含碳气溶胶研究进展：有机碳和元素碳

含碳气溶胶是我国大气区域性复合型污染的重要物种,对全球气候变化、辐射强迫、能见度、环境质量、人类健康等会产生重要影响.主要从含碳气溶胶来源及成因、环境影响、样品采集及测试等方面对国内外相关研究进行了评述,讨论了有机碳和元素碳研究中存在的关键和难点问题,并对其发展前景进行了展望.     

不同装煤方式和炭化室高度的焦炉周边环境空气总悬浮颗粒物碳组分特征

研究了山西省4座典型焦炉周边环境空气中总悬浮颗粒物(TSP)碳组分特征,分析了不同装煤方式和炭化室高度对其的影响。结果表明:(1)焦炉周边环境空气中TSP质量浓度为711.95～2 938.41μg/m3,其中有机碳(OC)、元素碳(EC)的质量浓度分别为189.45～595.90、285.38～806.71μg/m3,总碳占TSP的质量分数为44.81%～67.45%;捣固焦炉周边的TSP及其碳组分浓度高于顶装焦炉,炭化室高度越高的焦炉周边环境空气中TSP及其碳组分浓度越低。(2)4座焦炉周边环境空气TSP中OC和EC质量比为0.66～1.04,说明焦炉周边环境空气中碳组分以一次污染为主。(3)4座焦炉周边环境空气TSP中碳组分的分歧系数为0.092～0.490,均小于0.5,总体来说装煤方式和炭化室高度都对焦炉周边环境空气TSP中碳组分的分布有一定影响,特别是装煤方式和炭化室高度都不同的焦炉周边环境空气TSP中碳组分差异较大。     

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。     

广州典型灰霾期有机碳和元素碳的污染特征

使用小流量Partisol model 2000采样器每2 h采集广州典型灰霾期(2006年1月7～20日)PMlo样品,并用美国Sunset Laboratory Inc.的碳分析仪分析了有机碳和元素碳.结果显示,灰霾期PM10、有机碳和元素碳污染严重,最高浓度日均值(1月13日)分别为最低浓度日均值(1月20日)的10.1、7.6、3.0倍;大气污染存在一个明显的逐日上升和下降过程,上升期间PM10、有机碳和元素碳的日均增长率分别为(127±24)%、(125±16)%和(116±17)%.下降期间日均增长率分别为(-143±25)%、(-135±13)%和(-118±11)%.计算表明,二次有机碳污染严重,并随着灰霾污染的持续,占总有机碳比例增加.气团轨迹分析说明,珠江三角洲其他地区的污染对广州地区灰霾污染过程存在影响.     

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     

大气气溶胶中有机成分研究进展

有机物是大气气溶胶的重要组成部分,尤其是在细颗粒中,可占其干重的10%～70%。由于有机气溶胶的健康及气候效应,有机物的组成、源分布、颗粒行为等的研究越来越受到人们的重视。其中,有机物成分的鉴别和定量已成为近年来的研究热点。在分析中,就目前有机气溶胶的采样、有机成分提取、分离及定性、定量分析方法进行了综述,并比较了各种方法的优缺点。     

天津冬季PM2.5与PM10中有机碳、元素碳的污染特征

研究了天津冬季PM2.5和PM10中碳成分的污染特征.结果表明,天津冬季PM2.5和PM10的平均质量浓度分别为(124.4±60.9)、(224.6±131.2)μg/m3;总碳(TC)、有机碳(OC)与元素碳(EC)在PM2.5中的平均质量分数比在PM10中分别高出5.0%、3.6%、1.2%;PM2.5中OC、EC的相关系数较高,为0.95,表明OC、EC的来源相对简单,可能主要反应了燃煤和机动车尾气的贡献.OC/EC的平均值在PM2.5和PM10中分别为3.9、4.9.次生有机碳(SOC)在PM2.55和PM10中的平均质量浓度分别为14.9、23.4/μg/m3,分别占OC的48.5%(质量分数,下同)、49.8%,OC/EC较高可能主要与直接排放源有关;PM2.5中的OC1与OC2的比例明显高于PM10,而聚合碳(OPC)的比例又低于PM10,同时PM2.5与PM10中的EC1含量均较高,表明天津冬季燃煤取暖和机动车尾气是重要的污染源.     

