广州市灰霾与非灰霾期间大气中的低分子量羰基化合物

采用2,4-二硝基苯肼衍生-高压液相色谱检测的方法测定了广州市大气中灰霾期和非灰霾期4种低分子量醛酮化合物(甲醛、乙醛、丙酮和丙醛).在灰霾期,4种化合物的含量在1.00-32.19μg·m-3,以乙醛的平均含量最高;非灰霾期以丙酮的平均含量最高,与非灰霾期相比,灰霾期的4种醛酮化合物含量明显增加,甲醛/乙醛和乙醛/丙醛浓度比值以及4种醛酮化合物的相关分析结果表明,广州市低分子量醛酮化合物主要来自人为排放源,并且灰霾期甲醛、乙醛和丙醛具有相似的源和汇,灰霾期人体对甲醛和乙醛的平均暴露水平(分别为55.2μg·d-1和62.7μg·d-1)是非灰霾期(分别为22.8μg·d-1和27.8 μg·d-1)的2倍以上.     

广州大气低分子量羰基化合物的季节变化

对广州市区荔湾和五山两个代表性采样点的低分子量羰基化合物(甲醛、乙醛、丙酮和丙醛)进行了季节变化研究.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检测.按冬、夏两季进行样品采集,每次连续采样4 d.研究发现丙酮质量浓度最高,其次是甲醛和乙醛.夏季的羰基化合物质量浓度值高于冬季的.除丙酮外,甲醛、乙醛、丙醛的质量浓度是荔湾采样点高于五山采样点.甲醛/乙醛、乙醛/丙醛质量浓度比值显示广州大气中羰基化合物主要与人为来源有关.羰基化合物之间的相关性冬季好于夏季,暗示羰基化合物冬季来源比夏季简单.羰基化合物的来源主要有汽车排放、大气光化学反应,还可能与植物排放、烟草烟气、实验室所用溶剂有关.     

大气中羰基化合物的研究进展

羰基化合物是大气中重要的毒性挥发性有机物.近lO年来国内外学者对大气羰基化合物进行了较多的调查和研究.文章对相关调查研究的主要发现进行了系统的综述.文献资料显示.国内的研究主要集中在北京、广州、青岛、杭州和香港.尤其是广州.在最常检测到的羰基化合物中,甲醛、乙醛和丙酮的浓度相对较高.绝大部分研究发现,羰基化合物浓度呈现市区和工业区的高于郊区或乡村的,室内的高于室外的,夏季的高于冬季的,并且有明显的日变化规律.很多研究者根据甲醛/乙醛(C1/C2)和乙醛/丙醛(C2/C3)浓度比以及不同羰基化合物间的相关性来推断羰基化合物的可能来源,这些可能来源包括汽车尾气、大气光化学反应等.但上述方法不能判断羰基化合物的准确来源及不同释放源的贡献率.作者认为,应该借助碳同位素分析方法或其他新技术来加强大气羰基化合物的释放源及其贡献率的研究.此外,大气羰基化合物在不同气候条件下的形成、反应、迁移和转化机理也值得进一步研究.     

长沙市大气挥发性有机物的组成与来源

在长沙市一个国家空气质量监测站附近采用罐采样方法采集环境全空气样品,利用三级冷阱预浓缩-GC/Dean-switch/FID/FID技术分析59种非甲烷碳氢化合物,同步采用2,4-二硝基苯肼(DNPH)-高效液相色谱法测定醛酮类化合物,研究非甲烷碳氢化合物及醛酮类化合物的组成与来源.结果表明,大气非甲烷碳氢化合物的总平均体积分数为(43.31±33.86)×10~(-9),其中异戊烷的体积分数最大;醛酮类化合物总浓度为(9.17±3.16)μg·m~(-3),主要为丙酮、甲醛和乙醛且其贡献了总浓度的90%以上.结合主成分分析法分析非甲烷碳氢化合物的来源,结果表明,汽油挥发、尾气排放及溶剂使用是大气非甲烷碳氢化合物的主要来源,分别对总浓度贡献了16.65%、16.61%、22.65%;进一步利用比值分析法表明苯系物的主要来源是汽车排放,醛酮类化合物符合城区的比值特征.     

