中国秸杆焚烧及民用燃煤棕色碳排放的初步研究

近年来的研究表明,在BC(黑碳)和OC(有机碳)之间,还存在着一种有弱吸光能力的OC,因大多显棕黄色而被称为BrC(brown carbon,棕色碳). 广泛存在的秸杆焚烧和冬季大量民用燃煤的使用,使国内BrC排放严重,但鲜见对其排放量的测算. 采用七波段黑碳仪(aethalometer)方法,对夏季小麦秸杆焚烧过程及冬季民用炉燃煤过程产生的烟气进行现场监测,根据BrC与BC的光谱关联性差别,分化出R_BrC/BC(总光学衰减中BrC和BC的相对贡献). 结果表明:麦秆焚烧和民用燃煤烟气的R_BrC/BC分别为1.754±0.278和0.183±0.142. 借助R_BrC/BC值,结合现有的BC排放清单(2000年),初步推算出中国民用燃煤和秸杆田间焚烧BrC的排放总量(以BC当量计,下同)为(270.6±101.6)Gg,接近同期BC排放量的一半;其中秸杆焚烧的BrC排放量为(175.4±27.8)Gg,约占二者总量的65%;民用燃煤的BrC排放量为(95.2±73.7)Gg,约占35%. 该研究结果可为更全面的BrC排放测算奠定基础,并为研究BrC的大气化学及辐射强迫提供依据.      

基于在线观测的大气PM_(2.5)中棕色碳吸光贡献估算

使用三波长光声黑碳光度计(PASS-3)和气溶胶质谱仪(AMS),于2011年秋季在浙江城市点金华和2014年夏季河北区域点望都进行了大气在线观测,采用改进的光吸收Angstrom指数(AAE)的方法统计外推黑碳AAE值,估算这2个典型地区PM_(2.5)中棕色碳的吸光贡献.结果表明:经统计外推获得的金华和望都的黑碳AAE在405nm下的基准值分别是1.12和0.77,532nm下的基准值分别是0.87和0.63;进而估算金华和望都PM_(2.5)中的棕色碳在405nm下的吸光贡献分别为9.8%和22.3%;532nm下的吸光贡献分别为5.9%和15.2%,表明我国大气中气溶胶棕色碳在短波段下的吸光贡献和辐射强迫影响不可忽视.     

Aerosol light absorption in a coastal city in Southeast China: Temporal variations and implications for brown carbon

Light-absorbing carbonaceous aerosols including black carbon(BC) and brown carbon(BrC)play significant roles in atmospheric radiative properties. One-year measurements of aerosol light absorption at multi-wavelength were continuously conducted in Xiamen,southeast of China in 2014 to determine the light absorption properties including absorption coefficients(σabs) and absorption ?ngstr?m exponent(AAE) in the coastal city.Light absorptions of BC and BrC with their contributions to total light absorption were further quantified. Mean σabsat 370 nm and 880 nm were 56.6 ± 34.3 and 16.5 ± 11.2 Mm-1,respectively. σabspresented a double-peaks diurnal pattern with the maximum in the morning and the minimum in the afternoon. σabswas low in warm seasons and high in cold seasons. AAE ranged from 0.26 to 2.58 with the annual mean of 1.46, implying that both fossil fuel combustion and biomass burning influenced aerosol optical properties. σabsof BrC at 370 nm was 24.0 ± 5.7 Mm-1, contributing 42% to the total absorption. The highest AAE(1.52 ± 0.02) and largest BrC contributions(47% ± 4%) in winter suggested the significant influence of biomass burning on aerosol light absorption. Long-distance air masses passing through North China Plain and the Yangtze River Delta led to high AAE and BrC contributions. High AAE value of 1.46 in July indicated that long-range transport of the air pollutants from intense biomass burning in Southeast Asia would affect aerosol light absorption in Southeast China. The study will improve the understanding of light absorption properties of aerosols and the optical impacts of BrC in China.     