浙江省细颗粒物碳质气溶胶组分表征方法及污染特征研究

为深入探究大气细颗粒物(PM_2.5)碳质气溶胶组分(碳组分)表征方法，于2021年1-12月，在浙江省11个地市同期开展环境空气PM_2.5样品采集和分析工作，比较美国国家职业安全卫生研究所(NIOSH)协议和保护能见度多部门监测计划(IMPROVE)的代替协议(IMPROVE-A协议)测定样品的结果差异。结果表明：无氧阶段最高温度设置为870℃的NIOSH(NIOSH870)协议由于在氦气气氛下的解析温度高，测得PM_2.5样品中有机碳(OC)组分占比较IMPROVE-A协议大；对于IMPROVE-A协议而言，热光反射法校正的元素碳(EC)比热光透射法校正的结果大，在污染越严重、负载量越大的滤膜上，光学校正带来的差异越明显。通过开展浙江省部分地区的PM_2.5碳组分污染特征研究，发现PM_2.5中碳组分主要来自生物质燃烧、燃煤和机动车尾气排放。     

大气气溶胶中有机成分研究进展

有机物是大气气溶胶的重要组成部分，尤其是在细颗粒中，可占其干重的10％～70％。由于有机气溶胶的健康及气候效应，有机物的组成、源分布、颗粒行为等的研究越来越受到人们的重视。其中，有机物成分的鉴别和定量已成为近年来的研究热点。在分析中，就目前有机气溶胶的采样、有机成分提取、分离及定性、定量分析方法进行了综述，并比较了各种方法的优缺点。     

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。     

Characterization of carbonaceous species in PM2.5 in Xi'an during spring

The characterization of carbonaceous species in PM_2.5 during a spring period in a suburb of Xi'an, China was investigated. PM_2.5 samples were collected on quartz filters and analyzed for organic carbon (OC) and elemental carbon (EC). The thermal optical reflectance method was used. The minimum OC/EC ratio method was used to estimate the concentration of secondary organic carbon (SOC). The distribution of eight carbon fractions was investigated as well. The average mass concentrations of OC and EC were 15.90 and 8.38 μg/m³, respectively. The average OC/EC ratio ranged from 1.16 to 3.16 with an average value of 2.25. This implies the existence of SOC in PM_2.5. The mean SOC concentration was 7.20 μg/m³, accounting for 45.28% of total OC. This result suggests that SOC is a significant component of OC in the suburb of Xi'an. Results from the distribution of eight carbon fractions revealed that emissions from motor vehicle, coal combustion, and road dust were the main source of carbonaceous particles in the sampling period.     

An evaluation of measurement methods for organic, elemental and black carbon in ambient air monitoring sites

The carbonaceous components of Particulate Matter samples form a substantial fraction of their total mass, but their quantification depends strongly on the instruments and methods used. United Kingdom monitoring networks have provided many relevant data sets that are already in the public domain. Specifically, hourly organic carbon (OC) and elemental carbon (EC) were determined at four sites between 2003 and 2007 using Rupprecht and Pattashnik (R & P) 5400 automatic instruments. Since 2007, daily OC/EC measurements have been made by manual thermo-optical analysis of filter samples using a Sunset Laboratory Carbon Aerosol Analysis instrument. In parallel, long term daily measurements of Black Smoke, a quantity directly linked to black carbon (measured by aethalometers) and indirectly related to elemental carbon, have been made at many sites. The measurement issues associated with these techniques are evaluated in the context of UK measurements, making use of several sets of parallel data, with the aim of aiding the interpretation of network results. From the results available, the main conclusions are that the R & P 5400 instruments greatly under-read EC and total carbon (TC = OC + EC) at kerbside sites, probably due to the fact that the smaller particles are not sampled by the instrument; the R & P 5400 instrument is inherently difficult to characterise, so that all quantitative results need to be treated with caution; both aethalometer and Black Smoke (converted to black carbon) measurements can show reasonable agreement with elemental carbon results; and manual thermo-optical OC/EC results may under-read EC (and hence over-read OC), whether either transmittance or reflectance is used for the pyrolysis correction, and this effect is significant at rural sites.     

