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...     

徐州大气中醛酮化合物污染特征初步研究

优化了大气中15种醛酮类化合物的测定方法,选择徐州市区四个采样点,在臭氧浓度较高的4-9月开展为期两年的连续监测,分析其月度、年度组分和浓度水平及不同采样点污染特征。结果表明：优化后的方法实现丙酮和丙烯腈分离的同时,分析效率比国标方法提高近3倍;与其他城市相比,徐州醛酮类化合物浓度处于中等污染水平,2021年浓度较2020年低;醛酮类化合物受温度和人为因素影响较大,所有点位在平均气温最高的8月份浓度出现高值,位于4#点位由于受人为影响较大,醛酮类化合物浓度相比于其他点位浓度稍高。     

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.     

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.      

青岛市大气中醛酮类化合物的分析及浓度变化

自1997年12月～1998年7月,在覆盖整个青岛市区布设了6个采样点,用2,4-二硝基苯肼HPLC法测定了11种醛酮类羰基化合物在不同季节、不同时间的浓度.青岛市大气中甲醛、乙醛、丙酮及醛酮总量的平均浓度冬季分别为3.64,4.18,2.50,13.9mg/m3,夏季分别为9.95, 7.00,5.75,26.9mg/m3,夏季的浓度明显高于冬季,青岛市大气中甲醛占总羰基化合物的26.2%～37%,乙醛、丙酮分别占总羰基化合物的26.0%～30.1%和18.0%～21.4%.甲醛+乙醛+丙酮之和占总羰基化合物的74.3%～84.3%,甲醛和乙醛在冬、夏两季的相关性较差(R2=0.43),而乙醛和丙酮在夏季具有较强的相关性(R2=0.7399).     

大气中醛酮类羰基化合物的研究进展

本文从大气污染物发生光化学反应产生醛酮类化合物的反应机理，大气中醛酮类物质的分析方法、国内外对大气中醛酮类物质的研究状况及时空变化规律三个方面综述了大气中醛酮类物质的研究状况。     

广州大气挥发性醛酮类化合物的污染特征及来源研究

采用DNPH-HPLC-UV分析方法,研究了2006年广州夏季空气污染较严重日17种挥发性醛酮类化合物的污染特征及其初步来源.结果表明,广州大气中主要的醛酮类污染物是丙酮、甲醛、 2-丁酮和乙醛,其日均浓度分别为10.84、 9.29、 8.35和8.0 μg·m^-3,占总醛酮类化合物日均浓度的72.29%.城区省站测点总醛酮类化合物日均浓度最高,达到59.66 μg·m^-3,而郊区从化测点的总醛酮类化合物日均浓度最低,为43.51 μg·m^-3.各种化合物在不同垂直高度的采样点表现出不一致的浓度变化规律,而在水平方向上均表现出昼间明显高于夜间的日变化规律.大气中甲醛、乙醛和丙酮相关性好,具有较好的同源特征,而C1/C2、C2/C3比值分别为1.12、 7.51,反映出机动车尾气排放对大气醛酮类化合物具有相当重要的贡献.     

北京市典型餐饮企业油烟中醛酮类化合物污染特征

醛酮类化合物作为餐饮油烟的组成物质之一,是挥发性有机物(volatile organic compounds,VOCs)中化学反应活性较强的一类物质.但目前国内还没有针对餐饮源醛酮类化合物的排放特征进行较为系统的研究.为进一步明确餐饮源醛酮类化合物排放水平和控制现状,获取城市群餐饮源VOCs排放控制决策依据,本研究选取北京市8家不同类型的餐饮企业,采用涂布2,4-二硝基苯肼(DNPH)的硅胶采样管进行油烟样品采集,用超高效液相色谱(UPLC)对油烟样品中的醛酮类化合物进行测定.结果表明按基准风量折算后,8家餐饮企业排放的油烟中醛酮类化合物浓度高低依次是:烤鸭中式烧烤家常菜西式快餐学校食堂中式快餐川菜淮扬菜.餐饮企业油烟中醛酮类化合物(C1~C9)浓度水平范围为115.47~1 035.99μg·m-3.不同类型餐饮企业油烟中醛酮类化合物组分构成存在较为明显的差异,中式餐饮企业醛酮类化合物C1~C3物质所占比例均在40%以上.快餐类餐饮企业醛酮类化合物C4~C9所占比例明显高于其他类型餐饮企业.从醛酮类化合物控制现状来看,北京市目前主流高压静电式油烟净化器对醛酮类化合物的去除效果十分有限.     

