Structural diversity and fate of intact polar lipids in marine sediments

Marine sediments harbor an enormous quantity of microorganisms, including a multitude of novel species. The habitable zone of the marine sediment column begins at the sediment-water interface and probably extends to depths of several thousands of meters. Studies of the microbial diversity in this ecosystem have mostly relied on molecular biological techniques. We used a complementary method - analysis of intact polar membrane lipids - to characterize the in-situ microbial community in sediments covering a wide range of environmental conditions from Peru Margin, Equatorial Pacific, Hydrate Ridge, and Juan de Fuca Ridge. Bacterial and eukaryotic phospholipids were only detected in surface sediments from the Peru Margin. In contrast, deeply buried sediments, independent of their geographic location, were dominated by archaeal diether and tetraether lipids with various polar head groups and core lipids. We compared ring distributions of archaeal tetraether lipids derived from polar glycosidic precursors with those that are present as core lipids. The distributions of these related compound pools were distinct, suggestive of different archaeal sources, i.e., the polar compounds derive from sedimentary communities and the core lipids are fossil remnants from planktonic communities with possible admixtures of decayed sedimentary archaea. This in-situ production of distinct archaeal lipid populations potentially affects applications of the TEX86 paleotemperature proxy as demonstrated by offsets in reconstructed temperatures between both pools. We evaluated how varying cell and lipid stabilities will influence the sedimentary pool by using a box-model. The results are consistent with (i) a requirement of continuous inputs of freshly synthesized lipids in subsurface sediments for explaining the observed distribution of intact polar lipids, and (ii) decreasing lipid inputs with increasing burial depth.     

Advection and diffusion determine vertical distribution of microbial communities in intertidal sediments as revealed by combined biogeochemical and molecular biological analysis

Porewater advection stimulates nutrient exchange and microbial activity in shallow marine sediments, whereas element cycling in deeper diffusion-dominated sediments is comparatively slow due to limited nutrient supply. We studied the vertical distribution of microbial communities and organic matter (OM) cycling in these contrasting porewater regimes down to 5 m depth at an intertidal flat of the southern North Sea. Archaea, Bacteria and Eukarya were targeted, combining intact polar lipid (IPL) analysis with qualitative and quantitative molecular biological techniques. The largely sandy section 1 of the core (<75 cm) is characterized by rapid burial of fresh marine OM and intense porewater advection. This supply fuels heterotrophic microbes, as evident from the ¹³C isotopic composition of total organic carbon and IPL derivatives. Major sources of OM are algae and cyanobacteria, as suggested by the elevated amount of eukaryotic 18S rRNA gene copies and phosphate-free IPLs. The relative abundance of most phospholipids remained largely constant over the entire core, except for diphosphatidylglycerol, which represented about half of total IPL abundance in the lower part of section 1 (>50 cm) and the diffusion-dominated section 2 (75–490 cm). This suggests bacteria adapting their membranes in response to increasing physicochemical stress and starvation in the nutrient limited, fine grained sediments of section 2 with less bioavailable, predominantly terrestrial, OM. Relative amounts of bacterial acyl ether and diether phospholipids increased in this lower section and were assigned to sulfate reducers and yet uncultured myxobacteria. Archaea were an order of magnitude less abundant than Bacteria, and were affiliated mainly with Methanosarcinales and Methanomicrobiales. Accordingly, the archaeal IPL composition was typical for a methanogenic community. IPLs not exclusively derived from in situ microbial production emphasize that these biomarkers have to be interpreted with caution in sediments with complex hydrogeology. Our results demonstrate that contrasting subsurface flow regimes significantly impact on the vertical zonation of biogeochemical properties and microorganisms in marine sediments.     