广州地区大气棕色碳气溶胶光吸收特性

2014年冬季在广州番禺站利用校正后的7波段黑碳仪数据,计算棕色碳(BrC)在不同波长的光吸收特性,并结合气溶胶及气体成分在线监测仪(MARGA)和在线OCEC分析仪同步观测数据,分析了BrC的来源.结果表明:BrC在370、470、520、590和660 nm处对光吸收的贡献随波长增大而变小,不同波段的贡献分别为25. 9%、19. 7%、14. 1%、11. 6%和7. 7%; BrC光吸收系数、水溶性钾离子(K~+)和有机碳(OC)浓度大致呈现日间低,夜间高的趋势,说明生物质燃烧产物对BrC的光吸收系数贡献很大,傍晚附近农村地区逐渐活跃的秸秆燃烧活动和夜间稳定的边界层也有利于污染物累积; BrC光吸收系数与OC的比值在午后出现低值,说明二次有机气溶胶和老化的气溶胶的吸光能力较弱.相关性分析表明,BrC光吸收系数与K+离子和OC浓度的相关性最高,BrC光吸收系数与硝酸根(NO_3~-)和铵根(NH_4~+)离子也具有较高的相关性.     

南京北郊大气棕碳吸光特性、来源及其季节变化特征

大气棕碳(BrC)是对大气颗粒物中具有吸光能力的一类有机物的总称，其对空气能见度及气候系统均有重要影响.自2021年3月至2022年2月底于南京北郊利用黑碳仪测定了气溶胶中BrC的光吸收系数，利用最小相关性法分别定量一次(BrC_pri)和二次棕碳(BrC_sec)贡献，结合后向轨迹、潜在来源和日均变化，分析季节变化特征.结果表明，观测期间BrC的平均光吸收系数(370 nm)为(7.76±7.17)Mm^-1,对于总气溶胶光吸收贡献率为(22.0±8.8)%.不同波长下棕碳吸光系数在四季呈现U字形变化，即春季和冬季高，夏季和秋季低.BrC_pri和BrC_sec(370 nm)全年光吸收贡献分别为(62.9±21.4)%和(37.1±21.4)%;前者在四季均占主导，但随着波长增加，BrC_sec的贡献逐渐增加并最终占主导(如在660 nm时).除冬季以外，BrC在其他季节受到来自海上气团的显著影响，而冬季受当地及周边地区排放影响更为显著.交通排放在春、夏和秋季对一...     

秸秆燃烧气溶胶的气象反馈及其棕碳吸光效应

本文利用WRF-Chem模式模拟研究了2013年6月华北地区秸秆燃烧排放气溶胶的气象效应,并对秸秆燃烧产生的吸收性有机气溶胶(即棕碳或BrC)的光吸收效应进行分析.设置4组敏感性试验,通过与AERONET观测结果对比分析了BrC对光吸收的影响.结果表明:模式较好再现了研究时段内各变量变化;在不考虑BrC吸收的情况下,秸秆燃烧产生的气溶胶在主要的农业产区造成地表短波辐射的减弱,月平均值减弱约12.42W/m²,且造成近地面降温而2km以上高空增温,其中近地面温度降幅为0.12～3.64℃,致使边界层趋于稳定,垂直扩散能力减弱;气压整体升高,正变压中心与火点密集区域重合.同时,秸秆燃烧引发近地面较强的风辐散,抑制海洋高湿气团向秸秆燃烧区域的水平输送.在考虑BrC的吸收作用后,光学参数的模拟效果得到了一定提升,AAOD模拟值与观测值的拟合线性斜率由0.47升至0.53,AOD斜率值由0.19升至0.21.生物质燃烧排放BrC对气溶胶消光的影响显著,如AAOD与AOD均出现不同程度的上升.     

