源解析、环境效应分析、污染防治对策制定等。分析了含碳气溶胶采样偏差的产生原因,综述了目前研究所用的衡量采样偏差的方法,并分析了方法的优缺点,探讨了引起采样偏差的主要影响因素,最后对今后的相关研究方向进行了展望。     

朔州市市区环境空气PM_(10)中元素碳、有机碳分布特征

采集朔州市市区采暖季和非采暖季季PM10样品,测定其中元素碳(EC)和有机碳(OC)含量,并对碳组分的浓度水平、时空分布特征和主要来源进行了研究,结果表明:朔州市市区PM10中OC、EC平均浓度分别为(25.95±9.36)μg/m3和(26.58±10.36)μg/m3,总碳气溶胶(TAC)在PM10中的平均百分含量为30.1%;采暖季OC和EC浓度大于非采暖季,且OC、EC质量浓度大小在5个采样点位均呈现出点位5(工业开发区)点位2(居民区)点位1(商业、居民混合区)点位3(商业、文教混合区)点位4(相对清洁区)的变化规律,其中,点位5的OC、EC质量浓度最大,分别为(29.66±8.72)μg/m3和(31.40±10.42)μg/m3;PM10中OC/EC在采暖季和非采暖季比值均低于2,一次污染严重;OC和EC相关性较好,相关系数(R2)分别为0.85(采暖季)和0.69(非采暖季),说明PM10中的碳气溶胶主要来源于一次排放源,加强对燃煤烟尘、机动车尾气和生物质的燃烧等空气污染来源的控制对于改善朔州市环境空气质量有重要作用。     

水中有机碳的测定

人所共知,水中有机碳的测定,基于化学的和光化学的方法,将含碳有机杂质氧化成碳,或者利用适当的试剂和催化剂在600—1200℃温度下于反应器中热解,最后形成固定的二氧化碳。为了提高测定灵敏度,将得到的二氧化物于另一个反应器中,在催化     

大气气溶胶酸度的研究进展

大气气溶胶的环境效应、气候效应和健康效应均与气溶胶的物理化学性质直接相关,其中大气气溶胶酸度是其重要的性质之一。大气气溶胶酸度对酸沉降、灰霾的形成具有重要作用,并影响大气非均相化学反应,相关研究已成为国际研究的热点。对国内外学者近年来在大气气溶胶酸度对大气环境与人体健康的影响、大气气溶胶酸度的影响因素与变化规律、大气气溶胶酸度/酸化缓冲能力的测定与计算方法、大气气溶胶酸性成分采集系统等方面的研究进展作了较系统的综述,并对大气气溶胶酸度研究未来的发展进行了展望。     

碳同位素在溢油鉴定中的应用研究

通过分析中国代表性原油、氯仿沥青"A"组分碳同位素和正构烷烃单体碳同位素组成,探讨其在溢油鉴定中的应用.结果表明,原油的碳同位素组成具有母质继承效应,不同来源的原油及其氯仿沥青"A"组分的碳同位素类型曲线形状不同,可以利用这种规律进行溢油鉴定.碳同位素的抗风化性是其用于油指纹鉴别的最大优点.正构烷烃单体碳同位素分析使得有机质碳同位素研究进入分子级水平,因其特征性和稳定性正日益成为重要且有效的油类污染物的"环境示踪剂".     

西安市冬、夏两季PM2.5中碳气溶胶的污染特征分析

为研究西安市冬、夏两季大气颗粒物PM2.5中碳组分的污染变化规律,利用TEOM系列RP1400a采样仪于2010年冬季和夏季进行采样,测定了样品中的有机碳(OC)、无机碳(EC)和水溶性有机碳(WSOA)的含量。结果显示,PM2.5中OC和EC的季节平均浓度值冬季较高,分别是夏季的2.62,1.75倍,这表明西安市冬季碳气溶胶污染严重。OC和EC日变化在不同季节均呈现双峰分布特征,这主要是由交通源的排放和不利的气象条件造成的。OC和EC在冬、夏两季都有较强的相关性(R2分别为0.823和0.543),且OC/EC平均值分别为5.36和3.58,均大于2,表明采样各时段有二次有机碳(SOC)生成。     

