Improved protocols for large-volume injection and liquid chromatography–mass spectrometry analyses enable determination of various glycerol dialkyl glycerol tetraethers in a small amount of sediment and suspended particulate matter

Glycerol dialkyl glycerol tetraethers (GDGTs) have received considerable attention because they are useful indicators for paleoenvironment, organic matter source, and microbial community. In this study, a new simple method was developed for the analysis of GDGTs by using direct large-volume injection (LVI)–liquid chromatography (LC)–atmospheric pressure chemical ionization–mass spectrometry (APCI–MS) to reduce the usage of sediment or seawater suspended particulate matter (SPM) samples. The parameters of accelerated solvent extraction and LVI of target GDGTs were optimized. Under optimal conditions, the LVI approach (500 μL injection) coupled with LC–APCI–MS could determine various GDGTs even with 0.02–0.10 g of sediment samples or SPM samples collected from 0.2–1.0 L of marginal sea water or 10–20 L of open ocean seawater with satisfactory method precision (relative standard deviations ≤10.2%) and linearity (R2 ≥ 0.991). Compared with the classical method, the LVI–LC–APCI–MS required significantly reduced amount of sediment or SPM sample. Finally, the proposed method was applied to determine GDGTs in real sediment samples collected from hydrothermal vent sites at the Southwest Indian Ridges. Four groups of GDGTs, namely, isoprenoid GDGTs (isoGDGTs), branched GDGTs, H-GDGTs and OH-GDGTs, and archaeol, glycerol dialkanol diethers (GDDs) and glycerol monoalkanediol diethers (GMDs) were detected with only 0.02 g of sediment sample collected from Longqi and Tianzuo hydrothermal fields. The organic matter in the sediment sample from Tianzuo was significantly affected by hydrothermal activity. In addition, isoGDGTs in seawater SPM from the open area of Eastern Indian Ocean were investigated for the first time. Six common isoGDGTs were all detected in surface and subsurface SPM samples (filtering 10 L of seawater), which indicated that the LVI approach could noticeably reduce the workload of collecting seawater SPM on board and could be used to investigate conveniently the distribution of GDGTs in water column especially in open oceans and deep seas.