基于气溶胶光学特性的颗粒物来源分析

为初步探讨利用气溶胶光学指标判别污染物来源的适用性,选取天津市冬季一次重污染过程（2017年11月17—21日）,对气溶胶的七波段吸收系数、三波段散射系数及其化学组分进行在线观测及分析,研究气溶胶光学特性的变化,并结合化学组分定性分析污染过程不同阶段的污染来源.结果表明:SSA（单散射反照率）可以从散射性组分和吸光性组分对消光贡献的变化判断污染来源.污染积累期,颗粒物中散射性组分（SO₄2-、NO₃-、NH₄+）的增幅高于吸光性组分EC（元素碳）,导致污染积累期的SSA值高于污染前期和污染消散期,说明污染积累期存在较明显的二次转化过程.SAE（散射波长指数）可以从粒径角度推断污染来源.此次观测的污染积累期SAE值呈较明显的下降趋势,说明在细粒径段（2.5 μm以下）颗粒物粒径有增大的趋势,这主要与颗粒物中无机盐的吸湿增长及颗粒物之间的碰并有关.AAE（吸收波长指数）在一定程度上可以指示吸光颗粒物的类型.污染前期,BrC（棕色碳）在370、470 nm处对光吸收的贡献率分别为50.7%、33.8%;同期PM_2.5中ρ（Cl-）、ρ（K+）同步升高,卫星遥感显示,观测点周围有大量火点出现,推测主要受祭祖活动的影响.研究显示,气溶胶光学指标能够从散射性组分和吸光性组分对消光贡献变化、粒径变化、吸光颗粒物类型角度定性解析一部分污染来源,但其对于燃煤源和机动车等重要源类的指示作用还有待进一步研究.      

薪柴燃烧溶解性棕色碳排放特征及光学性质

对农村薪柴（杨木和毛竹）燃烧排放的4类溶解性棕色碳（BrC）组分,包括水溶性有机物（WSOM）、水溶性类腐殖质（HULIS_WS）、碱溶性有机物（ASOM）和碱溶性类腐殖质（HULIS_AS）的组成特征和光学性质进行了初步研究.结果显示,薪柴燃烧排放出大量的BrC,其中BrC_T（WSOM+ASOM）占烟气PM_2.5质量的46%~56%,排放因子为（7.5~16）g/kg.HULIS是薪柴燃烧排放BrC的重要组分,占BrC_T的44%~46%.4类BrC的特征吸收指数（SUVA₂₅₄）、光吸收效率（MAE₃₆₅）和Ångström指数（AAE）值分别为1.9~4.0m²/g、0.4~2.1m²/g和6.2~11.1,说明薪柴燃烧排放BrC具有较高的芳香度、较强的光吸收能力且其光吸收具有较强的波长依赖性.三维荧光光谱分析结果显示,薪柴燃烧排放BrC主要以类蛋白荧光物质组成为主,这与雨水和大气气溶胶中水溶性BrC以类腐殖质荧光物质组成为主的特征存在显著差异.相关性分析结果显示,BrC的MAE₃₆₅与HIX和SUVA₂₅₄呈现显著的正相关性,与E₂/E₃、FI、BIX和β：α呈现显著的负相关性,说明薪柴燃烧排放BrC的光吸收特性与其芳香性、腐殖化程度、自生源贡献和新鲜度等紧密相关.本研究结果有助于进一步认识生物质燃烧BrC的排放特征,为探索大气BrC的来源和环境效应提供数据基础和科学依据.     

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.      

不同环境功能区大气颗粒物中水溶性有机碳的污染特征及其吸光性研究

为了探究不同环境功能区水溶性有机碳(WSOC)光学特性的差异及其影响因素,本研究采集了江西农业大学(城区)、南昌梅岭森林公园(郊区)和庐山风景区(背景点)的大气细颗粒物(PM_2.5)样品.采用总有机碳分析仪和紫外可见分光光度计对WSOC浓度及吸光系数(Abs₃₆₅)、质量吸收效率(MAE₃₆₅)和吸收波长指数(AAE)进行测量与估算.结果表明,城区、郊区和背景点均存在不同程度的PM_2.5污染,浓度水平呈城区>郊区>背景点的趋势.WSOC浓度水平呈郊区>城区>背景点的趋势,郊区和城区WSOC浓度与PM_2.5浓度有显著的相关性,而背景点没有显著相关性,说明城区和郊区的WSOC与PM_2.5颗粒物来源更具有同源性.WSOC的Abs₃₆₅呈城区>郊区>背景点的特点,3个观测点WSOC均存在一定量的吸光性物质,且城区的WSOC含有更多的吸光性物质.WSOC的MAE₃₆₅呈城区>背景点...     

