2014年北京APEC期间大气醛酮污染物的污染特征与来源分析

于2014年11月北京APEC会议前后,调查了大气醛酮污染物的变化规律及污染特征. 结果表明甲醛、乙醛和丙酮是主要污染物,占总醛酮污染物的82.66%,特别是甲醛,约占40.12%. APEC会议期间北京采取相关措施后,总醛酮污染物浓度下降了64.10%,醛酮污染物在会议前后的变化趋势与PM_2.5等污染物相似. 会议期间和会议后甲醛、乙醛、丙酮和总醛酮污染物之间(R²为0.67~0.98)的相关性较好,说明其有相同来源; 但会议前的相关性较弱,(R²-0.11~0.42和R² 0.16~0.94),说明其来源不同. 计算所得的诊断参数如C1/C2、C2/C3和OC/EC比值显示,会议前来自汽车尾气与燃煤的复合源,而会议期间和会议后燃煤排放比例增加,特别是在会议后.     

沈阳市郊区环境空气中醛酮类化合物的污染特征与来源分析

为探究沈阳市郊区环境空气中醛酮类化合物的污染特征,于2017年8月24日—9月2日采用2,4-二硝基苯肼固相吸附/高效液相色谱方法对沈阳市郊区醛酮类化合物进行观测分析,利用美国环境保护局推荐的人体健康风险评价方法对部分有毒有害醛酮类化合物的人体健康风险进行了评价,并利用比值法对醛酮类化合物的来源进行了初步分析.结果表明:醛酮类化合物质量浓度日均值范围为23.16～38.38μg/m³;质量浓度最高的4种醛酮类化合物依次是丙酮、甲醛、正丁醛和乙醛,其质量浓度日均值的平均值分别为8.71、5.90、5.48和2.95μg/m³.对·OH消耗速率(L_OH)贡献较大的醛酮类化合物物种是正丁醛、甲醛和乙醛,臭氧生成潜势贡献(OFP)较大的醛酮类化合物物种是甲醛、正丁醛和乙醛,在研究区影响醛酮类化合物光化学反应活性的物种主要是甲醛、乙醛和正丁醛.研究区观测期间,环境空气中甲醛和乙醛的致癌性风险值分别为1.18×10^-5和5.91×10^-6,对暴露人群存在潜在的致癌风险;乙醛的非致癌风险值为...     

张家界森林大气中醛酮类化合物浓度变化特征

为探究中亚热带森林大气中醛酮类化合物浓度变化特征,于2014年8月—2015年1月在张家界森林公园采用 EPA TO-11A方法对张家界森林大气中醛酮类化合物质量浓度进行了监测.结果表明:张家界森林大气中主要的醛酮类化合物为甲醛、乙醛、丙酮、丙醛和MACR(甲基丙烯醛),质量浓度分别为4.32、0.95、3.01、0.48和0.51 μg/m3.大气中ρ(甲醛)、 ρ(乙醛)和ρ(MACR)的季节变化特征很明显,夏季和秋季醛酮类化合物质量浓度较高,冬季醛酮类化合物质量浓度较低.此外,醛酮类化合物质量浓度日变化显著,除了10月、12月受人为因素影响较大外,其余月份醛酮质量浓度最大值通常出现在13:00—15:00.张家界森林大气中C1/C2(ρ(甲醛)/ρ(乙醛))为5.72,比城市地区(C1/C2为1左右)高,但比偏远森林地区(C1/C2为10左右)低.ρ(甲醛)与ρ(乙醛)、 ρ(MACR)均呈正相关且达到显著水平,而ρ(丙酮)与ρ(甲醛)、 ρ(乙醛)与ρ(MACR)的相关性差.与文献报道的加拿大Ontario、墨西哥Langmuir等地区对比,张家界森林大气中醛酮类化合物质量浓度较高,但明显低于北京、上海等城市地区.研究显示,张家界森林大气中甲醛、乙醛和MACR主要来自森林地区植物排放的VOCs光氧化生成,丙酮除了来自植物排放的有机物光氧化分解外,还有其他人为源,进一步说明了张家界森林大气中醛酮类化合物浓度变化主要受光化学反应等自然影响,但人为因素的影响也不容忽略.      