万州城区空气污染过程中含碳气溶胶的变化特征

于2016年9月28日至10月15日在万州城区对气态污染物、颗粒物及其含碳气溶胶进行了在线连续观测,结合气象参数,分析了含碳气溶胶的污染特征。结果表明,此次持续污染过程主要由颗粒物污染造成,污染天PM_(10)和PM_(2.5)平均质量浓度分别为170.8、123.7μg/m~3,显著高于非污染天。污染天和非污染天PM_(2.5)、NO_x、有机碳(OC)及元素碳(EC)浓度的日变化都呈双峰,但污染天PM_(2.5)、NO_x和OC出现早峰值时间比非污染天推迟1～3h。污染天OC、EC的平均质量浓度分别为28.0、5.4μg/m~3,分别为非污染天的2.2、1.6倍。以非污染天的起始点作为参照点,得到污染天OC、EC的平均增长率分别为159.3%和73.0%,OC污染累积和二次转化贡献率分别为45.8%和54.2%,说明污染过程OC以二次转化为主。并用最小比值法估算了二次有机碳(SOC)含量,得到污染天和非污染天PM_(2.5)中SOC平均质量浓度分别为16.3、5.3μg/m~3,SOC在OC中的占比(以质量分数计)分别为56.1%和39.9%,污染天SOC占比增加,也证明污染过程OC以二次转化为主。污染天静风出现频率比非污染天高,在东南风的影响下,OC、EC易出现高浓度。     

生物碳吸附重金属模型及机制研究进展

为进一步加深对生物碳吸附重金属模型及机制的研究,在生物质热裂解模型、纤维素热裂解模型及生物碳吸附重金属模型进行系统总结、提炼和分析的基础上,构筑起一整套相对完善的生物碳吸附重金属模型及机制体系。该体系可与地理信息系统(GIS)结合,实现生物碳对重金属吸附过程的动态模拟,从而为生物碳与重金属关系的研究提供参考。     

Measurement of organic mass to organic carbon ratio in ambient aerosol samples using a gravimetric technique in combination with chemical analysis

Organic materials make up a significant fraction of ambient particulate mass. It is important to quantify their contributions to the total aerosol mass for the identification of aerosol sources and subsequently formulating effective control measures. The organic carbon (OC) mass can be determined by an aerosol carbon analyzer; however, there is no direct method for the determination of the mass of organic compounds, which also contain N, H, and O atoms in addition to C. The often-adopted approach is to estimate the organic mass (OM) from OC multiplying by a factor. However, this OC-to-OM multiplier was rarely measured for a lack of appropriate methods for OM. We report here a top-down approach to determine OM by coupling thermal gravimetric and chemical analyses. OM is taken to be the mass difference of a filter before and after heating at 550 °C in air for 4 h minus mass losses due to elemental carbon (EC), volatile inorganic compounds (e.g., NH₄NO₃), and loss of aerosol-associated water that arise from the heating treatment. The losses of EC and inorganic compounds are determined through chemical analysis of the filter before and after the heating treatment. We analyzed 37 ambient aerosol samples collected in Hong Kong during the winter of 2003, spring of 2004, and summer of 2005. A value of 2.1±0.3 was found to be the appropriate factor to convert OC to OM in these Hong Kong aerosol samples. If the dominant air mass is classified into two categories, then an OM-to-OC ratio of 2.2 was applicable to aerosols dominated by continent-originated air mass, and 1.9 was applicable to aerosols dominated by marine air mass.     

Investigation of a systematic offset in the measurement of organic carbon with a semicontinuous analyzer

Organic carbon (OC) was measured semicontinuously in laboratory experiments of steady-state secondary organic aerosol formed by hydrocarbon + nitrogen oxide irradiations. Examination of the mass of carbon measured on the filter for various sample volumes reveals a systematic offset that is not observed when performing an instrumental blank. These findings suggest that simple subtraction of instrumental blanks determined as the standard analysis without sample collection (i.e., by cycling the pump and valves yet filtering zero liters of air followed by routine chemical analysis) from measured concentrations may be inadequate. This may be especially true for samples collected through the filtration of small air volumes wherein the influence of the systematic offset is greatest. All of the experiments show that filtering a larger volume of air minimizes the influence of contributions from the systematic offset. Application of these results to measurements of ambient concentrations of carbonaceous aerosol suggests a need for collection of sufficient carbon mass to minimize the relative influence of the offset signal.     

The inportance of organic and elemental carbon in the fine atmospheric aerosol particles

During a field campaign the chemical character of fine (d<2.5 μm) aerosol particles was studied at K-puszta, Hungary within the framework of a project of the European Union. The organic and elemental carbon fraction, as well as the concentration of major inorganic constituents with respect to the total fine aerosol mass are presented in this paper. It was found that organic compounds constituted a significant fraction of the total fine aerosol mass, their contribution is comparable to or larger than that of the major water soluble ions. The diurnal variation of aerosol composition was also studied. It can be concluded that the relative abundance of the major constituents is practically the same during the day and at night. The samples were also classified and studied according to the air mass history. It is stated that the aerosol can be separated into two populations with different regression lines between organic and elemental carbon.     