广西背景大气中生物质燃烧对碳质气溶胶组成和吸光性的影响

碳质气溶胶是大气细颗粒物（PM_2.5）的重要组成部分,对空气质量、人体健康和气候变化均有重要影响.针对生物质燃烧（BB）这一碳质气溶胶的重要来源,于2017年11月至2018年10月在广西壮族自治区背景地区采集了PM_2.5样品,分析了样品中的碳质组成、糖类化合物和水溶性棕色碳（BrC）的吸光系数（b_abs）.使用气团老化指数（AAM）校正LG浓度以消除LG降解带来的影响,进而结合贝叶斯混合模型与分子示踪剂法量化了BB对有机碳（OC）的贡献率,并通过相关性分析法探讨了BrC的可能来源.结果表明,研究期间AAM指数平均值为0.40±0.28,表示LG存在光化学降解过程.农作物秸秆是广西地区最主要的生物质燃料类型,在未考虑LG降解下,全年玉米、水稻和甘蔗秸秆焚烧排放的OC分别占总OC的22%、23%和18%;考虑LG在大气中的降解后,相对贡献率分别降低至16%、21%和17%.LG的降解会导致BB对OC的贡献率评估被低估,经过AAM指数校正后,全年BB对OC的贡献率平均值为49.0%.水溶性BrC的b_abs全年的平均值为（8.7±10.7） Mm^-1,其中BB、化石燃料燃烧以及初级生物气溶胶排放可能是BrC的重要来源.     

西安冬季大气棕碳光学特征及辐射强迫

为探讨西安冬季不同大气污染状况（污染天和清洁天）大气细粒子（PM_2.5）及其一次棕碳（BrC_pri）和二次棕碳（BrC_sec）的光学特征及辐射效应,开展了高分辨率多波段光学参数观测,获得PM_2.5多波段光学吸收系数（b_abs）,通过进一步数据分析得到BrC_pri和BrC_sec的光谱依赖指数（AAE）及其相对黑碳（BC）的辐射强迫.结果显示,污染天时段370nm光学吸收（b_abs（370））和880nm光学吸收（b_abs（880））均值分别为（733±311） Mm^-1和（185±80） Mm^-1,分别高出清洁天约5.9倍和6.2倍.清洁天PM_2.5的AAE1.08~2.09,变化幅度大于污染天（1.28~1.79）.清洁天棕碳光学吸收（b_abs（BrC））在370nm波长对总吸收占比高于污染天,均超过30%.一次棕碳光学吸收（b_abs（BrC_pri））在清洁天和污染天均对b_abs（BrC）呈现高贡献,占比范围分别为76%~86%和82%~91%,说明一次排放仍然是造成西安冬季污染的重要原因.清洁天BrC、BrC_pri和BrC_sec的AAE均值分别为4.42、4.31和4.78,均高于污染天,说明清洁天粒子等效直径相对较小,老化程度较高导致BrC的高光谱依赖性.b_abs（BrC_sec）日间变化表明污染天凌晨高湿条件下的液相反应可能是BrC_sec形成的主要机制,比清洁天更为强烈,而污染天日间BrC_sec受光漂白的影响较大.最后估算了BrC_pri和BrC_sec的辐射强迫效应,在紫外波段（300~400nm）,污染天BrC_pri和BrC_sec相对BC的辐射强迫分别为62%和16%,而清洁天分别为59%和23%,表明BrC_pri和BrC_sec在西安冬季的辐射强迫效应不容忽视.     

