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Comparison of different real time VOC measurement techniques in a ponderosa pine forest

机译:不同实时VOC测量技术在Ponderosa松树林中的比较

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Volatile organic compound (VOC) mixing ratios measured by five independent instruments are compared at a forested site dominated by ponderosa pine (Pinus Ponderosa) during the BEACHON-ROCS field study in summer 2010. The instruments included a Proton Transfer Reaction Time of Flight Mass Spectrometer (PTR-TOF-MS), a Proton Transfer Reaction Quadrupole Mass Spectrometer (PTR-MS), a Fast Online Gas-Chromatograph coupled to a Mass Spectrometer (GC/MS; TOGA), a Thermal Dissociation Chemical Ionization Mass Spectrometer (PAN-CIMS) and a Fiber Laser-Induced Fluorescence Instrument (FILIF). The species discussed in this comparison include the most important biogenic VOCs and a selected suite of oxygenated VOCs that are thought to dominate the VOC reactivity at this particular site as well as typical anthropogenic VOCs that showed low mixing ratios at this site. Good agreement was observed for methanol, the sum of the oxygenated hemiterpene 2-methyl-3-buten-2-ol (MBO) and the hemiterpene isoprene, acetaldehyde, the sum of acetone and propanal, benzene and the sum of methyl ethyl ketone (MEK) and butanal. Measurements of the above VOCs conducted by different instruments agree within 20%. The ability to differentiate the presence of toluene and cymene by PTR-TOF-MS is tested based on a comparison with GC-MS measurements, suggesting a study-average relative contribution of 74% for toluene and 26% for cymene. Similarly, 2-hydroxy-2-methylpropanal (HMPR) is found to interfere with the sum of methyl vinyl ketone and methacrolein (MVK + MAC) using PTR-(TOF)-MS at this site. A study-average relative contribution of 85% for MVK + MAC and 15% for HMPR was determined. The sum of monoterpenes measured by PTR-MS and PTR-TOF-MS was generally 20–25% higher than the sum of speciated monoterpenes measured by TOGA, which included α-pinene, β-pinene, camphene, carene, myrcene, limonene, cineole as well as other terpenes. However, this difference is consistent throughout the study, and likely points to an offset in calibration, rather than a difference in the ability to measure the sum of terpenes. The contribution of isoprene relative to MBO inferred from PTR-MS and PTR-TOF-MS was smaller than 12% while GC-MS data suggested an average of 21% of isoprene relative to MBO. This comparison demonstrates that the current capability of VOC measurements to account for OH reactivity associated with the measured VOCs is within 20%.
机译:在2010年夏季的Beachon-Rocs田间研究中,将五种独立仪器测量的挥发性有机化合物(VOC)混合比在2010年夏季的Beachon-Rocs田间研究中,在柚子 - Rocs田间研究中。该仪器包括飞行质谱仪的质子转移反应时间(PTR-TOF-MS),质子转移反应四极杆质谱仪(PTR-MS),快速在线气相色谱仪,耦合到质谱仪(GC / MS; TOGA),热解离化学电离质谱仪(锅 - CIMS)和光纤激光诱导的荧光仪器(FILIF)。在该比较中讨论的物种包括最重要的生物转霉和选定的含氧VOCs,据认为将该特定部位的VOC反应性占据主导地位,以及在该位点显示低混合比的典型的人为VOC。甲醇的良好协议,氧化溶质2-甲基-3-丁烯-2-醇(MBO)和溶质异戊二烯,乙醛,丙酮和丙酮和丙酮和甲基乙基酮和(梅克)和丁塔尔。由不同仪器进行的上述VOC的测量值在20%以内。基于与GC-MS测量的比较测试PTR-TOF-MS对甲苯和CYHENE的存在的能力,表明甲苯的74%的研究平均相对贡献和26%。类似地,发现2-羟基-2-甲基丙醛(HMPR)在本地位于PTR-(TOF)-MS中干扰甲基乙烯基酮和甲基丙酮(MVK + MAC)的总和。确定了MVK + MAC 85%的研究 - 平均相对贡献和15%的HMPR。通过PTR-MS和PTR-TOF-MS测量的单萜的总和通常比TOGA测量的标称单萜的总和高20-25%,其中包括α-拼蛋烯,β-PINENE,CAMPHENE,CARENE,氨基,柠檬烯,桉树型和其他萜烯。然而,这种差异在整个研究中是一致的,并且可能指向校准的偏移,而不是测量Terpenes的总和的差异。异戊二烯相对于PTR-MS和PTR-TOF-MS的贡献来自PTR-MS和PTR-TOF-MS的贡献小于12%,而GC-MS数据表明相对于MBO的平均21%的异戊二烯。该比较表明,VOC测量的电流能力解释与测量VOC相关的OH反应性在20%以内。
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