采用质子传递反应-飞行时间质谱仪(Proton Transfer Reaction-Time of Flight-Mass Spectrometry,PTR-TOFMS)与气相色谱-质谱联用技术(Gas Chromatography-Mass Spectrometer,GC-MS)对不同品种武夷岩茶(水仙、肉桂)香气成分进行分析,结...采用质子传递反应-飞行时间质谱仪(Proton Transfer Reaction-Time of Flight-Mass Spectrometry,PTR-TOFMS)与气相色谱-质谱联用技术(Gas Chromatography-Mass Spectrometer,GC-MS)对不同品种武夷岩茶(水仙、肉桂)香气成分进行分析,结果表明:武夷水仙以反式橙花叔醇、(E,E)-2,4-庚二烯醛、芳樟醇及其氧化物等为主;武夷肉桂是反式橙花叔醇、α-法尼烯、苯甲醛为主,且在武夷山肉桂中存在高浓度的m/z 207、223、281、291几个未知化合物。2种分析技术所检测到的香气成分和相对含量比例差异显著,两者各有优劣,相互补充,联合分析更加完整,更有利于准确地进行香气分析,同时发现PTR-TOF-MS法更能真实地反映茶叶香气的完整信息。展开更多
The characteristics of wintertime volatile organic compounds(VOCs)in the North China Plain(NCP)region are complicated and remain obscure.VOC measurements were conducted by a proton transfer reaction time-of-flight mas...The characteristics of wintertime volatile organic compounds(VOCs)in the North China Plain(NCP)region are complicated and remain obscure.VOC measurements were conducted by a proton transfer reaction time-of-flight mass spectrometer(PTR-ToF-MS)at a rural site in the NCP from November to December 2018.Uncalibrated ions measured by PTRToF-MS were quantified and the overall VOC compositions were investigated by combining the measurements of PTR-ToF-MS and gas chromatography-mass spectrometer/flame ionization detector(GC-MS/FID).The measurement showed that although atmospheric VOCs concentrations are often dominated by primary emissions,the secondary formation of oxygenated VOCs(OVOCs)is non-negligible in the wintertime,i.e.,OVOCs accounts for 42%±7%in the total VOCs(151.3±75.6 ppbV).We demonstrated that PTR-MS measurements for isoprene are substantially overestimated due to the interferences of cycloalkanes.The chemical changes of organic carbon in a pollution accumulation period were investigated,which suggests an essential role of fragmentation reactions for large,chemically reduced compounds during the heavy-polluted stage in wintertime pollution.The changes of emission ratios of VOCs between winter 2011 and winter 2018 in the NCP support the positive effect of“coal to gas”strategies in curbing air pollutants.The high abundances of some key species(e.g.oxygenated aromatics)indicate the strong emissions of coal combustion in wintertime of NCP.The ratio of naphthalene to C8 aromatics was proposed as a potential indicator of the influence of coal combustion on VOCs.展开更多
Green leaf volatiles（GLVs） emitted by plants after stress or damage induction are a major part of biogenic volatile organic compounds（BVOCs）. Proton transfer reaction time-of-flight mass spectrometry（PTR-TOF-MS）...Green leaf volatiles（GLVs） emitted by plants after stress or damage induction are a major part of biogenic volatile organic compounds（BVOCs）. Proton transfer reaction time-of-flight mass spectrometry（PTR-TOF-MS） is a high-resolution and sensitive technique for in situ GLV analyses, while its performance is dramatically influenced by humidity, electric field,etc. In this study the influence of gas humidity and the effect of reduced field（E/N） were examined in addition to measuring calibration curves for the GLVs. Calibration curves measured for seven of the GLVs in dry air were linear, with sensitivities ranging from 5 to10 ncps/ppbv（normalized counts per second/parts per billion by volume）. The sensitivities for most GLV analyses were found to increase by between 20% and 35% when the humidity of the sample gas was raised from 0% to 70% relative humidity（RH） at 21°C, with the exception of（E）-2-hexenol. Product ion branching ratios were also affected by humidity,with the relative abundance of the protonated molecular ions and higher mass fragment ions increasing with humidity. The effect of reduced field（E/N） on the fragmentation of GLVs was examined in the drift tube of the PTR-TOF-MS. The structurally similar GLVs are acutely susceptible to fragmentation following ionization and the fragmentation patterns are highly dependent on E/N. Overall the measured fragmentation patterns contain sufficient information to permit at least partial separation and identification of the isomeric GLVs by looking at differences in their fragmentation patterns at high and low E/N.展开更多