采用Carbonyl色谱柱超高效液相色谱法分析13种醛酮化合物

醛酮类化合物具有慢性毒性,在日常的家具、塑料制品中多含有该类化合物,会自动释放至空气中,随着时间逐步积累而浓度增加,在此种环境下会对人的呼吸道和神经系统等产生损害,因此空气中醛酮类化合物受到人们的关注.国家环保总局最新颁布的标准GB27630—2011《乘用车内空气质量评价指南》中规定甲醛、乙醛和丙烯醛的含量分别不得超过0.10、     

酸雨地区大气中痕量低脂肪醛的分析

实验采用国产PT-C_(18)收集管富集大气中低碳脂肪醛,用2,4-二硝基苯肼与醛类生成苯腙,然后在高压液相色谱中测定。甲醛、乙醛,丙醛在形成衍生物后色谱分离效果良好,西南酸雨地区大气中低脂肪醛的测定证实了此法的可用性。     

北京市西城区居民室内空气低分子量羰基化合物污染调查

2009年11月—12月对北京市西城区7个社区210户家庭室内的低分子量羰基化合物进行了采样分析.实验采用2,4二-硝基苯肼（DNPH）涂布的硅胶柱采样,液相色谱分析检测.结果表明,所有家庭都检测到甲醛、乙醛、丙酮和丙烯醛,其质量浓度水平相对较高;室内装修会增加室内羰基化合物的污染;甲醛和乙醛人体暴露水平评估结果表明北...     

保定市餐饮源排放PM_(2.5)中有机污染物特征及来源分析

餐饮源是城市大气细颗粒物PM_(2.5)的一个重要来源,为了解餐饮源PM_(2.5)排放特征及来源,测定了室外烧烤和食堂两种不同类型餐饮源排放的PM_(2.5)浓度以及PM_(2.5)中的有机污染物;利用气相色谱-质谱仪(GC/MS)检测出主要污染物为正构烷烃、酸类、醛类、酮类、酯类、烯烃、多环芳烃等有机污染物,通过与大气对照样品的对比分析,对污染物的来源做了简要解析.比对结果显示,室外烧烤样品PM_(2.5)浓度为905.6±160.9μg·m~(-3)、食堂样品PM_(2.5)浓度为343.9±30.6μg·m~(-3)、大气对照样品PM_(2.5)浓度为76.7±1.7μg·m~(-3).室外烧烤是食堂排放PM_(2.5)质量浓度的2—3.4倍,是环境大气PM_(2.5)质量浓度的9.5—13.6倍.烧烤油烟排放的PM_(2.5)中有机物主要为有机酸(47.29%),其次是醛酮类(12.97%);校园食堂油烟样品中除了烷烃类(45.2%),脂肪酸类(11.76%)和醛酮类(8.84%)排放也较明显;脂肪酸类可能由动物脂肪灼烧产生,而醛、酮类物质可能来源于香精等食品添加剂的高温分解.大气对照样品中检测到少量醛酮类有机物,未检测到酸类有机物,由此推测醛、酮、酸可能是餐饮油烟中典型排放的污染物.     