Assessing the ratio of archaeol to caldarchaeol as a salinity proxy in highland lakes on the northeastern Qinghai–Tibetan Plateau

The ratio of archaeol to caldarchaeol (the ACE index) has been proposed recently as an index for paleosalinity reconstruction and is based principally on archaeal core lipids (CLs) from coastal salt pans (Turich, C., Freeman, K.H., 2011. Archaeal lipids record paleosalinity in hypersaline systems. Organic Geochemistry 42, 1147–1157). We have examined possible relationships between salinity and ACE in both CLs and intact polar lipids (IPLs) from suspended particulate matter (SPM) and surface sediments of lakes and surrounding soils on the northeastern Qinghai–Tibetan Plateau. Our results showed that ACE values were positively correlated with salinity in all samples; however, CL ACE values were systematically higher than IPL ACE values, probably due to different degradation kinetics of intact polar (IP) archaeol and IP caldarchaeol. On the other hand, surface sediment ACE values from both CLs and IPLs were lower than SPM ACE values, probably due to enhanced production of caldarchaeol relative to archaeol in the sediment. Our results demonstrate that the ACE proxy reflects changes in salinity in diverse environments on the Qinghai–Tibetan Plateau, which is promising for paleosalinity reconstruction; however, caution should be used when applying the salinity proxy before we have a better understanding of degradation kinetics of archaeal IPLs and in situ production of caldarchaeol and archaeol in sediments.     

Petroleum degradation and associated microbial signatures at the Chapopote asphalt volcano, Southern Gulf of Mexico

At the Chapopote Knoll in the Southern Gulf of Mexico, deposits of asphalt provide the substrate for a prolific cold seep ecosystem extensively colonized by chemosynthetic communities. This study investigates microbial life and associated biological processes within the asphalts and surrounding oil-impregnated sediments by analysis of intact polar membrane lipids (IPLs), petroleum hydrocarbons and stable carbon isotopic compositions (δ¹³C) of hydrocarbon gases. Asphalt samples are lightly to heavily biodegraded suggesting that petroleum-derived hydrocarbons serve as substrates for the chemosynthetic communities. Accordingly, detection of bacterial diester and diether phospholipids in asphalt samples containing finely dispersed gas hydrate suggests the presence of hydrocarbon-degrading bacteria. Biological methanogenesis contributes a substantial fraction to the methane captured as hydrate in the shallow asphalt deposits evidenced by significant depletion in ¹³C relative to background thermogenic methane. In sediments, petroleum migrating from the subsurface stimulates both methanogenesis and methanotrophy at a sulfate-methane transition zone 6-7 m below the seafloor. In this zone, microbial IPLs are dominated by archaeal phosphohydroxyarchaeols and archaeal diglycosidic diethers and tetraethers. Bacterial IPLs dominate surface sediments that are impregnated by severely biodegraded oil. In the sulfate-reduction zone, diagnostic IPLs indicate that sulfate-reducing bacteria (SRB) play an important role in petroleum degradation. A diverse mixture of phosphohydroxyarchaeols and mixed phospho- and diglycosidic archaeal tetraethers in shallow oil-impregnated sediments point to the presence of anaerobic methane-oxidizing ANME-2 and ANME-1 archaea, respectively, or methanogens. Archaeal IPLs increase in relative abundance with increasing sediment depth and decreasing sulfate concentrations, accompanied by a shift of archaeol-based to tetraether-based archaeal IPLs. The latter shift is suggested to be indicative of a community shift from ANME-2 and/or methanogenic archaea in shallower sediments to ANME-1/methanogenic archaea and possibly benthic archaea in deeper sediments.     

Comparison of extraction and work up techniques for analysis of core and intact polar tetraether lipids from sedimentary environments