沈阳市环境空气中醛酮类化合物污染现状初探

通过对沈阳地区环境空气中醛酮类化合物的测定,初步了解其醛酮类化合物的污染现状。采用2,4-二硝基苯肼吸附柱采集环境空气样品,高效液相色谱法对样品进行分析。结果表明:沈阳市5个监测点位中冬季浑南二点位醛酮类污染物浓度最低,冬季二毛点位醛酮类污染物浓度最高。冬夏两季的环境空气中均检出丙酮和乙醛,冬季醛酮类污染物浓度总和高于夏季。     

大气中醛的分析方法探讨

对目前我国大气监测中推荐的测定甲醛的酚试剂法和乙酰丙酮法作了改进,酚试剂法将反应时间30min改为80min,乙酰丙酮法将在室温下反应120min改为在70℃水浴中反应5min。干扰实验表明,其他醛类对乙酰丙酮法测甲醛无干扰,所测结果为甲醛,酚试剂法所测结果不仅为甲醛同时还有乙醛等其他醛类,因此可用它代表总醛。     

Pollution survey of carbonyl compounds in train air

The train is an important vehicle in China, but its air quality has important impacts on passengers’ health. In this work, pollution from carbonyl compounds was measured in the air of six trains. The objectives of this work were to investigate carbonyl compound levels in selected air from trains, identify their emission sources, and assess the intake of carbonyl compounds for passengers. The methods for sampling and analyzing 10 carbonyl compounds such as formaldehyde, acetaldehyde, acrolein, acetone, propionaldehyde, crotonaldehyde, butyraldehyde, benzaldehyde, cyclohexanone, and valeraldehyde in indoor air were proposed with the sampling efficiency, recovery, and detection limit being 92%–100%, 91%–104%, and 0.26–0.82 ng/m³, respectively. It was indicated that the total concentrations of carbonyl compounds were 0.159–0.2828 mg/m³ with the average concentration of 0.2330 mg/m³. The average concentrations of form aldehyde, acetaldehyde and acetone were 0.0922, 0.0499, and 0.0580 mg/m³, accounting for 42.6%, 21.4%, and 24.9% of the total concentrations of carbonyl compounds, respectively. The carbonyl compounds probably came from woodwork and cigarette smoking. The intake of carbonyl compounds for the passengers was approximately 0.043–0.076 mg/h. The carbonyl compounds in train air could be harmful to human health. Translated from Environmental Science, 2006, 27(1) 91–94 [译自: 环境科学]     

Characteristics of odorous carbonyl compounds in the ambient air around a fishery industrial complex of Yeosu, Korea

In this study,the amounts of odorous carbonyl compounds(OCCs) including acetaldehyde(Acet-A),propionaldehyde(Pron-A),butylaldehyde(Buty-A),iso-valeric aldehyde(Iso-Vale-A) and n-valeric aldehyde(N-Vale-A) emitted from a fishery industrial complex near the exhibition facilities of "Expo 2012 Yeosu Korea" were measured.Acet-A was found to be the most abundant OCC,and the total concentrations of the OCCs were the highest in the summer.However,due to vehicular exhaust and photochemical reactions,the concentrations of some of the OCCs presented their highest levels in the fall.A significant correlation between Acet-A and Buty-A was found at the major fishery facilities(r = 0.816,p = 1.87E-15,n = 60) and at the border areas(r = 0.809,p = 3.40E-12,n = 48) of this fishery industrial complex.The concentrations of OCCs at the border areas were not worse than those at the urban areas in other places,indicating that the concentrations of ambient OCCs at the border areas were not greatly influenced by manmade activities.     

Characteristics and anthropogenic sources of carbonyl sulfide in Beijing

Atmospheric mixing ratios of carbonyl sulfide(COS) in Beijing were intensively measured from March 2011 to June 2013. COS mixing ratios exhibited distinct seasonal variation, with a maximum average value of 849 ± 477 pptv in winter and a minimal value of 372 ± 115 pptv in summer. The seasonal variation of COS was mainly ascribed to the combined effects of vegetation uptake and anthropogenic emissions. Two types of significant linear correlations(R2 0.66) were found between COS and CO during the periods from May to June and from October to March, with slopes(ΔCOS/ΔCO) of 0.72 and 0.14 pptv/ppbv, respectively. Based on the emission ratios of COS/CO from various sources, the dominant anthropogenic sources of COS in Beijing were found to be vehicle tire wear in summer and coal burning in winter. The total anthropogenic emission of COS in Beijing was roughly estimated as 0.53 ± 0.02 Gg/year based on the local CO emission inventory and the ΔCOS/ΔCO ratios.     

Characteristics and anthropogenic sources of carbonyl sulfide in Beijing

Atmospheric mixing ratios of carbonyl sulfide (COS) in Beijing were intensively measured from March 2011 to June 2013. COS mixing ratios exhibited distinct seasonal variation, with a maximum average value of 849 ± 477 pptv in winter and a minimal value of 372 ± 115 pptv in summer. The seasonal variation of COS was mainly ascribed to the combined effects of vegetation uptake and anthropogenic emissions. Two types of significant linear correlations (R² > 0.66) were found between COS and CO during the periods from May to June and from October to March, with slopes (ΔCOS/ΔCO) of 0.72 and 0.14 pptv/ppbv, respectively. Based on the emission ratios of COS/CO from various sources, the dominant anthropogenic sources of COS in Beijing were found to be vehicle tire wear in summer and coal burning in winter. The total anthropogenic emission of COS in Beijing was roughly estimated as 0.53 ± 0.02 Gg/year based on the local CO emission inventory and the ΔCOS/ΔCO ratios.     