Controlled exposures of volunteers to respirable carbon and sulfuric acid aerosols.

Respirable carbon or fly ash particles are suspected to increase the respiratory toxicity of coexisting acidic air pollutants, by concentrating acid on their surfaces and so delivering it efficiently to the lower respiratory tract. To investigate this issue, we exposed 15 healthy and 15 asthmatic volunteers in a controlled-environment chamber (21 degrees C, 50 percent relative humidity) to four test atmospheres: (i) clean air; (ii) 0.5-microns H2SO4 aerosol at approximately 100 micrograms/m3, generated from water solution; (iii) 0.5-microns carbon aerosol at approximately 250 micrograms/m3, generated from highly pure carbon black with specific surface area comparable to ambient pollution particles; and (iv) carbon as in (iii) plus approximately 100 micrograms/m3 of ultrafine H2SO4 aerosol generated from fuming sulfuric acid. Electron microscopy showed that nearly all acid in (iv) became attached to carbon particle surfaces, and that most particles remained in the sub-micron size range. Exposures were performed double-blind, 1 week apart. They lasted 1 hr each, with alternate 10-min periods of heavy exercise (ventilation approximately 50 L/min) and rest. Subjects gargled citrus juice before exposure to suppress airway ammonia. Lung function and symptoms were measured pre-exposure, after initial exercise, and at end-exposure. Bronchial reactivity to methacholine was measured after exposure. Statistical analyses tested for effects of H2SO4 or carbon, separate or interactive, on health measures. Group data showed no more than small equivocal effects of any exposure on any health measure.(ABSTRACT TRUNCATED AT 250 WORDS)     

Directions for combustion engine aerosol measurement in the 21st century

The Coordinating Research Council convened two Real-Time PM Measurement Workshops in December 2008 and March 2009 to take an intensive look at the current status and future directions of combustion aerosol measurement. The purpose was to examine the implications of parallel rapid developments over the past decade in ambient aerosol science, engine aftertreatment technology, and aerosol measurement methodology, which provide benefits and challenges to the stakeholders in air quality management. The workshops were organized into sessions targeting key issues in ambient and source combustion particulate matter (PM). These include (1) metrics to characterize and quantify PM, (2) the need to reconcile ambient and source measurements, (3) the role of atmospheric transformations on modeling emissions and exposures, (4) the impact of sampling conditions on PM measurement, and (5) the potential benefits of novel PM instrumentation. This paper distills the material presented by subject experts and the insights derived from the in-depth discussions that formed the core of each session. The paper's objectives are to identify areas of consensus that allow wider practical application of the past decade's advances in combustion aerosol measurement to improve emissions and air quality modeling, develop emissions reduction strategies, and to recommend directions for progress on issues in which uncertainties remain.     

Elemental and organic carbon in urban canyon and background environments in Budapest,Hungary

As part of an international research project, aerosol samples were collected by several filter-based devices on Nuclepore polycarbonate membrane, Teflon membrane and quartz fibre filters over separate daylight periods and nights, and on-line aerosol measurements were performed by TEOM and aethalometer within an urban canyon (kerbside) and at a near-city background site in Budapest, Hungary from 23 April–5 May 2002. Aerosol masses in PM2.0, PM10–2.0, PM2.5, PM10 size fractions and of TSP were determined gravimetrically; atmospheric concentrations of organic (OC) and elemental carbon (EC) for PM2.5 (or PM2.0), PM10 fractions and for TSP were measured by thermal–optical transmission method. Repeatability of the mass determination by Nuclepore filters seems to be 5–6%. Collections on Teflon filters yielded smaller mass on average by 8(±12)% than that for the Nuclepore filters. Quartz filters overestimated the PM10 mass in comparison with the Nuclepore filters due primarily to sampling artefacts on average by 10(±16)% at the kerbside. Tandem filter set-ups were utilised for correcting the sampling artefacts for OC by subtraction method. At the kerbside, the aerosol mass was made up on average of 35(±4)% of organic matter (OM) in the PM10 fraction, while the contribution of OM to the PM2.5 mass was 43(±9)%. At the background, OM also accounted for 43(±13)% of the PM2.0 mass. On average, EC made up 14(±6)%, 7(±2)% and 4.5(±1.1)% of the mass in the PM2.5, PM10 fractions and TSP, respectively, at the kerbside; while its contribution was only 2.1(±0.5)% in the PM2.0 fraction in the near-city background. Temporal variability for PM mass, OC and EC concentrations was related to road traffic, local meteorology and long-range transport of air masses. It was concluded that a direct coupling between the atmospheric concentration levels and vehicle circulation can be identified within the urban canyon, nevertheless, the local meteorology in particular and long-range transport of air masses have much more influence on the air quality than changes in the source intensity of road traffic. Concentration ratios of OC/EC were evaluated, and the amount of secondary organic aerosol (SOA) was estimated by using EC as tracer for the primary OC emissions. Mean contribution and standard deviation of the SOA to the OM in the PM2.5 size fraction at the kerbside over daylight periods and nights were of 37(±18) and 46(±16)%, respectively.     