Carbonaceous aerosol characteristics in outdoor and indoor environments of Nanchang, China, during summer 2009

A study of carbonaceous aerosol was initiated in Nanchang, a city in eastern China, for the first time. Daily and diurnal (daytime and nighttime) PM2.5 (particulate matter with aerodynamic diameter < or =2.5 microm) samples were collected at an outdoor site and in three different indoor environments (common office, special printing and copying office, and student dormitory) in a campus of Nanchang University during summer 2009 (5-20 June). Daily PM10 (particulate matter with aerodynamic diameter < or =10 microm) samples were collected only at the outdoor site, whereas PM2.5 samples were collected at both indoor and outdoor sites. Loaded PM2.5 and PM10 samples were analyzed for organic and elemental carbon (OC, EC) by thermal/optical reflectance following the Interagency Monitoring of Protected Visual Environments-Advanced (IMPROVE-A) protocol. Ambient mass concentrations of PM10 and PM2.5 in Nanchang were compared with the air quality standards in China and the United States, and revealed high air pollution levels in Nanchang. PM2.5 accounted for about 70% of PM10, but the ratio of OC and EC in PM2.5 to that in PM10 was higher than 80%, which indicated that OC and EC were mainly distributed in the fine particles. The variations of carbonaceous aerosol between daytime and nighttime indicated that OC was released and formed more rapidly in daytime than in nighttime. OC/EC ratios were used to quantify secondary organic carbon (SOC). The differences in SOC and SOC/OC between daytime and nighttime were useful in interpreting the secondary formation mechanism. The results of (1) OC and EC contributions to PM2.5 at indoor sites and the outdoor site; (2) indoor-outdoor correlation of OC and EC; (3) OC-EC correlation; and (4) relative contributions of indoor and outdoor sources to indoor carbonaceous aerosol indicated that OC indoor sources existed in indoor sites, with the highest OC emissions in I2 (the special printing and copying office), and that indoor EC originated from outdoor sources. The distributions of eight carbon fractions in emissions from the printer and copier showed obviously high OC1 (>20%) and OC2 (approximately 30%), and obviously low EC1-OP (a pyrolyzed carbon fraction) (<10%), when compared with other sources.     

Characterization of Carbonaceous Species of Ambient PM2.5 in Beijing,China

Abstract

One-week integrated fine particulate matter (i.e., particles <2.5 μm in diameter; PM_2.5) samples were collected continuously with a low-flow rate sampler at a downtown site (Chegongzhuang) and a residential site (Tsinghua University) in Beijing between July 1999 and June 2000. The annual average concentrations of organic carbon (OC) and elemental carbon (EC) at the urban site were 23.9 and 8.8 μg m^?3, much higher than those in some cities with serious air pollution. Similar weekly variations of OC and EC concentrations were found for the two sampling sites with higher concentrations in the winter and autumn. The highest weekly variations of OC and EC occurred in the winter, suggesting that combustion sources for space heating were important contributors to carbonaceous particles, along with a significant impact from variable meteorological conditions. High emissions coupled with unfavorable meteorological conditions led to the max weekly carbonaceous concentration the week of November 18–25, 1999. The weekly mass ratios of OC:EC ranged between 2 and 4 for most samples and averaged 2.9, probably suggesting that secondary OC (SOC) is present most weeks. The range of contemporary carbon fraction, based on the C14 analyses of eight samples collected in 2001, is 0.330–0.479. Estimated SOC accounted for ～38% of the total OC at the two sites. Average OC and EC concentrations at Tsinghua University were 25% and 18%, respectively, higher than those at Chegongzhuang, which could be attributed to different local emissions of primary carbonaceous particles and gaseous precursors of SOC, as well as different summer photochemical intensities between the two locations.     

