摘要
基于稀释通道采样系统和室内模拟燃烧实验,实测采集两种民用燃煤(蜂窝煤和块煤)燃烧排放的细颗粒物(PM_(2.5)),利用离子色谱分析样品中的Na~+、NH_4~+、Mg~(2+)、K~+、Ca~(2+)、F~-、Cl~-、NO_3~-和SO_4~(2-)等9种水溶性离子,计算得到相关排放因子,并结合能源统计年鉴,基于"自上而下"方法获得2013年全国(除港、澳、台地区)民用燃煤排放PM_(2.5)中水溶性离子的排放总量,以人口密度数据作为空间分布权重因子,建立全国1km×1km的网格化清单.结果表明,除Ca~(2+)和Mg~(2+)以外,蜂窝煤燃烧排放水溶性离子排放因子普遍高于块煤燃烧排放,因而需对块煤加工成蜂窝煤的多种有害组分的减排效果进行系统评估.9种水溶性离子中SO_4~(2-)离子排放因子远高于其他水溶性离子的排放因子;对于蜂窝煤和块煤,分别为494mg/kg和105mg/kg.从阴阳离子当量浓度之比(2.0~2.5)来看,民用燃煤排放一次颗粒物呈酸性.民用燃煤水溶性离子人均排放量最多的省份是山东、河北和北京,分别为520.2,401.1,362.7g/人;单位面积排放强度最高的是山东、北京和上海,分别为323.9,287.3,197.9kg/km~2.从民用燃煤离子单位面积排放强度和人均排放量来看,北京和山东均需要对该类源减排引起足够重视.高分辨率空间分布显示民用燃煤排放水溶性离子分布有以下几个特点:(1)东部高于西部;(2)平原、盆地多;山地、高原少;(3)受到自然地理环境因素和经济发展水平制约,主要集中分布于平原、盆地及河谷地区人口密布,从应对冬季大气重污染过程的角度,需加大对民用燃煤排放水溶性离子及其气态前体物的管控力度.
Emission factors(EFs) for 9water-soluble ions of Na+, NH_4~+, Mg~(2+), K~+, Ca~(2+), F~-, Cl~-, NO_3~- and SO_4~(2-) in PM_(2.5)from raw coal and honeycomb coal burning were obtained by dilution sampling system and domestic burning test. The total emission amounts of water-soluble ions from residential coal burning in 2013 of China were calculated. An 1km×1km grid cell-based emission inventory was established. Results showed that the EFs of water soluble ions from honeycomb coal burning were higher than those emitted from the raw coal burning except for Ca~(2+) and Mg~(2+). It is urgently to assess the emission reduction effect of hazardous chemical components of changing the raw coal into honey coal. The EFs of SO_4~(2-) were highest than other ions, which were 494mg/kg and 105mg/kg for honey coal and raw coal, respectively. The particles emitted from domestic coal burning were acidity, with ∑anion/∑cation ratios ranging in 2.0~2.5. For per capita emission, Shandong, Hebei and Beijing were the top three provinces with higher emission amounts, which were 520.16, 401.1 and 362.7gram per capita, respectively. For emission intensity, Shandong, Beijing and Shanghai hold the highest values, as 323.9, 287.3 and 197.9kg/km2, respectively. The emission of ions from domestic coal burning in Beijing and Shandong should be paid more attention. For the high spatial resolution emission inventories of ions from domestic coal burning, they exhibited the following features:(1) eastern China exhibited higher values than those for western China;(2) they were higher in plains and basins than those in plateau and mountainous region;(3) they mainly constraint by the geographical environment factors and economic development level, which maybe related with the historical trend of population evolution. Human beings are mainly concentrated in the main plains, basins and river valleys, therefore from the view of alleviating heavy air pollution processes in winter, the water-soluble ions and their gaseous precusors should be strictly reduced.
引文
[1]Chen Y J,Jiang X H,Zhi G R,et al.Black carbon emissions from residential coal combustion and reduction strategy(in Chinese).Sci China Ser D-Earth Sci,2009,39(11):1554-1559.
[2]于国光,王铁冠,吴大鹏.薪柴燃烧源和燃煤源中多环芳烃的成分谱研究[J].生态环境,2007,16(2):285-289.
[3]Shen G,Yang Y,Wang W,et al.Emission factors of particulate matter and elemental carbon for crop residues and coals burned in typical household stoves in China[J].Environmental Science and Technology,2010,44(18):7157-7162.
[4]王琴,张大伟,刘保献,等.基于PMF模型的北京市PM2.5来源的时空分布特征[J].中国环境科学,2015,35(10):2917-2924.