Characteristics and anthropogenic sources of carbonyl sulfide in Beijing

Atmosphericmixing ratios of carbonyl sulfide (COS) in Beijingwere intensivelymeasured from March 2011 to June 2013. COS mixing ratios exhibited distinct seasonal variation, with a maximumaverage value of 849 ± 477 pptv in winter and a minimal value of 372 ± 115 pptv in summer. The seasonal variation of COS was mainly ascribed to the combined effects of vegetation uptake and anthropogenic emissions. Two types of significant linear correlations (R² > 0.66) were found between COS and CO during the periods from May to June and from October to March, with slopes (ΔCOS/ΔCO) of 0.72 and 0.14 pptv/ppbv, respectively. Based on the emission ratios of COS/CO from various sources, the dominant anthropogenic sources of COS in Beijing were found to be vehicle tire wear in summer and coal burning in winter. The total anthropogenic emission of COS in Beijing was roughly estimated as 0.53 ± 0.02 Gg/year based on the local CO emission inventory and the ΔCOS/ΔCO ratios.     

环境大气中半/中等挥发性有机物(S/IVOCs)的测量技术进展

总结了环境大气中半/中等挥发性有机物（S/IVOCs）的主要测量技术及其进展,重点介绍了基于气相色谱技术和化学电离质谱技术的测量方法.S/IVOCs的测量主要由气相色谱技术开始发展,并随着质谱技术的发展而不断发展.基于气相色谱技术的测量方法,能够直接测量非极性化合物,但在面对组分多达千万种的复杂体系时,传统的一维色谱相对耗时,而且由于峰容量不够,峰重叠现象十分严重,难以实现全组分的准确分离.新近发展的多维分离系统如全二维气相色谱,通过正交的分离系统,能够实现复杂体系中物种组分的准确、快速分离.目前基于化学电离质谱技术的在线测量方法已经逐渐应用于S/IVOCs的测量,虽然在物种定性方面相对较弱,但其可提供高时间分辨率的测量结果,帮助分析S/IVOCs在大气中的快速变化.在未来的研究中,高时间分辨率和全组分准确测量是S/IVOCs研究的关键.     

环境大气中半/中等挥发性有机物(S/IVOCs)的测量技术进展

总结了环境大气中半/中等挥发性有机物（S/IVOCs）的主要测量技术及其进展,重点介绍了基于气相色谱技术和化学电离质谱技术的测量方法.S/IVOCs的测量主要由气相色谱技术开始发展,并随着质谱技术的发展而不断发展.基于气相色谱技术的测量方法,能够直接测量非极性化合物,但在面对组分多达千万种的复杂体系时,传统的一维色谱相对耗时,而且由于峰容量不够,峰重叠现象十分严重,难以实现全组分的准确分离.新近发展的多维分离系统如全二维气相色谱,通过正交的分离系统,能够实现复杂体系中物种组分的准确、快速分离.目前基于化学电离质谱技术的在线测量方法已经逐渐应用于S/IVOCs的测量,虽然在物种定性方面相对较弱,但其可提供高时间分辨率的测量结果,帮助分析S/IVOCs在大气中的快速变化.在未来的研究中,高时间分辨率和全组分准确测量是S/IVOCs研究的关键.     

Real-world emission characteristics of carbonyl compounds from agricultural machines based on a portable emission measurement system

Emissions of carbonyl compounds from agricultural machines cannot be ignored. Carbonyl compounds can cause the formation of ozone (O₃) and secondary organic aerosols, which can cause photochemical smog to form. In this study, 20 agricultural machines were tested using portable emission measurement system (PEMS) under real-world tillage processes. The exhaust gases were sampled using 2,4-dinitrophenylhydrazine cartridges, and 15 carbonyl compounds were analyzed by high-performance liquid chromatography. Carbonyl compound emission factors for agricultural machines were 51.14–3315.62 mg/(kg-fuel), and were 2.58 ± 2.05, 0.86 ± 1.07 and 0.29 ± 0.20 g/(kg-fuel) for China 0, China II and China III emission standards, respectively. Carbonyl compound emission factor for sowing seeds of China 0 agricultural machines was 3.32 ± 1.73 g/(kg-fuel). Formaldehyde, acetaldehyde and acrolein were the dominant carbonyl compounds emitted. Differences in emission standards and tillage processes impact ozone formation potential (OFP). The mean OFP was 20.15 ± 16.15 g O₃/(kg-fuel) for the China 0 emission standard. The OFP values decreased by 66.9% from China 0 to China II, and 67.4% from China II to China III. The mean OFP for sowing seeds of China 0 agricultural machines was 25.92 ± 13.84 g O₃/(kg-fuel). Between 1.75 and 24.22 times more ozone was found to be formed during sowing seeds than during other processes for China 0 and China II agricultural machines. Total carbonyl compound emissions from agricultural machines in China was 19.23 Gg in 2019. The results improve our understanding of carbonyl compound emissions from agricultural machines in China.     

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 25 th to 27 th 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 was5.8 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 and0.40 ppb/ppb, respectively. More research on industrial carbonyl emission characteristics is needed to understand carbonyl sources better.     

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.