摘要
An automated cumulative sampling system and a method that combines a two-step cryo-concentrated system and gas chromatography/mass spectrometry （CCS-GC/MS） are introduced. The method is evaluated by a set of special experiments and the results are presented. The lowest measurement detection limit was expanded from 10^-6 nmol mol^-1 to 10^-12 nmol mol^-1 by using CCS-GC/MS instead of the simpler method of gas chromatography/mass spectrometry （GC/MS）, with the average responsible factor of 39 object compounds being 2.9 × 10^-12. When the volume of air sample reached 1000 cm^3, the lowest detection limit reached up to 7 × 10^-12-40 × 10^-12 nmol mol^-1. The CCS-GC/MS method can potentially identify all objective chemical species in an atmospheric sample, with an average 2.5 s bias error of retention time for 39 gas chromatography （GC） peaks. Within the range 0-400×10^-9 nmol mol^-1, the concentration of 39 kinds of objective compounds can be individually calculated very accurately by a standard curve [average r^2 （coefficient of determination） value of above 0.99]. The recovery efficiency was 88%-111%, with an average of 100.8% ±5.6%. The bias error of precision was 2%-14%, with an average of 6.6%.
An automated cumulative sampling system and a method that combines a two-step cryo-concentrated system and gas chromatography/mass spectrometry （CCS-GC/MS） are introduced. The method is evaluated by a set of special experiments and the results are presented. The lowest measurement detection limit was expanded from 10^-6 nmol mol^-1 to 10^-12 nmol mol^-1 by using CCS-GC/MS instead of the simpler method of gas chromatography/mass spectrometry （GC/MS）, with the average responsible factor of 39 object compounds being 2.9 × 10^-12. When the volume of air sample reached 1000 cm^3, the lowest detection limit reached up to 7 × 10^-12-40 × 10^-12 nmol mol^-1. The CCS-GC/MS method can potentially identify all objective chemical species in an atmospheric sample, with an average 2.5 s bias error of retention time for 39 gas chromatography （GC） peaks. Within the range 0-400×10^-9 nmol mol^-1, the concentration of 39 kinds of objective compounds can be individually calculated very accurately by a standard curve [average r^2 （coefficient of determination） value of above 0.99]. The recovery efficiency was 88%-111%, with an average of 100.8% ±5.6%. The bias error of precision was 2%-14%, with an average of 6.6%.