文摘采用质子传递反应-飞行时间质谱仪(Proton Transfer Reaction-Time of Flight-Mass Spectrometry,PTR-TOFMS)与气相色谱-质谱联用技术(Gas Chromatography-Mass Spectrometer,GC-MS)对不同品种武夷岩茶(水仙、肉桂)香气成分进行分析,结果表明:武夷水仙以反式橙花叔醇、(E,E)-2,4-庚二烯醛、芳樟醇及其氧化物等为主;武夷肉桂是反式橙花叔醇、α-法尼烯、苯甲醛为主,且在武夷山肉桂中存在高浓度的m/z 207、223、281、291几个未知化合物。2种分析技术所检测到的香气成分和相对含量比例差异显著,两者各有优劣,相互补充,联合分析更加完整,更有利于准确地进行香气分析,同时发现PTR-TOF-MS法更能真实地反映茶叶香气的完整信息。
基金supported by the National Key R&D Plan of China(No.2019YFE0106300)the National Natural Science Foundation of China(No.41877302)+3 种基金Guangdong Natural Science Funds for Distinguished Young Scholar(No.2018B030306037)Key-Area Research and Development Program of Guangdong Province(No.2019B110206001)Guangdong Innovative and Entrepreneurial Research Team Program(No.2016ZT06N263)supported by Special Fund Project for Science and Technology Innovation Strategy of Guangdong Province(No.2019B121205004)
文摘The characteristics of wintertime volatile organic compounds(VOCs)in the North China Plain(NCP)region are complicated and remain obscure.VOC measurements were conducted by a proton transfer reaction time-of-flight mass spectrometer(PTR-ToF-MS)at a rural site in the NCP from November to December 2018.Uncalibrated ions measured by PTRToF-MS were quantified and the overall VOC compositions were investigated by combining the measurements of PTR-ToF-MS and gas chromatography-mass spectrometer/flame ionization detector(GC-MS/FID).The measurement showed that although atmospheric VOCs concentrations are often dominated by primary emissions,the secondary formation of oxygenated VOCs(OVOCs)is non-negligible in the wintertime,i.e.,OVOCs accounts for 42%±7%in the total VOCs(151.3±75.6 ppbV).We demonstrated that PTR-MS measurements for isoprene are substantially overestimated due to the interferences of cycloalkanes.The chemical changes of organic carbon in a pollution accumulation period were investigated,which suggests an essential role of fragmentation reactions for large,chemically reduced compounds during the heavy-polluted stage in wintertime pollution.The changes of emission ratios of VOCs between winter 2011 and winter 2018 in the NCP support the positive effect of“coal to gas”strategies in curbing air pollutants.The high abundances of some key species(e.g.oxygenated aromatics)indicate the strong emissions of coal combustion in wintertime of NCP.The ratio of naphthalene to C8 aromatics was proposed as a potential indicator of the influence of coal combustion on VOCs.
基金supported by the Chinese National Natural Science Foundation (41175110)the funding for the Distinguished Professor of Jiangsu Province
文摘Green leaf volatiles（GLVs） emitted by plants after stress or damage induction are a major part of biogenic volatile organic compounds（BVOCs）. Proton transfer reaction time-of-flight mass spectrometry（PTR-TOF-MS） is a high-resolution and sensitive technique for in situ GLV analyses, while its performance is dramatically influenced by humidity, electric field,etc. In this study the influence of gas humidity and the effect of reduced field（E/N） were examined in addition to measuring calibration curves for the GLVs. Calibration curves measured for seven of the GLVs in dry air were linear, with sensitivities ranging from 5 to10 ncps/ppbv（normalized counts per second/parts per billion by volume）. The sensitivities for most GLV analyses were found to increase by between 20% and 35% when the humidity of the sample gas was raised from 0% to 70% relative humidity（RH） at 21°C, with the exception of（E）-2-hexenol. Product ion branching ratios were also affected by humidity,with the relative abundance of the protonated molecular ions and higher mass fragment ions increasing with humidity. The effect of reduced field（E/N） on the fragmentation of GLVs was examined in the drift tube of the PTR-TOF-MS. The structurally similar GLVs are acutely susceptible to fragmentation following ionization and the fragmentation patterns are highly dependent on E/N. Overall the measured fragmentation patterns contain sufficient information to permit at least partial separation and identification of the isomeric GLVs by looking at differences in their fragmentation patterns at high and low E/N.