[5]Chen S,Xu L,Zhang Y,et al.Direct observations of organic aerosols in common wintertime hazes in North China:insights into direct emissions from Chinese residential stoves[J].Atmospheric Chemistry and Physics,2017,17(2):1259-1270.
[6]Li W,Xu L,Liu X,et al.Air pollution–aerosol interactions produce more bioavailable iron for ocean ecosystems[J].Science Advances,2017,3(3):e1601749.
[7]姚青,韩素芹,蔡子颖.天津采暖期大气PM2.5中重金属元素污染及其生态风险评价[J].中国环境科学,2013,33(9):1596-1600.
[8]Wang G,Zhang R,Gomez M E,et al.Persistent sulfate formation from London Fog to Chinese haze[J].Proceedings of the National Academy of Sciences,2016,113(48):13630-13635.
[9]Liu J,Mauzerall D L,Chen Q,et al.Air pollutant emissions from Chinese households:A major and underappreciated ambient pollution source[J].Proceedings of the National Academy of Sciences,2016,113(28):7756-7761.
[10]Chan Y C,Simpson R W,Mctainsh G H,et al.Source apportionment of visibility degradation problems in Brisbane(Australia)using the multiple linear regression techniques[J].Atmospheric Environment,1999,33(19):3237-3250.
[11]Yang L,Wang D,Cheng S,et al.Influence of meteorological conditions and particulate matter on visual range impairment in Jinan,China[J].Science of the Total Environment,2007,383(1):164-173.
[12]唐孝炎,张远航,邵敏.大气环境化学[M].北京:高等教育出版社,2006.
[13]Spengler J D,Brauer M,Koutrakis P.Acid air and health[J].Environmental Science and Technology,1990,24(7):946-956.
[14]Firket J.1931.The cause of the symptoms found in the Meuse Valley during the fog of December[J].Bull Acad R Med Belg,1930,11:683-741.
[15]孙玉富,于光前.燃煤污染型地方性氟中毒防治研究进展及防治策略[J].中华预防医学杂志,2007,41(3):227-229.
[16]蹇新华,李华兵,蹇曾山.燃煤污染型氟中毒与环境氟关系的调查[J].中国地方病防治杂志,1988,3(6):1368-369.
[17]黎秉铭,黎莉,江成忠.地方性氟中毒环境地球化学病因的探讨[J].中国环境科学,1995,15(1):0-0.
[18]黄卫,毕新慧,张国华,等.民用蜂窝煤燃烧排放颗粒物的化学组成和稳定碳同位素特征[J].地球化学,2014,(6):640-646.
[19]王书肖,赵秀娟,李兴华,等.工业燃煤链条炉细粒子排放特征研究[J].环境科学,2009,30(4):963-968.
[20]Li X,Wang S,Duan L,et al.Particulate and trace gas emissions from open burning of wheat straw and corn stover in China[J].Environmental Science and Technology,2007,41(17):6052-6058.
[21]Cao G L,Zhang X,Gong S L,et al.Investigation on emission factors of particulate matter and gaseous pollutants from crop residue burning[J].Journal of Environmental Sciences,2008,20(1):50-55.
[22]He L Y,Hu M,Zhang Y H,et al.Fine particle emissions from on-road vehicles in the Zhujiang Tunnel,China[J].Environmental Science and Technology,2008,42(12):4461-4466.
[23]祝晓燕,段雷,唐桂刚,等.中国工业源大气盐基阳离子排放量估算[J].清华大学学报:自然科学版,2004,44(9):1176-1179.
[24]Chen Y,Sheng G,Bi X,et al.Emission factors for carbonaceous particles and polycyclic aromatic hydrocarbons from residential coal combustion in China[J].Environmental Science and Technology,2005,39(6):1861-1867.
[25]Chen Y,Zhi G,Feng Y,et al.Measurements of emission factors for primary carbonaceous particles from residential raw‐coal combustion in China[J].Geophysical Research Letters,2006,33(20).
[26]Chen Y,Tian C,Feng Y,et al.Measurements of emission factors of PM2.5,OC,EC,and BC for household stoves of coal combustion in China[J].Atmospheric Environment,2015,109:190-196.
[27]田贺忠,曲益萍.2005年中国燃煤大气砷排放清单[J].环境科学,2009,30(4):956-962.
[28]田贺忠,曲益萍,王艳,等.2005年度中国燃煤大气硒排放清单[J].中国环境科学,2009,29(10):1011-1015.
[29]刘海彪,孔少飞,王伟,等.中国民用煤燃烧排放细颗粒物中重金属的清单[J].环境科学,2016,(8):2823-2835.
[30]刘源,张元勋,魏永杰,等.民用燃煤含碳颗粒物的排放因子测量[J].环境科学学报,2007,27(9):1409-1416.