Characterization of carbon nanoparticles in ambient aerosols by scanning electron microscopy and model calculations

Size-selected aerosol samples were analyzed by scanning electron microscopy (SEM) to explore (1) the relative concentration of individual and aggregated carbon nanoparticles (C-NPs) and (2) the combustion behavior of C-NP agglomerates. SEM analysis of low-coverage aerosol deposits showed that most of the C-NP matter is present in the form of chain-type agglomerates. The individual C-NPs in the agglomerates are remarkably similar in diameter (40+/-5 nm) and appear to be very tightly bound to the neighboring NPs. Comparison with literature data suggests that the agglomerates originated from diesel exhaust. After gently removing the water-soluble compounds from relatively thick layers of aerosol matter, the residues were exposed to increasing temperatures, for 1 hr at each step, followed by SEM analysis of the same sample area. C-NP agglomerates were found to disappear rapidly at temperatures exceeding approximately 470 degrees C. This observation constitutes the first direct visualization of the combustion of what appears to be the most important fraction of elemental carbon in ambient aerosol matter. The experimental studies were complemented by simple model calculations that aimed at assessing the size-dependent mass fraction of individual C-NPs in ambient aerosol matter. The results suggest that the mass fraction decreases from 20+/-10% at particle diameters of approximately 30-40 nm to less than 0.1% above 300 nm.     

Aerosol black carbon and ozone measurements at Mt. Krvavec EMEP/GAW station,Slovenia

We report on one-year continuous measurements of aerosol black carbon at the EMEP/GAW regional air quality station on Mt. Krvavec in Slovenia, where ozone concentration has been monitored routinely since 1991. The results show several characteristic BC and O₃ concentration patterns with positive and negative correlation.     

Application of satellite remote-sensing data for source analysis of fine particulate matter transport events

Satellite sensors have provided new datasets for monitoring regional and urban air quality. Satellite sensors provide comprehensive geospatial information on air quality with both qualitative imagery and quantitative data, such as aerosol optical depth. Yet there has been limited application of these new datasets in the study of air pollutant sources relevant to public policy. One promising approach to more directly link satellite sensor data to air quality policy is to integrate satellite sensor data with air quality parameters and models. This paper presents a visualization technique to integrate satellite sensor data, ground-based data, and back trajectory analysis relevant to a new rule concerning the transport of particulate matter across state boundaries. Overlaying satellite aerosol optical depth data and back trajectories in the days leading up to a known fine particulate matter with an aerodynamic diameter of <2.5 microm (PM2.5) event may indicate whether transport or local sources appear to be most responsible for high PM2.5 levels in a certain location at a certain time. Events in five cities in the United States are presented as case studies. This type of analysis can be used to help understand the source locations of pollutants during specific events and to support regulatory compliance decisions in cases of long distance transport.     

Directions for Combustion Engine Aerosol Measurement in the 21st Century

Abstract

The Coordinating Research Council convened two Real-Time PM Measurement Workshops in December 2008 and March 2009 to take an intensive look at the current status and future directions of combustion aerosol measurement. The purpose was to examine the implications of parallel rapid developments over the past decade in ambient aerosol science, engine aftertreatment technology, and aerosol measurement methodology, which provide bene?ts and challenges to the stakeholders in air quality management. The workshops were organized into sessions targeting key issues in ambient and source combustion particulate matter (PM). These include (1) metrics to characterize and quantify PM, (2) the need to reconcile ambient and source measurements, (3) the role of atmospheric transformations on modeling emissions and exposures, (4) the impact of sampling conditions on PM measurement, and (5) the potential bene?ts of novel PM instrumentation. This paper distills the material presented by subject experts and the insights derived from the in-depth discussions that formed the core of each session. The paper’s objectives are to identify areas of consensus that allow wider practical application of the past decade’s advances in combustion aerosol measurement to improve emissions and air quality modeling, develop emissions reduction strategies, and to recommend directions for progress on issues in which uncertainties remain.