Methanol and ethanol analysis in marine sediment pore water

Low-molecular-weight (LMW) alcohols are produced during the microbial degradation of organic matter from precursors such as lignin, pectin, and carbohydrates. The biogeochemical behavior of these alcohols in marine sediment is poorly constrained but potentially central to carbon cycling. Little is known about LMW alcohols in sediment pore waters because of their low concentrations and high water miscibility, both of which pose substantial analytical challenges. In this study, three alternative methods were adapted for the analysis of trace amounts of methanol and ethanol in small volumes of saline pore waters: direct aqueous injection (DAI), solid-phase microextraction (SPME), and purge and trap (P&T) in combination with gas chromatography (GC) coupled to either a flame ionization detector (FID) or a mass spectrometer (MS). Key modifications included the desalination of samples prior to DAI, the use of a threaded midget bubbler to purge small-volume samples under heated conditions and the addition of salt during P&T. All three methods were validated for LMW alcohol analysis, and the lowest detection limit (60 nM and 40 nM for methanol and ethanol, respectively) was achieved with the P&T technique. With these methods, ambient concentrations of volatile alcohols were determined for the first time in marine sediment pore waters of the Black Sea and the Gulf of Mexico. A strong correlation between the two compounds was observed and tentatively interpreted as being controlled by similar sources and sinks at the examined stations.

(Table 1) Dissolved organic carbon and dissolved sugar of interstitial water of DSDP Holes 96-618, 96-619 and 96-623

Preliminary data on dissolved organic carbon (DOC) and dissolved sugars in interstitial water samples collected at Sites 618, 619, and 623 of Deep Sea Drilling Project Leg 96 are presented. At Site 618 in Orca Basin, the DOC content of the interstitial water peaks in the hypersaline sulfate reduction zone. The sugar content reaches a maximum and the DOC content begins to decrease at the depth of methane gas generation. Below that depth, the sugar and DOC contents are about constant. At Site 619 in Pigmy Basin, the DOC content increases slightly with depth in the sulfate reduction and the methane fermentation zones. The sugar content is lower in the sulfate reduction zone than in the methane fermentation zone; sugar concentration increases and fluctuates with methane gas percentages within the methane fermentation zone. At Site 623 in the lower fan region of the Mississippi Fan, there is no sulfate reduction zone. The DOC and sugar contents of the interstitial water are almost constant with depth.