[31]Zhang Y,Schauer J J,Zhang Y,et al.Characteristics of particulate carbon emissions from real-world Chinese coal combustion[J].Environmental Science and Technology,2008,42(14):5068-5073.
[32]Zhi G,Chen Y,Feng Y,et al.Emission characteristics of carbonaceous particles from various residential coal-stoves in China[J].Environmental Science and Technology,2008,42(9):3310-3315.
[33]孔少飞,白志鹏,陆炳.民用燃料燃烧排放PM2.5和PM10中碳组分排放因子对比[J].中国环境科学,2014,34(11):2749-2756.
[34]海婷婷,陈颖军,王艳,等.民用燃煤源中多环芳烃排放因子实测及其影响因素研究[J].环境科学,2013,34(7):2533-2538.
[35]窦晗,常彪,魏志成,等.国内民用燃煤烟气中多环芳烃排放因子研究[J].环境科学学报,2007,27(11):1783-1788.
[36]付晶莹,江东,黄耀欢.中国公里网格人口分布数据集(Population Grid_China)[EB/OL].全球变化科学研究数据出版系统,http://www.geodoi.ac.cn/webcn/doi.aspx?Id=131.
[37]国家统计局工业交通统计司,国家发展和改革委员会能源局.中国能源统计年鉴2013[M].北京:中国统计出版社,2014.
[38]Bond T C,Covert D S,Kramlich J C,et al.Primary particle emissions from residential coal burning:Optical properties and size distributions[J].Journal of Geophysical Research:Atmospheres,2002,107(D21).
[39]马思萌,王丽涛,魏哲,等.邯郸市PM2.5及其化学组分的季节性变化[J].环境工程学报,2016,10(7):3743-3750.
[40]温天雪,王跃思,张凯.采暖季北京大气PM10中硫酸盐与硫氧化率的观测研究[J].中国科学院研究生院学报,2007,24(5):584-589.
[41]雒昆利,徐立荣.中国华北地区和西北地区动力煤氟的排放量[J].科学通报,2002,47(11):873-877.
[42]山东省质量技术监督局发布全省民用散煤和民用型煤质量标准[EB/OL].(2016-11).http://www.zbny.org/content/?122-156-2147.html.
[43]Ge S,Xu X,Chow J C,et al.Emissions of air pollutants from household stoves:honeycomb coal versus coal cake[J].Environmental Science and Technology,2004,38(17):4612-4618.
[44]Engelbrecht J P,Swanepoel L,Chow J C,et al.The comparison of source contributions from residential coal and low-smoke fuels using CMB modeling,in South Africa[J].Environmental Science and Policy,2002,5(2):157-167.
[45]Waston J G,Chow J C,Houck J E.PM2.5 Chemical Source Profiles for Vehicle Exhaust,Vegetative Burning,Geological Materials,and Coal Burning in Northwestern Colorado during1995[J].Chemosphere,2001,43(8):1141-1151.
[46]张育涵,胡涵庆,李金娟.使用固硫添加剂减少煤燃烧SO2排放的研究[J].中原工学院学报,2010,21(3):4-7.
[47]黄仁建,陈新,李凤华,等.湖南中部燃煤型氟中毒病区的氟化物来源研究[J].环境与健康杂志,2008,(12):966-969.
[48]黄山秀,马名杰,沈玉霞,等.我国型煤技术现状及发展方向[J].中国煤炭,2010,(1):84-87.
[49]Zheng B,Zhang Q,Zhang Y,et al.Heterogeneous chemistry:A mechanism missing in current models to explain secondary inorganic aerosol formation during the January 2013 haze episode in North China[J].Atmospheric Chemistry and Physics,2015,15(4):2031-2049.
[50]中华人民共和国环境保护部《.2013中国环境状况公报》.2014.
[51]黄园淅,杨波.从胡焕庸人口线看地理环境决定论[J].云南师范大学学报:哲学社会科学版,2012,(1):68-73.
[52]高晓梅.我国典型地区大气PM2.5水溶性离子的理化特征及来源解析[D].济南:山东大学,2012.
[53]Zhang T,Cao J J,Tie X X,et al.Water-soluble ions in atmospheric aerosols measured in Xi'an,China:seasonal variations and sources[J].Atmospheric Research,2011,102(1):110-119.
[54]Lai S,Zou S,Cao J,et al.Characterizing ionic species in PM2.5and PM10 in four Pearl River Delta cities,South China[J].Journal of Environmental Sciences,2007,19(8):939-947.
[55]王玮,王英,苏红梅,等.北京市沙尘暴天气大气气溶胶酸度和酸化缓冲能力[J].环境科学,2001,22(5):25-28.
[56]曾凡刚,王玮.大气气溶胶酸度和酸化缓冲能力研究[J].中国环境监测,2001,17(4):13-16.