北京大气中醛酮化合物污染特征与来源分析

为研究北京大气中醛酮化合物的污染特征,利用2,4-二硝基苯肼采样管采样-高效液相色谱仪分析的方法,于2020年1月—12月以及2020年5月26—29日对北京城区评价点(车公庄)大气中的13种醛酮化合物开展常规和加密监测分析,于2020年9月17—21日对北京城区评价点和北京东南边界点(永乐店)开展同步监测分析,并对醛酮化合物的来源进行了初步分析.结果表明：(1)2020年北京城区大气中醛酮化合物总浓度为(25.1±8.5)μg/m³,其中丙酮、甲醛和乙醛的贡献率分别为43.1%、30.7%和15.6%.臭氧生成潜势呈甲醛>乙醛>丙酮的特征,其中甲醛和乙醛对臭氧生成潜势的贡献率分别为66.5%和23.0%.(2)醛酮化合物总浓度呈夏季>春季>秋季>冬季的特征,甲醛和乙醛浓度日变化均呈“双峰”特征,均在12:00—15:00达第1个峰值,在17:00—19:00达第2个峰值.(3)同步监测期间,车公庄和永乐店的醛酮化合物总浓度分别为(24.4±7.8)(24.1±7.5)μg/m³,车公庄丙酮、甲醛的贡献率分别较永...     

Levels, sources and health risks of carbonyls and BTEX in the ambient air of Beijing, China

The atmospheric concentrations of carbonyls and BTEX (benzene, toluene, ethylbenzene, m,p-xylene and o-xylene) were measured simultaneously at a same sampling site in Beijing from September 2008 to August 2010. The average concentrations of the total measured carbonyls during autumn, winter, spring, and summer were 37.7, 31.3, 39.7, 50.5 μg/m³, respectively, and maximal values for their diurnal variations usually happened at noontime. In contrast to carbonyls, the average concentrations of the total measured BTEX during the four seasons were 27.2, 31.9, 23.2, 19.1 μg/m³, respectively, and minimal values for their diurnal variations always occurred in the early afternoon. The average concentration for carbonyls increased about 24% from September 2008-August 2009 to September 2009-August 2010, for BTEX, increased about 15%. Integrated life time cancer risks for three carcinogens (benzene, formaldehyde and acetaldehyde) in Beijing exceeded the value of 1E-06, and the hazard quotient (HQ) of non-cancer risk of exposure to formaldehyde exceeded unity.     

上海市大气羰基化合物水平研究

建立乙腈-水-四氢呋喃三元梯度洗脱方法,利用HPLC-UV分离定量22种羰基化合物,并成功地分离了丙酮和丙烯醛.选取了2个采样点(工业区和商业区)对上海市大气中的羰基化合物进行了研究.结果表明,甲醛、乙醛、丙酮和2-丁酮(C1-C4羰基化合物)是上海市大气浓度较高的化合物,它们分别占羰基化合物总量的78.95%(工业区)和77.63%(商业区).在工业区,甲醛、乙醛、丙酮和2-丁酮的平均浓度分别为10.36、15.32、9.95和4.56μg/m3;在商业区,它们的平均浓度分别为10.00、10.04、7.80和2.81μg/m3.工业区的C1-C4羰基化合物平均水平要高于商业区.羰基化合物总量亦是工业区(53.64μg/m3)高于商业区(41.96μg/m3).羰基化合物的昼夜变化在工业区和商业区也比较一致,均是早高峰和晚上这2个时段的浓度很高,而其它时段较低.     