Glycerol dibiphytanyl glycerol tetraether-based intact polar lipids (IPL GDGTs) are used as biomarkers for living Archaea and are analyzed utilizing a variety of extraction and quantification techniques. Most IPL GDGT studies have used a modified Bligh–Dyer extraction method, but it has been suggested that Soxhlet extraction may be more efficient for environmental samples and biomass. We investigated the impact of three different extractions (Soxhlet, Bligh–Dyer and accelerated solvent extraction, ASE), two IPL quantification methods and two work up techniques (Na₂SO₄ and SiO₂ column) on the amount and distribution of CL (core lipid)- and IPL-derived GDGTs and crenarchaeol-based IPLs in marine sediments from the Arabian Sea and Icelandic shelf, as well as a microbial mat from a Dutch beach. The different extraction procedures gave a similar yield of CL- and IPL-derived GDGTs. Direct analysis of crenarchaeol IPLs showed, however, that, while GDGTs with a monohexose head group were not affected by the extraction method, there was a large effect on IPL GDGTs containing dihexose or hexose, phosphohexose head groups. Quantification of IPL-derived GDGTs by way of either separation over a silica column or by subtraction of CL GDGTs in the total lipid extract before and after hydrolysis gave similar results, but the ‘subtraction-method’ had a relatively large quantification error. However, the silica column, as well as drying over a Na₂SO₄ column, resulted in a loss of the hexose, phosphohexose IPLs by up to 80%. Based on the results, a modified Bligh–Dyer extraction with as little further treatment as possible is recommended to allow measurement of the full range of IPL GDGTs in sediments.     

Differential degradation of intact polar and core glycerol dialkyl glycerol tetraether lipids upon post-depositional oxidation

Archaeal and bacterial glycerol dialkyl glycerol tetraether lipids (GDGTs) are used in various proxies, such as TEX₈₆ and the BIT index. In living organism, they contain polar head groups (intact polar lipids – IPLs). IPL GDGTs have also been detected in ancient marine sediments and it is unclear whether or not they are fossil entities or are part of living cells. In order to determine the extent of degradation of IPL GDGTs over geological timescales, we analyzed turbidite deposits, which had been partly reoxidized for several kyr after deposition on the Madeira Abyssal Plain. Analysis of core lipid (CL) and IPL-derived GDGTs showed a reduction in concentration by two orders of magnitude upon post-depositional oxidation, while IPL GDGTs with a mono- or dihexose head group decreased by 2–3 orders of magnitude. The BIT index for CL- and IPL-derived GDGTs increased substantially upon oxidation from 0.1 to up to 0.5. Together with changing MBT/CBT values, this indicates preferential preservation of soil-derived branched GDGTs over marine isoprenoid GDGTs, combined with in situ production of branched GDGTs in the sediment. The TEX₈₆ value for IPL-derived GDGTs decreased by 0.07 upon oxidation, while that of CL GDGTs showed no significant change. Isolation of IPLs revealed that the TEX₈₆ value for monohexose GDGTs was 0.55, while the that for dihexose GDGTs was substantially higher, 0.70. Thus, the decrease in TEX₈₆ for IPL-derived GDGTs was in agreement with the dominance of monohexose GDGTs in the oxidized turbidite, probably caused by a combination of in situ production as well as selective preservation of terrestrial isoprenoid GDGTs. Due to the low amount of IPL GDGTs vs. CL GDGTs, the impact of IPL degradation on CL-based TEX₈₆ paleotemperature estimates was negligible.     

Stable carbon isotopic compositions of intact polar lipids reveal complex carbon flow patterns among hydrocarbon degrading microbial communities at the Chapopote asphalt volcano