Characteristics and sources of PM2.5 and carbonaceous species during winter in Taiyuan,China

Continuous observation of PM_2.5 was conducted in Taiyuan, a heavily polluted city in China, during high pollution season from December 2005 to February 2006. The results of this study showed that PM_2.5 and carbonaceous species pollution were serious during winter in Taiyuan. The organic carbon (OC) and element carbon (EC) were accounted for 18.6±11.2% and 2.9±1.6% of PM_2.5, respectively, which indicated that carbonaceous aerosols were key components for control fine particles pollution in Taiyuan. Coal combustion was a dominant source of OC and EC of PM_2.5 in the urban area of Taiyuan during winter. The impact of local and remote particle sources on urban air quality was assessed using PM_2.5 concentration rose and 3-day back trajectories of air masses arriving at Taiyuan. The meteorological conditions were found to affect the ambient concentrations of PM_2.5, OC, EC and OC/EC ratio.     

Concentrations of carbonaceous species in particles at Seoul and Cheju in Korea

Concentrations of elemental carbon (EC) and organic carbon (OC) in particles at Seoul and Cheju Island, Korea were observed in 1994. PM₁₀ and PM_2.5 were collected by a modified SCAQS (Southern California Air Quality Study) sampler from Seoul during June 1994 and PM_2.5 were collected by a low-volume sampler at Cheju Island during July and August 1994. The selective thermal oxidation method with MnO₂ catalyst was used for analysis. The EC concentrations from Seoul were higher than those at Los Angeles, USA during the SCAQS study while the OC concentrations were comparable to those during the SCAQS study. At Cheju Island, the OC concentrations were higher than those at other clean areas in the world but the EC concentrations were lower than or comparable to those at other clean areas in the world. The OC to EC ratios of Seoul suggest that the carbonaceous species are mostly from primary emission sources. In Cheju, during July 1994 air pollutant levels were high and it was suggested that atmospheric transformation/transport of organics and biogenic emissions were main sources of carbonaceous species in particles. The carbonaceous species levels were low during August 1994 and it was suggested that the levels could be considered as marine background concentrations in the region during summer.     

Characterization of carbonaceous species of ambient PM2.5 in Beijing, China

One-week integrated fine particulate matter (i.e., particles <2.5 microm in diameter; PM2.5) samples were collected continuously with a low-flow rate sampler at a downtown site (Chegongzhuang) and a residential site (Tsinghua University) in Beijing between July 1999 and June 2000. The annual average concentrations of organic carbon (OC) and elemental carbon (EC) at the urban site were 23.9 and 8.8 microg m(-3), much higher than those in some cities with serious air pollution. Similar weekly variations of OC and EC concentrations were found for the two sampling sites with higher concentrations in the winter and autumn. The highest weekly variations of OC and EC occurred in the winter, suggesting that combustion sources for space heating were important contributors to carbonaceous particles, along with a significant impact from variable meteorological conditions. High emissions coupled with unfavorable meteorological conditions led to the max weekly carbonaceous concentration the week of November 18-25, 1999. The weekly mass ratios of OC:EC ranged between 2 and 4 for most samples and averaged 2.9, probably suggesting that secondary OC (SOC) is present most weeks. The range of contemporary carbon fraction, based on the C14 analyses of eight samples collected in 2001, is 0.330-0.479. Estimated SOC accounted for approximately 38% of the total OC at the two sites. Average OC and EC concentrations at Tsinghua University were 25% and 18%, respectively, higher than those at Chegongzhuang, which could be attributed to different local emissions of primary carbonaceous particles and gaseous precursors of SOC, as well as different summer photochemical intensities between the two locations.     

Characterization of carbonaceous aerosols over Delhi in Ganga basin: seasonal variability and possible sources