Investigation of carbonyl compound sources at a rural site in the Yangtze River Delta region of China

Carbonyl compounds are important intermediates in atmospheric photochemistry, but their primary sources are still not understood well. In this work, carbonyls, hydrocarbons, and alkyl nitrates were continuously measured during November 2011 at a rural site in the Yangtze River Delta region of China. Mixing ratios of carbonyls and hydrocarbons showed large fluctuations during the entire measurement. The average level for total measured volatile organic compounds during the pollution episode from 25th to 27th November, 2011 was 91.6 ppb, about 7 times the value for the clean period of 7th–8th, November, 2011. To preliminarily identify toluene sources at this site, the emission ratio of toluene to benzene (T/B) during the pollution episode was determined based on photochemical ages derived from the relationship of alkyl nitrates to their parent alkanes. The calculated T/B was 5.8 ppb/ppb, significantly higher than the values of 0.2–1.7 ppb/ppb for vehicular exhaust and other combustion sources, indicating the dominant influence of industrial emissions on ambient toluene. The contributions of industrial sources to ambient carbonyls were then calculated using a multiple linear regression fit model that used toluene and alkyl nitrates as respective tracers for industrial emission and secondary production. During the pollution episode, 18.5%, 69.0%, and 52.9% of measured formaldehyde, acetaldehyde, and acetone were considered to be attributable to industrial emissions. The emission ratios relative to toluene for formaldehyde, acetaldehyde, and acetone were determined to be 0.10, 0.20 and 0.40 ppb/ppb, respectively. More research on industrial carbonyl emission characteristics is needed to understand carbonyl sources better.     

广州医院低分子量羰基化合物研究

2004年1月2日-3月20日对广州市区4家医院室内外的低分子量羰基化合物进行了检测.实验方法是应用羰基化合物和2,4-二硝基苯肼(DNPH)迅速反应生成衍生物,产物在高效液相色谱上进行检测;每家医院连续采样5 d.结果表明:广州医院丙酮的质量浓度最高,其次是乙醛和甲醛,除甲醛外,室内羰基化合物的质量浓度稍高于室外;羰基化合物之间的相关性不好,可能是它们的来源比较复杂,如车辆排放、建筑装饰材料、医用试剂等,其中广泛使用酒精消毒可能是医院乙醛质量浓度偏高的原因.对医院甲醛、乙醛在人体内的暴露水平做了讨论,与其他类似场所相比,医院的暴露风险相对较小.      

Investigation of carbonyl compound sources at a rural site in the Yangtze River Delta region of China

Carbonyl compounds are important intermediates in atmospheric photochemistry, but their primary sources are still not understood well. In this work, carbonyls, hydrocarbons, and alkyl nitrates were continuously measured during November 2011 at a rural site in the Yangtze River Delta region of China. Mixing ratios of carbonyls and hydrocarbons showed large fluctuations during the entire measurement. The average level for total measured volatile organic compounds during the pollution episode from 25th to 27th November, 2011 was 91.6 ppb, about 7 times the value for the clean period of 7th-8th, November, 2011. To preliminarily identify toluene sources at this site, the emission ratio of toluene to benzene (T/B) during the pollution episode was determined based on photochemical ages derived from the relationship of alkyl nitrates to their parent alkanes. The calculated T/B was 5.8 ppb/ppb, significantly higher than the values of 0.2-1.7 ppb/ppb for vehicular exhaust and other combustion sources, indicating the dominant influence of industrial emissions on ambient toluene. The contributions of industrial sources to ambient carbonyls were then calculated using a multiple linear regression fit model that used toluene and alkyl nitrates as respective tracers for industrial emission and secondary production. During the pollution episode, 18.5%, 69.0%, and 52.9% of measured formaldehyde, acetaldehyde, and acetone were considered to be attributable to industrial emissions. The emission ratios relative to toluene for formaldehyde, acetaldehyde, and acetone were determined to be 0.10, 0.20 and 0.40 ppb/ppb, respectively. More research on industrial carbonyl emission characteristics is needed to understand carbonyl sources better.     