Seepage of asphalt forms the basis of a cold seep system at 3000 m water depth at the Chapopote Knoll in the southern Gulf of Mexico. Anaerobic microbial communities are stimulated in the oil-impregnated sediments as evidenced by the presence of intact polar membrane lipids (IPLs) derived from archaea and Bacteria at depths up to 7 m below the seafloor. Detailed investigation of stable carbon isotope composition (δ¹³C) of alkyl and acyl moieties derived from a range of IPL precursors with distinct polar head groups resolved the complexity of carbon metabolisms and utilization of diverse carbon sources by uncultured microbial communities. In surface sediments most of the polar lipid-derived fatty acids with phosphatidylethanolamine (PE), phosphatidylglycerol (PG) and diphosphatidylglycerol (DPG) head groups could be tentatively assigned to autotrophic sulfate-reducing bacteria, with a relatively small proportion involved in the anaerobic oxidation of methane. Derivatives of phosphatidyl-(N)-methylethanolamine (PME) were abundant and could be predominantly assigned to heterotrophic oil-degrading bacteria. Archaeal IPLs with phosphate-based hydroxyarchaeols and diglycosidic glyceroldibiphytanylglyceroltetraethers (GDGTs) were assigned to methanotrophic archaea of the ANME-2 and ANME-1 cluster, respectively, whereas δ¹³C values of phosphate-based archaeols and mixed phosphate-based and diglycosidic GDGTs point to methanogenic archaea. At a 7 m deep sulfate-methane transition zone that is linked to the upward movement of gas-laden petroleum, a distinct increase in abundance of archaeal IPLs such as phosphate-based hydroxyarchaeols and diglycosidic archaeol and GDGTs is observed; their δ¹³C values are consistent with their origin from both methanotrophic and methanogenic archaea. This study reveals previously hidden, highly complex patterns in the carbon-flow of versatile microbial communities involved in the degradation of heavy oil including hydrocarbon gases that would not have been evident from classical compound-specific isotope analyses of either bulk IPL or apolar lipid derivatives.     

Phosphate-free ornithine lipid contents in Desulfovibrio spp. respond to growth temperature

Eight sulfate-reducing Desulfovibrio strains isolated from intertidal sediments of the North Sea were investigated for their intact polar lipid (IPL) composition. They contained two types of IPLs, phospholipids and aminolipids. The dominating phospholipids were phosphatidylethanolamine (PE), phosphatidylglycerol (PG) and, in lower concentration, diphosphatidylglycerol (DPG). Aminolipids formed a significant IPL fraction in all strains and high resolution tandem mass spectrometry assigned them as phosphate-free ornithine lipids (OLs). In intertidal flat sediments microorganisms may face strong temperature change on varying timescales and it is crucial for the microbes to maintain constant membrane fluidity, e.g. by modification of their membrane lipid composition. We therefore investigated whether or not these strains employ the same strategies for adjusting their membrane composition to growth temperature and, in particular, how OLs are modified. In all strains the relative OL content was found to be higher at higher growth temperature, in most cases at the expense of PE content and less often PG content. The fatty acid (FA) side chains of the main PE and PG species were similar, i.e. both were dominated by C₁₇ or C₁₈, whereas C₁₅ FAs were additionally found as major OL side chains. The temperature-related side chain variation was similar for all IPLs: unsaturated FA content was lower at higher temperature. The corresponding FA patterns after hydrolysis revealed elevated branched FA content and anteiso/iso ratio at higher growth temperature. As the temperature-related changes in the IPL side chains were similar for all strains, we conclude that side chain modification plays a major role in the maintenance of membrane fluidity at higher temperature and that alternative roles of OLs in the membrane adaptation of Desulfovibrio spp. other than melting point adjustment are possible.     

Identification and distribution of intact polar branched tetraether lipids in peat and soil

Branched glycerol dialkyl glycerol tetraether lipids (GDGTs) are membrane lipids of soil bacteria that occur ubiquitously in soil, but their occurrence as intact polar lipids (IPLs) has not been well studied. Here, we report the identification and distribution of IPL-branched GDGTs throughout a depth profile of a Swedish peat bog. In addition to two reported glycosidic IPL branched GDGTs, we identified IPL branched GDGTs with a hexose-glycuronic acid, phospho-hexose, or hexose-phosphoglycerol head group, based on mass spectrometry. A selected reaction monitoring (SRM) assay was developed to monitor changes in head group distribution with depth. The abundance of the IPL branched GDGTs increased below the water table, suggesting that they were primarily produced in this part of the peat. This was supported by the concentrations of core lipid and IPL-derived branched GDGTs, which also substantially increased below the water table. However, individual IPL trends differed, which may be due to changes in the microbial community composition with depth or to different degradation rates for the different IPL branched GDGTs. The SRM method was also applied to two different soil types, which showed that similar IPL branched GDGTs as those in peat were present, albeit with different distributions.     