The mass concentration of carbonaceous species, organic carbon (OC), and elemental carbon (EC) using a semicontinuous thermo-optical EC-OC analyzer, and black carbon (BC) using an Aethalometer were measured simultaneously at an urban mega city Delhi in Ganga basin from January 2011 to May 2012. The concentrations of OC, EC, and BC exhibit seasonal variability, and their concentrations were ～2 times higher during winter (OC 38.1?±?17.9 μg m^?3, EC 15.8?±?7.3 μg m^?3, and BC 10.1?±?5.3 μg m^?3) compared to those in summer (OC 14.1?±?4.3 μg m^?3, EC 7.5?±?1.5 μg m^?3, and BC 4.9?±?1.5 μg m^?3). A significant correlation between OC and EC (R?=?0.95, n?=?232) indicate their common emission sources with relatively lower OC/EC ratio (range 1.0–3.6, mean 2.2?±?0.5) suggests fossil fuel emission as a major source of carbonaceous aerosols over the station. On average, mass concentration of EC was found to be ～38 % higher than BC during the study period. The measured absorption coefficient (b_abs) was significantly correlated with EC, suggesting EC as a major absorbing species in ambient aerosols at Delhi. Furthermore, the estimated mass absorption efficiency (σ_abs) values are similar during winter (5.0?±?1.5 m² g^?1) and summer (4.8?±?2.8 m² g^?1). Significantly high aerosol loading of carbonaceous species emphasize an urgent need to focus on air quality management and proper impact assessment on health perspective in these regions.     

PM2.5 carbon measurements in two urban areas: Seoul and Kwangju,Korea

24-h PM_2.5 carbonaceous samples were collected between 27 November and 9 December 1999 in Seoul, and between 7 and 20 June 2000 in Kwangju to investigate characteristics of carbonaceous species, and the relationship between elemental carbon (EC) and Aethalometer-based black carbon (BC) measurements. 5-min PM_2.5 BC and criteria air pollutant data were also measured using the Aethalometer and ambient air monitoring system. The PM_2.5 samples were analyzed for EC and OC using a selective thermal manganese dioxide oxidation (TMO) method. The daily average EC and OC concentrations in Seoul were higher in the winter than in the summer (Atmos. Environ. 35 (2001a) 657). It was found that difference between ambient BC levels in the two cities was not directly proportional to the population ratio (∼8) or diesel traffic ratio (∼5.9) since particulate matter or BC concentration is strongly influenced by a result of varying traffic and meteorological conditions at the site. Using the primary OC/EC ratio approach, the results suggest that most of the measured OC in Kwangju is of primary origin during the summer. In Seoul, the observed OC includes additional secondary organic aerosol during the wintertime conditions. The relationship between the 24-h TMO-EC and Aethalometer BC measurements in PM_2.5 reflected very good agreement for the two urban sites, with correlation coefficients of R²=0.99 and 0.92, and BC/EC slopes of 0.93 and 1.07, respectively. It was found that comparing TMO-EC to BC at a different location in Korea, a different scaling factor was needed.     

Spatial variability of carbonaceous aerosols and associated source tracers in two cites in the Midwestern United States

Semi-continuous and 24-h averaged measurements of fine carbonaceous aerosols were made concurrently at three sites within each of two U.S. Midwestern Cities; Detroit, Michigan and Cleveland, Ohio; during two, one-month intensive campaigns conducted in July of 2007 and January & February of 2008. A comparison of 24-h measurements revealed substantial intra-urban variability in carbonaceous aerosols consistent with the influence of local sources, and excesses in both PM_2.5 organic carbon (OC) and elemental carbon (EC) were identified at individual sites within each city. High time-resolved black carbon (BC) measurements indicated that elemental carbon concentrations were higher at sites adjacent to freeways and busy surface streets, and temporal patterns suggested that excess EC at sites adjacent to freeways was dominated by mobile source emissions while excesses in EC away from traffic corridors was dominated by point/area source emissions. The site-to-site variability in OC concentrations was approximately 7% within the neighborhood scale (0.5–4 km) and between 4 and 27% at the urban scale (4–100 km). In contrast, measurements of organic source tracers, in conjunction with a Chemical Mass Balance (CMB) source-apportionment model, indicated that the spatial variation in the contribution of both mobile and stationary sources to PM_2.5 OC often exceeded the variation in OC mass concentration by a factor of 3 or more. Markers for mobile sources, biomass smoke, natural gas, and coal combustion differed by as much as 60% within the neighborhood scale and by greater than 200% within the urban scale. The observations made during this study suggest that the urban excess of carbonaceous aerosols is much more complex than has been previously reported and that a more rigorous, source-oriented approach should be taken in order to assess the risk associated with exposure to carbonaceous aerosols within the industrialized environments of the Midwestern United States.