南京北郊PM2.5中有机组分的吸光性质及来源

对南京北郊2018年9月~2019年9月PM_2.5中有机组分的吸光性质进行了研究,并利用PM_2.5化学组成及主成分分析法分析该地区吸光性有机碳（棕碳,brown carbon,BrC）的主要来源.结果表明,水溶性有机碳（water-soluble organic carbon,WSOC）和甲醇可提取有机碳（methanol extractable organic carbon,MEOC）在365 nm处光吸收系数（Abs_365,w和Abs_365,m）的平均值分别为（3.22±2.18）Mm^-1和（7.69±4.93）Mm^-1.Abs_365,w和Abs_365,m分别与WSOC（r=0.72,P<0.01）和MEOC（r=0.62,P=0.04）的质量浓度显著相关,均表现为冬高夏低,夜高昼低的时间变化特征.这可归结于冬季和夜间的气象特征（例如边界层高度降低和大气稳定度升高）、冬季一次源排放的增加以及夏季和白天更强的"光漂白作用".Abs_365,m/Abs_365,w的年均值（2.60±0.92）远高于MEOC/WSOC（质量浓度比值,1.37±0.30）,表明MEOC中非水溶性组分的吸光作用更强,在BrC的吸光作用中占主导地位.WSOC、MEOC、Abs_365,m和K⁺均未表现出强相关性（r<0.60）,因此生物质燃烧不是该地区BrC的主要一次来源.WSOC和MEOC质量吸收效率（MAE_365,w和MAE_365,m）及其比值（MAE_365,m/MAE_365,w）的季节变化和Abs₃₆₅相同.MEOC中非水溶性组分的MAE₃₆₅［（4.10±5.15）m²·g^-1］分别是MAE_365,w和MAE_365,m的6.0和2.9倍,支持BrC的吸光作用受非水溶性有机组分主导这一推断.和WSOC的埃氏吸收指数（Å_WSOC）相比,MEOC的埃氏吸收指数（Å_MEOC）随时间变化更显著,这可能与非水溶性吸光组分排放的季节变化有关.主成分分析结果显示,本研究PM_2.5中有机组分的吸光作用主要来源于二次形成过程和人为活动相关的一次排放,而不是生物质燃烧.     