2010年广州亚运期间空气质量与污染气象条件分析

利用2010年11月4日～12月10日广州地区NO2、O3、SO2、PM、能见度实测资料,区域空气污染指数RAQI及大气输送扩散特征参数,分析广州亚运期间空气质量与气象条件变化特征.结果表明,亚运期间空气质量比亚运前后好,能见度比亚运前后大,PM1和PM2.5浓度比亚运前后小,能见度与PM1和PM2.5有较好的反相关;亚运期间NO2和SO2日均值和小时均值均达到国家一级标准,PM10日均值和O3小时均值均满足国家二级标准,污染物得到较好的控制;广州地区SO2受本地源和外地源远距离输送叠加影响,NO2受本地源影响较大;广州周边城市NO2、SO2和PM10有向广州输送的潜势,而广州O3有向其周边城市扩散的潜势;亚运期间污染气象条件比亚运前后有利,亚运期间污染物浓度降低得益于政府实施的减排措施及良好的气象条件.     

珠江口西岸冬季海陆风背景下羰基化合物的初步研究

于2008年12月7~9日对珠江三角洲新垦的大气环境进行连续加强观测,采用DNPH-HPLC/UV分析方法测量了冬季海陆风条件下大气挥发性羰基化合物的组成及浓度水平,研究了污染特征和来源.结果表明,新垦大气中共检测到17种挥发性羰基化合物,浓度变化范围为7.78′10-9~31.78′10-9,大多数物质地面浓度高于楼顶.其中浓度最高的污染物是丙酮,其次是甲醛和乙醛,三者占总羰基化合物浓度的比例高于70%.大气挥发性羰基化合物的浓度分布呈现出以12月8日为代表的受城区污染物长距离输送影响的变化规律,以及以12月7日和12月9日为代表的受海陆风影响的变化规律.甲醛/乙醛和乙醛/丙醛的特征比值及各成分相关性分析表明它们主要来自城区人为污染源的排放,其组成和含量的变化与污染物长距离输送过程和海陆风影响有密切关系.大气光化学反应生成的二次产物和当地植被排放亦是重要来源.     

Urban air pollution in Brazil: Acetaldehyde and other carbonyls

We have measured ambient levels of carbonyls in three major urban areas of Brazil: Sao Paulo, Rio de Janeiro and Salvador. The most abundant carbonyls were acetaldehyde (up to 63 μg m⁻³, or 35 ppb) followed by formaldehyde (up to 42 μg m⁻³, or 34 ppb), and acetone (up to 20 ppb). Levels of 10 other aliphatic and aromatic carbonyls were in the range 0–5 ppb. Total carbonyl concentrations were in the range 11–75 ppb. Indoor levels were also measured at several locations in Salvador. High levels of acetaldehyde, 430 μg m⁻³ or 240 ppb, were measured in a highway tunnel.Using carbonyl/CO concentration ratios, mobile source emissions of carbonyls are estimated for the Sao Paulo area. Ambient levels of acetaldehyde and acetaldehyde/formaldehyde concentration ratios in Brazil are compared to those for other urban areas, and are briefly discussed in relation with the large scale use of ethanol as a vehicle fuel.     

北京市2009年8月大气颗粒物污染特征

为研究2008年8月北京奥运会1a之后北京市大气颗粒物的污染特征,于2009年8月对北京市大气颗粒物PM10、PM2.5样品进行采集,测量其质量浓度并对其中的水溶性离子组分进行分析.研究发现2009年8月北京市大气颗粒物PM10、PM2.5质量浓度日均值分别为176.9μg/m3和102.5μg/m3.PM10质量浓度比2008年观测值上升了180%,比2007年降低了10%; PM2.5质量浓度比2008年观测值上升了126%,比2007年上升了31%.水溶性离子是大气颗粒物的重要组分,分别占PM10和PM2.5质量浓度的43%和61%.对比发现,污染天气条件下PM2.5/PM10和NO3-/SO42-比值升高,移动源是北京地区主要的污染物来源.风向风速和降水等天气条件对颗粒物质量浓度有很大影响,其中0.5~1.0m/s的东南风条件下大气颗粒物污染最为严重.     

基于PMF和源示踪物比例法的大气羰基化合物来源解析:以南京市观测为例

大气羰基化合物在对流层大气化学中发挥着重要作用,其受到直接排放和二次生成的共同影响,来源研究面临挑战.本研究基于2017年3月在南京市开展的羰基化合物观测,分别利用源示踪物比例法(STR)和正交矩阵因子模型(PMF)对羰基化合物进行来源解析,并将二者结果进行比较,以探讨导致来源解析不确定性的因素.本研究共检测出11种羰...     

