气相色谱-脉冲氦离子化检测法(GC-PDHID)分析大气中分子氢(H2)浓度

在商用Agilent7890A型气相色谱的基础上,通过自组装、集成及调试,建成了基于气相色谱-脉冲氦离子化检测器(GCPDHID,gas chromatography-pulsed discharge helium ionization detector)观测大气中H2浓度的高精度分析系统.系统采用保留时间定性,峰高定量,最低检测限约为1×10-9(摩尔分数,下同).对浓度约为600×10-9的标气重复进样140次用峰高定量的标准偏差优于0.3×10-9.系统对409.30×10-9~867.74×10-9浓度范围的大气H2具有较好的线性响应.系统使用2瓶标气定量,满足世界气象组织/全球大气观测计划(WMO/GAW)对本底大气H2观测的比对目标.2013年1~11月在广州城区开展大气H2采样观测,采集的样品运回北京实验室利用所建系统进行浓度分析,结果表明该城区大气H2浓度在450×10-9~700×10-9之间波动,观测到最低值出现在每日14:00(北京时,下同),最高值在20:00,其大气H2季节变化趋势与北半球同纬度站点情况类似.

Gas Chromatography with a Pulsed Discharge Helium Ionization Detector for Measurement of Molecular Hydrogen(H2) in the Atmosphere

A high precision GC system with a pulsed discharge helium ionization detector was set up based on the commercial Agilent 7890A gas chromatography. The gas is identified by retention time and the concentration is calculated through the peak height. Detection limit of the system is about 1×10^-9(mole fraction, the same as below). The standard deviation of 140 continuous injections with a standard cylinder(concentration is roughly 600×10^-9) is better than 0.3×10^-9. Between 409.30×10^-9 and 867.74×10^-9, molecular hydrogen mole fractions and peak height have good linear response. By using two standards to quantify the air sample, the precision meets the background molecular hydrogen compatibility goal within the World Meteorological Organization/Global Atmosphere Watch(WMO/GAW) program. Atmospheric molecular hydrogen concentration at Guangzhou urban area was preliminarily measured by this method from January to November 2013. The results show that the atmospheric molecular hydrogen mole fraction varies from 450×10^-9 to 700×10^-9 during the observation period, with the lowest value at 14:00(Beijing time, the same as below) and the peak value at 20:00. The seasonal variation of atmospheric hydrogen at Guangzhou area was similar with that of the same latitude stations in northern hemisphere.