Simultaneous determination of seawater trimethylamine and methanol by purge and trap gas chromatography using dual nitrogen-phosphorus detector and flame-ionization detector

Abstract

Compounds containing one carbon atom or no carbon-carbon bond (C1 compounds), such as trimethylamine and methanol, are important climate relevant gases in the atmosphere and play key roles in global warming. The ocean is a significant source or sink of such compounds, while the concentrations of trimethylamine and methanol in seawater remain largely unconstrained due to the analytical challenges involved. Therefore, it is necessary to establish a continuous, rapid and sensitive method for the determination of these compounds with high polarity, volatility or solubility at low seawater concentrations. Here we developed a purge and trap system, coupled to a gas chromatography equipped with dual nitrogen phosphorus detector (NPD) and flame ionization detector (FID) for the simultaneous online analysis of trimethylamine and methanol at nanomolar range using a small sample volume (~ 10 mL). The dual detection of trimethylamine and methanol with NPD or FID was achieved by installing a capillary flow splitter between the capillary column and detectors. After modification and optimization of the setup and conditions, excellent linearity (R2 > 0.99) and repeatability (< 6%) were obtained for both compounds; the detection limits for trimethylamine and methanol were 0.3 nM and 17.6 nM, respectively. Using this method, water samples collected from coastal and open ocean were analyzed; trimethylamine and methanol concentrations ranged from 0.6 to 18.8 nM and 26.0 to 256.2 nM, respectively. Collectively, this method allowed for online, rapid, sensitive and simultaneous quantification of trace trimethylamine and methanol concentrations with low-cost instrumentation and small sample volume, which makes it promising for further application in volatile compounds analysis in marine environments.