长沙市夏季大气臭氧生成对前体物的敏感性分析

本文利用长沙市区环境空气质量监测站点在线观测资料,结合罐采样-三级冷阱预浓缩-气相色谱法分析非甲烷烃类化合物和衍生化-高效液相色谱法分析醛酮类化合物,基于观测的光化学模型分析了长沙市区2017年5月和9月部分时段臭氧生成对前体物的敏感性.结果表明,观测期间长沙市区臭氧浓度日变化均呈现典型的单峰特征,峰值浓度出现在15时左右,凌晨高浓度一氧化氮呈现对臭氧明显的滴定效应;5月非甲烷烃浓度和醛酮总浓度较9月高,非甲烷烃主要组成为烷烃和芳香烃类,其次为植物源烃类,而甲醛、乙醛和丙酮为醛酮类化合物主要组分.白天随着光化学过程的发展,非甲烷烃被逐渐消耗,其活性浓度随之降低.模型分析发现:5月份氮氧化物和植物源烃类对长沙市区臭氧生成贡献最大,削减氮氧化物对臭氧控制最为有效;而9月臭氧生成对烯烃和芳香烃最为敏感,削减人为源烯烃和芳香烃对臭氧控制最为有效.     

卤代醛/酮消毒副产物的生成潜能及其前驱物的结构特征

卤代醛和卤代酮类消毒副产物因具有"致畸、致癌、致突变"作用而倍受关注.对卤代醛/酮类消毒副产物控制及其前体物识别对饮用水安全保障具有重要意义.以大分子酸、疏水性酸、芳香族类亲水酸、亲水酸、糖类和氨基酸6类共14种常见有机物为对象,研究了不同有机物在氯化消毒过程中的卤代醛/酮生成潜力.结果表明,富里酸、柠檬酸、苹果酸、L-苏氨酸和L-天冬酰胺具有较高的卤代醛/酮生成势.有机物生成卤代醛/酮的过程包括2个阶段:前体物首先经氧化、脱羧等过程生成乙醛和丙酮,乙醛和丙酮被逐步氯代而生成氯代醛和氯代酮.实际水体的消毒实验表明,卤代醛/酮的生成势与水样中有机物的浓度无必然联系,但与水样中醇羟基及羰基官能团的含量呈正相关(R~2=0.69—0.98).     

Characteristics of carbonyls and volatile organic compounds (VOCs) in residences in Beijing,China

Volatile organic compounds (VOCs) and carbonyl compounds were measured both indoors and outdoors in 50 residences of Beijing in heating (December, 2011) and non-heating seasons (April/May, 2012). SUMMA canisters for VOCs and diffusive samplers for carbonyl compounds were deployed for 24 h at each site, and 94 compounds were quantified. Formaldehyde, acetone and acetaldehyde were the most abundant carbonyl compounds both indoors and outdoors with indoor median concentrations being 32.1, 21.7 and 15.3 μg·m⁻³, respectively. Ethane (17.6 μg·m⁻³), toluene (14.4 μg·m⁻³), propane (11.2 μg·m⁻³), ethene (8.40 μg·m⁻³), n-butane (6.87 μg·m⁻³), and benzene (5.95 μg·m⁻³) showed the high median concentrations in indoor air. Dichloromethane, p-dichlorobenzene (p-DCB) and toluene exhibited extremely high levels in some residences, which were related with a number of indoor emission sources. Moreover, isoprene, p-dichlorobenzene and carbonyls showed median indoor/outdoor (I/O) ratios larger than 3, indicating their indoor sources were prevailing. Chlorinated compounds like CFCs were mainly from outdoor sources for their I/O ratios being less than 1. In addition, indoor concentrations between two sampling seasons varied with different compounds. Carbonyl compounds and some chlorinated compounds had higher concentrations in the non-heating season, while alkanes, alkenes, aromatic compounds showed an increase in the heating season. Indoor concentration of VOCs and carbonyls were influenced by locations, interior decorations and indoor activities, however the specific sources for indoor VOCs and carbonyls could not be easily identified. The findings obtained in this study would significantly enhance our understandings on the prevalent and abundant species of VOCs as well as their concentrations and sources in Beijing residences.     

