ALBERT

Description: 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.

Description: Among the most extreme habitats on Earth, dark, deep, anoxic brines host unique microbial ecosystems that remain largely unexplored. As the terminal step of anaerobic degradation of organic matter, methanogenesis is a potentially significant but poorly constrained process in deep-sea hypersaline environments. We combined biogeochemical and phylogenetic analyses as well as incubation experiments to unravel the origin of methane in hypersaline sediments of Orca Basin in the northern Gulf of Mexico. Substantial concentrations of methane (up to 3.4 mM) coexisted with high concentrations of sulfate (16-43 mM) in two sediment cores retrieved from the northern and southern parts of Orca Basin. The strong depletion of 13C in methane (-77 to -89 per mill) pointed towards a biological source. While low concentrations of competitive substrates limited the significance of hydrogenotrophic and acetoclastic methanogenesis, the presence of non-competitive methylated substrates (methanol, trimethylamine, dimethyl sulfide, dimethylsulfoniopropionate) supported the potential for methane generation through methylotrophic methanogenesis. Thermodynamic calculations demonstrated that hydrogenotrophic and acetoclastic methanogenesis were unlikely to occur under in situ conditions, while methylotrophic methanogenesis from a variety of substrates was highly favorable. Likewise, carbon isotope relationships between methylated substrates and methane supported methylotrophic methanogenesis as the major source of methane. Stable isotope tracer and radiotracer experiments with 13C bicarbonate, acetate and methanol as well as 14C-labeled methylamine indicated that methylotrophic methanogenesis was the predominant methanogenic pathway. Based on 16S rRNA gene sequences, halophilic methylotrophic methanogens related to the genus Methanohalophilus dominated the benthic archaeal community in the northern basin but also occurred in the southern basin. High abundances of methanogen lipid biomarkers such as intact polar and polyunsaturated hydroxyarchaeols were detected in sediments from the northern basin, with lower abundances in the southern basin. Strong 13C-depletion of saturated and monounsaturated hydroxyarchaeol were consistent with methylotrophic methanogenesis as the major methanogenic pathway. Collectively, the availability of methylated substrates, thermodynamic calculations, experimentally determined methanogenic activity as well as lipid and gene biomarkers strongly suggested methylotrophic methanogenesis as predominant pathway of methane formation in the presence of sulfate in Orca Basin sediments.

Description: Methylated amines and sulfides are ubiquitous organic nitrogen and sulfur compounds in the marine environment and could serve as important energy substrates to methanogens inhabiting anoxic sediments. However, their abundance and isotopic values remain largely unconstrained in marine sediments. In this study, we investigated the distribution of trimethylamine (TMA), dimethylsulfide (DMS) and dimethylsulfoniopropionate (DMSP) in Aarhus Bay, Denmark and provided the first report for their stable carbon isotopic composition. Simultaneous measurement of those two compounds in small volumes of pore waters and sediments was accomplished with gas chromatography in combination with either a purge and trap system for quantification or a headspace method for carbon isotopic analysis. TMA in the solid phase (exchangeable pool, 0.3-6.6 µmol/kg wet sediment; base-extractable pool, 2-18 µmol/kg) was much more abundant than the dissolved pool (〈 20 nM), indicating strong adsorption of TMA to sediments. Likewise, total base-hydrolyzable DMS(P)t (including DMS and base-released DMS from DMSP) in sediment was at least three orders of magnitude higher (11-65 µmol/kg) than the dissolved pool of DMS(P)d in the pore water (including DMS and dissolved DMSP; 1-12 nM). TMA and DMS(P) contents in the solid phase peaked in the surface sediment, consistent with their phytodetrital origin. TMA was more 13C-depleted than DMS(P) (TMA: -36.4 per mil to -39.2 per mil; DMS: -18.6 per mil to -23.4 per mil), presumably due to different biological or biosynthetic origins of the respective methyl groups. Both compounds showed a downcore decrease in their solid-phase concentration, a feature that was attributed to microbial degradation, but progressive enrichment in 13C (up to 4 per mil) with depth was observed only for DMS(P). The considerable pool size of TMA and DMS(P) outlined in this study and geochemical evidence of their degradability suggested these two compounds could be potentially important substrates for methane production in sulfate-reducing environments.

Description: Non-methane hydrocarbons (NMHCs) are abundant volatile organic compounds in the atmosphere, their photodegradation produces reactive oxygen species which can react with NOx compounds and thus contribute to ozone formation. In marine surface waters, NMHCs are generally supersaturated relative to the atmosphere, thus marine emissions represent a significant source of NMHCs in the atmosphere.Seawater samples were collected monthly using a 5 L plexiglass water sampler from surface (〈1 m) and subsurface (~1 m above bottom) layers at 14 study sites in Jiaozhou Bay during September 2016 and August 2017.Seawater NMHCs concentrations were measured with a customized purge and trap preconcentration setup coupled to a gas chromatography-mass spectrometer.

Description: Seawater samples were collected monthly using a 5 L plexiglass water sampler from surface (〈1 m) and subsurface (~1 m above bottom) layers at 14 study sites in Jiaozhou Bay during September 2016 and August 2017. Seawater NMHCs concentrations were measured with a customized purge and trap preconcentration setup coupled to a gas chromatography-mass spectrometer.Jiaozhou_Bay_2016-2017.