生物质锅炉羰基化合物排放特征分析

为了探讨生物质锅炉羰基化合物的排放特征,采用气袋采样-PFPH衍生-GC/MS分析的方法测量了6台生物质锅炉排放烟气中的21种羰基化合物.结果表明,这些生物质锅炉的烟气中羰基化合物排放特征存在明显差异,总体而言,己醛和丙醛浓度在测定的21种目标化合物中比重最高,分别占总量的29%~47%和19%~31%,其次为甲醛和丙酮,乙醛和壬醛.通过羰基化合物排放量与消耗的燃料质量比值估算了排放因子,6台锅炉羰基化合物排放因子介于3.06~18.29mg/kg之间,平均为9.45±6.05mg/kg.采用最大增量反应活性法（MIR）评价了羰基化合物的化学反应活性及臭氧生成潜势（OFP）,平均总的臭氧生成潜势（以O₃计）为5.97gO₃/gVOCs;己醛、丙醛、甲醛对OFP的贡献尤为明显,丙酮虽然占有较高的质量浓度,但对OFP的贡献较低.     

奥运前期与奥运期间北京市大气细颗粒物特征比较分析

利用城市生态系统研究站对北京市奥运前后(2008年6～9月)大气中细颗粒物(PM2.5)进行连续监测,获得不同阶段PM2.5日平均浓度的动态特征,分析气象因素、人为控制管理措施对颗粒物浓度的影响.结果表明,近北五环的生态中心站点(RCEES)颗粒物日均浓度平均值为0.067 mg.m-3,奥运期间的颗粒物浓度(0.060 mg.m-3)比奥运前期(0.081 mg.m-3)减少了约26%.而位于南二环市中心的教学植物园站点(JX)颗粒物浓度平均含量为0.078 mg.m-3.JX站点奥运期间的颗粒物浓度(0.069 mg.m-3)比奥运前期(0.095 mg.m-3)减少了约27%.各个阶段PM2.5的日变化都基本呈现双峰态势.第一个峰值出现在08:00～10:00左右,RCEES站点颗粒物浓度为0.068 mg.m-3,JX站点浓度值为0.089 mg.m-3;另一个峰值出现在晚20:00～22:00左右,RCEES和JX站点颗粒物浓度为0.079 mg.m-3和0.083 mg.m-3,这主要与上班交通高峰导致的尾气排放污染和道路扬尘污染等有关.研究气象参数发现奥运期间与奥运前期气象条件无显著差异,属于高温高湿风力不大的典型北京夏季天气条件.奥运期间颗粒物浓度与温度呈显著正相关(P<0.01),而与风速、相对湿度及降水相关性不显著(P>0.05).而连续多年大气污染综合治理措施和奥运空气质量保障措施的实施,产生了显著环境效益.在自然因素相差不大的条件下,人为控制因素对奥运期间颗粒物的下降起到主导作用.     

列车车厢内醛酮化合物的污染状况

建立了室内及公共场所空气中10种醛酮(甲醛、乙醛、丙烯醛、丙酮、丙醛、丁烯醛、丁醛、苯甲醛、环己酮、戊醛)的采集、前处理及分析方法,采样效率为92%～100%,回收率为91%～104%,检测限为0.26 ng/m³～0.82 ng/m³.调查评价了6辆列车车厢空气中醛酮的污染状况.结果表明,列车车厢空气中醛酮的总浓度为0.1591 mg/m³～0.2828 mg/m³,平均浓度为0.2330 mg/m³,其中甲醛、乙醛、丙酮的平均浓度分别为0.0922 mg/m³、0.0499 mg/m³、0.0580 mg/m³,占总平均浓度的42.6%、21.4%、24.9%.初步确定列车车厢空气中的醛酮化合物来自木制品和抽烟的混合源.乘客的醛酮吸入量约为0.043 mg/h～0.076 mg/h.     