Atmospheric light absorption—A review

The atmosphere interacts both with incoming as well as outgoing light. Two main processes take place: light scattering and light absorption. Whereas light scattering redistributes any ligh energy in the atmosphere, light absorption converts the light energy to internal energy of the absorbing molecules and eventually transfers it to the surrounding gas as heat.Atmospheric gases absorb light in distinct spectral regions usually at more or less broad bands. Best known is the broad absorption of ozone in the far u.v., being essential for the existence of the biological macromolecules on Earth. Gases known as greenhouse gases, e.g. CO₂, CH₄, N₂O and water vapor absorb a wide range of infrared radiation, and thus are responsible for the greenhouse effects. Since the lifetime of these gases (except water vapor) is considerable, their distribution around the globe is fairly homogeneous.The atmospheric aerosol gives the major contribution to the atmospheric light absorption in the visible and near u.v. and near i.r. Graphitic (black) carbon, the main constituent of soot, is almost exclusively responsible for the light absorption of the particles. The light absorption by aerosols is continuous and covers the whole visible spectral range. It only depends slightly on wavelength.The optical properties of elemental carbon are determined by the size of the particles and their complex refractive index. A variety of refractive indices can be found in the literature for elemental carbon, most likely caused by different production and thus composition of the particles. Soot particles are very efficient in attenuating light; for the average size the particles have more than twice the mass extinction coefficient compared to transparent particles such as ammonium sulfate. The light absorption coefficient of a mixture of elemental carbon and transparent materials is higher for internal than for external mixtures. When incorporated into transparent particles, the absorption properties of elemental carbon can be multiplied and the single scattering albedo will decrease in comparison to an external mixture of the same materials.There are different methods to measure the light absorption coefficient of suspended particles. They can be separated in three groups, depending on the effect or methodology they use, but no standard procedure has been adopted so far.Soot is produced by all combusttion processes. Since most fires on Earth are due to humans, then indirectly humans are the major source of light-absorbing aerosol particles. On a global scale black carbon amounts to 1.1–2.5% of the anthropogenic particles and to 0.2–1% of the total emitted particles. The emission factors for elemental carbon are highest for small sources such as diesel motors or fireplaces.The light-absorbing aerosol consists of fine particles, with most particles having diameters less than a few tenths of a micrometer. Particles in the size range of soot particles have an average lifetime of 7 days in the atmosphere, therefore they can be transported over large distances and are also found in remote regions. Since light-absorbing particles have a variety of sources and sinks and they are involved in precipitation cycles, their distribution on the globe is inhomogeneous. Light-absorption coefficients of the atmospheric aerosol reported in the literature differ by more than four orders of magnitudes at different locations, but nevertheless black carbon particles have been found even at very remote areas, such as the South Pole.Although light-absorbing particles are a minority component in the atmospheric aerosol, their effects cannot be neglected: since the mass extinction coefficient of soot is higher by a factor of two to three compared to transparent particles, light-absorbing substances in the atmosphere can cause at some locations up to half of the visibility reduction; light-absorbing substances in the atmosphere can be responsible for the brown appearance of urban hazes and the discoloration of the sky.The light absorption of the atmosphere in the visible (which mainly is due to particulate matter) has to be taken into account when considering radiative properties and climatic consequences. A small temperature increase due to absorption in the visible is to be expected. The value is around a few tenths of a Kelvin, but no general statement on its magnitude is possible, since a large spatial and temporal variation exists and other factors like surface albedo, the optical depth of the aerosol, its incorporation in clouds and humidity growth of the aerosol have to be considered.     

Industrial and wildfire aerosol pollution over world heritage Lake Baikal

Lake Baikal is the biggest reservoir of fresh water with unique flora and fauna; presently it is negatively affected by climate change, water warming, industrial emissions, shipping, touristic activities, and Siberian forest fires. The assessment of air pollution - related Baikal's ecosystem damage is an unsolved problem. Ship, based expedition exploring the Baikal atmospheric aerosol loading, was performed over the lake area in July 2018. We combine the aerosol near - water and vertical distributions over the Lake Baikal basin with meteorological observations and air mass transportation simulations. Lidar sounding of aerosol fields in the troposphere assesses the atmospheric background in the pristine areas and the pollution during fire-affected periods. Aerosol optical properties (scattering and spectral absorption) converted to the particle number size, black carbon (BC) mass, and Absorption Angstrom Exponent (AAE) provide the inside into aerosol characterization. Transport of industrial emissions from Krasnoyarsk and Irkutsk regions, and wildfire plumes from Republic of Yakutia relates the pollution sources to the increased concentrations of fine particle numbers, PM₁₀ and BC mass over Southern and Northern/Central Baikal, respectively. The highest PM₁₀ and BC are associated to the harbor and touristic areas of intensive shipping and residential biomass burning. Deposition estimates applied to aerosol data exhibit the pollution fluxes to water surface over the whole Baikal area. AAE marks the impact of coal combustion, residential biomass burning, and wildfires indicating the high pollution level of the Lake Baikal ecological system .     

强还原与生物炭对土壤酶活性和温室气体排放的影响

本研究设置未修复对照(CK)、土壤强还原处理(RSD)、生物炭修复(BC)以及RSD与生物炭联合修复(RSD+BC),采用培养实验对比研究不同修复处理对设施蔬菜地土壤酶活性和温室气体(CO2和N2O)排放的影响.结果表明:相比CK,RSD和RSD+BC处理显著提高了β-葡萄糖苷酶(βG)、纤维二糖水解酶(CBH)、过氧...