Indoor carbonyl compounds in an academic building in Beijing, China: concentrations and influencing factors

Carbonyl compounds in indoor air are of great concern for their adverse health effects. Between February and May, 2009, concentrations of 13 carbonyl compounds were measured in an academic building in Beijing, China. Total concentration of the detected carbonyls ranged from 20.7 to 189.1 μg·m^-3, and among them acetone and formaldehyde were the most abundant, with mean concentrations of 26.4 and 22.6 μg·m^-3, respectively. Average indoor concentrations of other carbonyls were below 10 μg·m^-3. Principal component analysis identified a combined effect of common indoor carbonyl sources and ventilation on indoor carbonyl levels. Diurnal variations of the carbonyl compounds were investigated in one office room, and carbonyl concentrations tended to be lower in the daytime than at night, due to enhanced ventilation. Average concentrations of carbonyl compounds in the office room were generally higher in early May than in late February, indicating the influence of temperature. Carbonyl source emission rates from both the room and human occupants were estimated during two lectures, based on one-compartment mass balance model. The influence of human occupants on indoor carbonyl concentrations varies with environmental conditions, and may become significant in the case of a large human occupancy.     

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.     

13C isotope evidence for photochemical production of atmospheric formaldehyde, acetaldehyde, and acetone pollutants in Guangzhou

Ambient formaldehyde, acetaldehyde, and acetone are harmful air pollutants with potential carcinogenic effects on human health. They are considered as important photochemical products from photo-oxidation of atmospheric hydrocarbons. However, little is known on the effet of photodegradation of air pollutants on δ¹³C values. Here, we report the first ¹³C isotope evidence for the photochemical production of ambient formaldehyde, acetaldehyde, and acetone. Air samples were collected each day during early morning, noon, early afternoon, and late afternoon on 17–19 September 2008 in Guangzhou by drawing air through 2,4-dinitrophenylhydrazine-coated cartridges. The samples were analyzed using high-performance liquid chromatography for concentration analysis and then using gas chromatography-combustion-isotope ratio mass spectrometry for δ¹³C analysis. Our results show that ambient formaldehyde, acetaldehyde, and acetone were enriched by 1–5 ‰ in ¹³C in the early afternoon relative to other sampling durations, and they also exhibited the highest concentrations in the early afternoon. Measured δ¹³C values of formaldehyde, acetaldehyde, and acetone were in the range from ?37.15 to ?29.01 ‰. The observed enrichment in ¹³C implied important photochemical production together with the highest concentrations in the early afternoon. Especially, measured δ¹³C range from ?37.15 to ?29.01 ‰ was in accordance with forecasted δ¹³C range from ?43 to ?28 ‰ based on the mass balance in ¹³C between the carbonyls and its major hydrocarbon precursors, providing important ¹³C isotope evidence for the photochemical production of ambient formaldehyde, acetaldehyde, and acetone.     

Carbonyl compound leaching from polyethylene terephthalate into bottled water under sunlight exposure

Polyethylene terephthalate bottles containing natural spring water were used to study the leaching effect of carbonyl compounds after one year storage under real conditions of exposure. Ultraviolet-B and ultraviolet-A spectra of direct sunlight were acquired during the experiment. Leaching of acetone, acetaldehyde, and formaldehyde reached steady state after 210 days of outdoor storage, with the following concentrations: 434 ± 22, 345 ± 18, and 94 ± 5 µg/L, respectively. The increase due to sunlight exposure in comparison with laboratory storage in the dark was around 10%, 16%, and 36%. The leaching process of all three carbonyl compounds was found to follow the first-order kinetics. Photo-degradation of Polyethylene terephthalate bottles and the appearance of carboxyl end-groups were followed by attenuated total reflectance infrared spectra. After 313 days of storage under direct sunlight, new peaks appeared in the regions of 1770–1920 cm^?1 and 1685–1490 cm^?1. Cations, anions, total dissolved solids, pH, and conductivity were also measured during the storage period. Additionally, microbiological measurements as well as statistical analyses were also carefully discussed.     

