PTR-MS在线监测大气挥发性有机物研究进展

PTR-MS是近年来兴起的一种痕量挥发性有机物在线检测技术,它测量响应时间短,灵敏度高。已经广泛应用在环境监测领域。文章介绍了它的工作原理和装置结构,给出了一些大气挥发性有机物监测的例子,并对该在线监测技术的发展方向进行了一些展望。     

深圳大学城园区典型OVOCs污染特征与来源解析

采用质子转移反应质谱仪（PTR-MS）对深圳大学城园区2017年不同季节（分干湿两季）的6种典型OVOCs和其他非甲烷烃类（NMHCs）进行连续在线监测,分析其干湿季的浓度特征与日变化规律,并应用光化学龄的参数化方法开展OVOCs的来源解析.结果表明,在观测的6种OVOCs中,甲醇的平均浓度最高,达10×10^-9~12×10^-9,其次是乙酸、丙酮和乙醛,约2~5×10^-9,甲酸和丁酮的含量最低,仅1×10^-9~2×10^-9.通过日变化观察到的OVOCs湿季峰值浓度时间明显早于干季,乙醛表现出与臭氧（O₃）相似的日变化特征,揭示了其可能存在二次来源;甲醇和丁酮的峰值浓度时间均早于O₃,可能存在重要的一次排放源.采用光化学龄模型解析出日间污染物来源比例：在污染较重的干季,甲醇、乙醛、丙酮和丁酮的人为一次源占主导,甲酸和乙酸的二次源是主要贡献者;在较清洁的湿季,天然源成为乙醛、丙酮、丁酮、甲酸和乙酸的主要来源.     

Understanding primary and secondary sources of ambient oxygenated volatile organic compounds in Shenzhen utilizing photochemical age-based parameterization method

Oxygenated volatile organic compounds(OVOCs) are key intermediates in the atmospheric photooxidation process. To further study the primary and secondary sources of OVOCs,their ambient levels were monitored using a proton-transfer reaction mass spectrometer(PTR-MS) at an urban site in the Pearl River Delta of China. Continuous monitoring campaigns were conducted in the spring, summer, fall, and winter of 2016. Among the six types of OVOC species, the mean concentrations of methanol were the highest in each season(up to 13–20 ppbv), followed by those of acetone, acetaldehyde and acetic acid(approximately 2–4 ppbv), while those of formic acid and methyl ethyl ketone(MEK) were the lowest(approximately 1–2 ppbv). As observed from a diurnal variation chart, the OVOCs observed in Shenzhen may have been affected by numerous factors such as their primary and secondary sources and photochemical consumption. The photochemical age-based parameterization method was used to apportion the sources of ambient OVOCs. Methanol had significant anthropogenic primary sources but negligible anthropogenic secondary sources during all of the seasons. Acetone, MEK and acetic acid were mostly attributed to anthropogenic primary sources during each season with smaller contributions from anthropogenic secondary sources. Acetaldehyde had similar contributions from both anthropogenic secondary and anthropogenic primary sources throughout the year.Meanwhile, anthropogenic primary sources contributed the most to formic acid.     

质子转移反应质谱在线测量大气挥发性有机物及来源研究——以深圳夏季为例

含氧挥发性有机物(OVOCs)在光化学烟雾形成过程中起到重要作用,其分析技术在近些年才有突破性发展.为了解深圳大气中含氧挥发性有机物和NMHCs的组成和浓度的演变规律与来源特征,2011年夏季在深圳利用先进的质子转移反应质谱技术对①生物质燃烧示踪物、②生物源排放挥发性有机物、③芳香烃类以及④含氧挥发性有机物等4类VOCs进行了为期4个月的观测.结果显示,深圳OVOCs和NMHCs浓度水平普遍高于国外,且本地甲苯、甲醇和异戊二烯有较强排放,它们的浓度分别为(3.86±5.85)、(16.06±13.88)和(0.75±1.12)ppbv(parts per billion by volume:10-9),主要受本地的溶剂使用挥发以及夏季高温高日照的影响;不同类VOCs有不同的月际变化,但大部分VOCs浓度5月份最高,6月份最低,分析表明这是气象条件和排放源源强变化的综合作用结果;通过研究OVOCs的日变化曲线发现OVOCs不仅来源于一次源的排放,还源于NMHCs的二次转化,其中甲醇和丙酮可能还源于生物质燃烧,乙醛和MEK还受生物源排放的影响;最后结合反向轨迹发现深圳夏季源于洋面的气团对苯乙烯和C9芳香烃的传输作用较大,源于内陆的气团对MEK、乙醛和甲苯的传输作用较大,而甲醇、丙酮、苯等主要受本地源排放的控制.     