Seasonal,diurnal and nocturnal variations of carbonyl compounds in the semi-urban environment of Orléans,France

Atmospheric carbonyls were measured at a semi-urban site in Orléans, France, from October 2010to July2011. Formaldehyde, acetaldehyde and acetone were found to be the most abundant carbonyls, with average concentrations of 3.1, 1.0, 2.0 ppb, respectively in summer, 2.3, 0.7, 2.2 ppb, respectively in autumn, 2.2, 1.0, 2.1 ppb, respectively in spring,and 1.5, 0.7, 1.1 ppb, respectively in winter. Photo-oxidation of volatile organic compounds(VOCs) was found to make a remarkable contribution to atmospheric carbonyls in the semi-urban site based on the distinct seasonal and diurnal variations of the carbonyls, as well as the significantly positive correlations between the carbonyls and ozone. The significantly negative correlations between NO x and O_3 as well as the carbonyls and the positive correlations between wind speed and O_3 as well as the carbonyls implied that the carbonyls and O_3 at the semi-urban site were probably formed during air mass transport from neighboring cities.     

The pollution levels, variation characteristics, sources and implications of atmospheric carbonyls in a typical rural area of North China Plain during winter

Atmospheric carbonyls were measured at a typical rural area of the North China Plain (NCP) from November 13 to December 24, 2017 to investigate the pollution characteristics, sources and environmental implications. Fifteen carbonyls were detected, and formaldehyde, acetaldehyde and acetone accounted for about 81% at most. The concentration of the total carbonyls in heavily polluted days was twice more than that in clean days. In contrast to other carbonyls, m-tolualdehyde exhibited relatively high concentrations in the clean days in comparison with the polluted days. The ratios of three principal carbonyls to CO showed similar daily variations at different pollution levels with significant daytime peaks. Multiple linear regression analysis revealed that the contributions of background, primary and secondary sources to three principal carbonyls showed similar variation trends from the clean level to the heavily polluted level. The OH formation rate of formaldehyde showed a similar variation trend to its photodegradation rate, reaching the peak value at noon, which is important to maintain relatively high OH levels to initiate the oxidation of various gas-phase pollutants for secondary pollutant formation at the rural site. OH radical consumption rate and ozone formation potential (OFP) calculations showed that formaldehyde and acetaldehyde were the dominant oxidative species among measured carbonyls. As for OH radical consumption, n-butyraldehyde and m-tolualdehyde were important contributors, while for ozone formation potential, n-butyraldehyde and propionaldehyde made significant contributions. In addition, the contribution of carbonyl compounds to secondary organic aerosol (SOA) formation was also important and needs further investigation.     

武汉军运会前后臭氧及其前体物的特征和来源

利用湖北省超级站2019年10~11月的臭氧、NO_x(=NO+NO₂)和102种VOCs物质的小时数据分析了军运会期间臭氧污染变化;基于DSMACC箱型模式模拟不同VOCs和NO_x浓度下臭氧的光化学生成敏感性;采用PMF模型对前体物VOCs进行源解析,并估算不同源类的臭氧生成潜势.结果显示,军运会保障前臭氧日最大8小时浓度(最大MDA8:219.51μg/m³)超过国家二级标准,保障期臭氧MDA8浓度(135.11μg/m³)明显下降,保障后浓度回升(140.98μg/m³).军运会保障前中期臭氧浓度的差异受气象条件影响更明显,而保障后臭氧浓度的上升主要是因为前体物浓度的大幅增加.根据DSMACC模拟的EKMA曲线,武汉市军运会期间臭氧的光化学生成主要受VOCs浓度变化的影响.进一步对VOCs进行源解析,结果显示,保障前VOCs对臭氧生成贡献较大的源类是燃烧源、石油化工和机动车,分别占23.0%、22.8%和22.5%;保障期间VOCs的主要来源是机动车(38.4%)和燃烧源(25.5%);保障后则主要是石油化工(32.6%)和燃料挥发(25.7%).三个阶段对比发现,军运会的保障方案对石油化工源减排效果明显,但对机动车和燃烧源排放的限制效果并不显著.武汉市应该更注重对燃烧、燃料挥发和机动车排放的治理.