珠江三角洲冲积平原种植热带果树的土壤条件探讨

以广州市番禺区万顷沙十五涌的土壤为例，探讨珠江三角洲冲积平原种植热带果树的土壤条件。该地土壤位于珠江三角洲冲积平原，是由工人围海造田而成的，有关部门计划在此大面积种植木瓜、杨桃、番石榴等热带果树。通过在种植果树前进行土壤本底调查，摸清土壤养分含量状况，找出土壤存在问题，并结合果树生长的需要，提出土壤利用改良意见。降低地下水位，合理施肥，建立合理的间套作制度，是提高和稳定土壤肥力的基本措施。     

环渤海北部沿海地区表层土壤中PAHs的污染特征及风险评价

系统采集了环渤海北部沿海地区31个表层土壤样品,利用GC/MS分析了16种USEPA优控多环芳烃(PAHs)的含量和组分特征,运用主成分因子载荷法揭示了其污染来源,并初步评价了其风险水平.结果表明,沿海地区65%的土壤已被污染,最高污染样点PAHs含量达920.4ng·g-1,平均含量309.5ng·g-1,与国内外相关研究比较,处于中低等污染水平.各类燃料的不完全燃烧是该地区土壤中PAHs的主要来源,石油类挥发或泄漏对采油区土壤中PAHs的累积影响显著.     

Indoor air quality in elementary schools of Lisbon in spring

Analysis of indoor air quality (IAQ) in schools usually reveals higher levels of pollutants than in outdoor environments. The aims of this study are to measure indoor and outdoor concentrations of NO₂, speciated volatile organic compounds (VOCs) and carbonyls at 14 elementary schools in Lisbon, Portugal. The investigation was carried out in May–June 2009. Three of the schools were selected to also measure comfort parameters, such as temperature and relative humidity, carbon dioxide (CO₂), carbon monoxide (CO), total VOCs, and bacterial and fungal colony-forming units per cubic metre. Indoor concentrations of CO₂ in the three main schools indicated inadequate classroom air exchange rates. The indoor/outdoor (I/O) NO₂ ratio ranged between 0.36 and 0.95. At the three main schools, the total bacterial and fungal colony-forming units (CFU) in both indoor and outdoor air were above the advised maximum value of 500 CFU/m³ defined by Portuguese legislation. The aromatic compounds benzene, toluene, ethylbenzene and xylenes, followed by ethers, alcohols and terpenes, were usually the most abundant classes of VOCs. In general, the indoor total VOC concentrations were markedly higher than those observed outdoors. At all locations, indoor aldehyde levels were higher than those observed outdoors, particularly for formaldehyde. The inadequate ventilation observed likely favours accumulation of pollutants with additional indoor sources.     

预浓缩/柱箱制冷GCMS/FID法测定大气中117种挥发性有机物

建立了罐采样、吸附剂辅助电子制冷预浓缩-柱箱制冷GCMS/FID同时测定大气中117种挥发性有机物(VOCs)的方法.样品经填充吸附剂的电子制冷预浓缩系统除水、除CO2、浓缩和热脱附后,采用柱箱制冷及GCMS/FID的多维切割单元,将5种C2-C3组分切到二维色谱柱进行分离并进入FID检测,甲醛及其他111种VOCs组...     

应用紫外及荧光光谱法研究三种醛类污染物对牛腺DNA的损伤作用

应用紫外光谱移动法和溴乙锭荧光法对三种醛类化合物与牛腺ＤＮＡ的加合以及它们引起的ＤＮＡ－ＤＮＡ交联进行了检测。结果表明,甲醛和乙醛能够与ＤＮＡ形成共价加合物,与四种脱氧核苷加合顺序分别为ｄＧ〉ｄＣ〉ｄＡ〉ｄＴ和ｄＡ〉ｄＧ〉ｄＣ〉ｄＴ,丙烯醛与ＤＮＡ的加合不能用紫外光谱移动法测定。甲醛能够显著地引起ＤＮＡ－ＤＮＡ的交联;乙醛也有这种作用,但不显著;丙烯醛的交联作用未测出,可能是由于羰基碳正电性较弱,