Biogas from the organic fraction of municipal solid waste: Dealing with contaminants for a solid oxide fuel cell energy generator

The present work investigates electricity production using a high efficiency electrochemical generator that employs as fuel a biogas from the dry anaerobic digestion of the organic fraction of municipal solid waste (OFMSW).The as-produced biogas contains several contaminants (sulfur, halogen, organic silicon and aromatic compounds) that can be harmful for the fuel cell: these were monitored via an innovative mass spectrometry technique that enables for in-line and real-time quantification.A cleaning trap with activated carbons for the removal of sulfur and other VOCs contained in the biogas was also tested and monitored by observing the different breakthrough times of studied contaminants.The electrochemical generator was a commercial Ni anode-supported planar Solid Oxide Fuel Cell (SOFC), tested for more than 300 h with a simulated biogas mixture (CH₄ 60 vol.%, CO₂ 40 vol.%), directly fed to the anode electrode. Air was added to promote the direct internal conversion of CH₄ to H₂ and CO via partial oxidation (POx).The initial breakthrough of H₂S from the cleaning section was also simulated and tested by adding ～1 ppm(v) of sulfur in the anode feed; a full recovery of the fuel cell performance after 24 h of sulfur exposure (～1 ppm(v)) was observed upon its removal, indicating the reliable time of anode exposure to sulfur in case of exhausted guard bed.     

Volatile organic compounds at swine facilities: A critical review

Volatile organic compounds (VOCs) are regulated aerial pollutants that have environmental and health concerns. Swine operations produce and emit a complex mixture of VOCs with a wide range of molecular weights and a variety of physicochemical properties. Significant progress has been made in this area since the first experiment on VOCs at a swine facility in the early 1960s. A total of 47 research institutions in 15 North American, European, and Asian countries contributed to an increasing number of scientific publications. Nearly half of the research papers were published by U.S. institutions.Investigated major VOC sources included air inside swine barns, in headspaces of manure storages and composts, in open atmosphere above swine wastewater, and surrounding swine farms. They also included liquid swine manure and wastewater, and dusts inside and outside swine barns. Most of the sample analyses have been focusing on identification of VOC compounds and their relationship with odors. More than 500 VOCs have been identified. About 60% and 10% of the studies contributed to the quantification of VOC concentrations and emissions, respectively. The largest numbers of VOC compounds with reported concentrations in a single experimental study were 82 in air, 36 in manure, and 34 in dust samples.The relatively abundant VOC compounds that were quantified in at least two independent studies included acetic acid, butanoic acid (butyric acid), dimethyl disulfide, dimethyl sulfide, iso-valeric, p-cresol, propionic acid, skatole, trimethyl amine, and valeric acid in air. They included acetic acid, p-cresol, iso-butyric acid, butyric acid, indole, phenol, propionic acid, iso-valeric acid, and skatole in manure. In dust samples, they were acetic acid, propionic acid, butyric acid, valeric acid, p-cresol, hexanal, and decanal. Swine facility VOCs were preferentially bound to smaller-size dusts.Identification and quantification of VOCs were restricted by using instruments based on gas Chromatography (GC) and liquid chromatography (LC) with different detectors most of which require time-consuming procedures to obtain results. Various methodologies and technologies in sampling, sample preparation, and sample analysis have been used. Only four publications reported using GC based analyzers and PTR-MS (proton-transfer-reaction mass spectrometry) that allowed continuous VOC measurement. Because of this, the majority of experimental studies were only performed on limited numbers of air, manure, or dust samples. Many aerial VOCs had concentrations that were too low to be identified by the GC peaks.Although VOCs emitted from swine facilities have environmental concerns, only a few studies investigated VOC emission rates, which ranged from 3.0 to 176.5 mg d⁻¹ kg⁻¹ pig at swine finishing barns and from 2.3 to 45.2 g d⁻¹ m⁻² at manure storages. Similar to the other pollutants, spatial and temporal variations of aerial VOC concentrations and emissions existed and were significantly affected by manure management systems, barn structural designs, and ventilation rates.Scientific research in this area has been mainly driven by odor nuisance, instead of environment or health concerns. Compared with other aerial pollutants in animal agriculture, the current scientific knowledge about VOCs at swine facilities is still very limited and far from sufficient to develop reliable emission factors.