Factors controlling the distribution of anaerobic methanotrophic communities in marine environments: Evidence from intact polar membrane lipids

Three distinct types of microbial consortia appear to mediate the anaerobic oxidation of methane with sulfate as electron acceptor in marine sediments and are distributed ubiquitously. These consortia consist of ANerobic MEthanotrophic (ANME) archaea of the ANME-1, ANME-2 and ANME-3 clades and their sulfate-reducing bacterial partners either of the Desulfosarcina-Desulfococcus (ANME-1/DSS and ANME-2/DSS) or Desulfobulbus spp. (ANME-3/DBB) branches. Frequently one consortium type dominates the community, but the selective factors are not well constrained. Here we analyzed patterns in the composition of intact polar lipids extracted from bacterial and archaeal communities of different marine seep environments. Further, we investigated if different environmental and geographical factors were responsible for the observed patterns, and hence could be important in the selection of seep communities. Intact polar lipids (IPLs) provide a more robust distinction of the composition of extant communities than their less polar derivatives. In ANME-1/DSS-dominated communities, glycosidic- and phospho-glyceroldialkylglyceroltetraethers were abundant, while ANME-2/DSS and ANME-3/DBB-dominated communities showed abundant archaeol-based IPLs, either with glycosidic and phospho-headgroups or only phospho-headgroups, respectively. The relative proportion of bacterial IPLs varied widely from 0% to 93% and was generally lower in samples of the ANME-1 type, suggesting lower bacterial biomasses in the respective communities. In addition to these lipid signatures, distinctive features were related to the habitat characteristics of these communities: lower amounts of phosphate-based IPLs were generally observed in communities from calcified microbial mats compared to sediments, which may reflect phosphate limitation. Based on statistical analyses of IPLs and environmental data this study constrained for the first time the occurrence of three environmental factors controlling the distribution of different ANME-associated communities in a wide range of hydrocarbon seep systems. Habitats dominated by ANME-1/DSS communities were characterized by high temperature and low oxygen content in bottom waters (or even anoxia), while ANME-2/DSS and ANME-3/DBB-dominated sediments were located in settings with lower temperatures and higher oxygen content in bottom waters. Furthermore, ANME-2/DSS communities were particularly prominent in environments in which a relatively high supply of sulfate was sustained.     

Intact Polar and Core Tetraether Lipids in Sediments from the Haiyang 4 Cold-seep of the Northern South China Sea and their Implications

A number of cold seeps have been discovered in the northern South China Sea (SCS) including the Haiyang 4 cold-seep area where Core 973-5 was collected. Intact polar lipids (IPLs) and core lipids (CLs) were analyzed separately in sediments from Core 973-5. The most abundant lipid biomarkers were isoprenoidal GDGTs (isoGDGTs), with Crenarchaeol and GDGT-0 predominating. IPL-isoGDGTs and CL-isoGDGTs were mainly derived from Thaumarchaeota. IPL-isoGDGTs were mainly produced and retained in situ thus containing most of the in situ microbiological information. Branched GDGTs were predominantly derived from generated in marine production, and mixed with some terrestrial inputs. All IPLs groups presented a high value in the sulfate-methane transition zone (SMTZ). Furthermore, IPL and CL-MI, IPL-R0/4 showed the highest values within the SMTZ, while IPL and CL-R4/i had the lowest values at the SMTZ, suggesting that the contribution of Methanophila and methanogenic to GDGTs increased, while the contribution of ammonia-oxidizing Archaea to GDGTs decreased at the SMTZ.     

海洋沉积物中现存微生物化学标志物完整极性膜脂研究进展

完整极性膜脂作为活的微生物细胞的化学标志物,能够反映海洋沉积物中现存微生物群落结构和生物量等信息.与生物学方法相比,完整极性膜脂分析技术具有无需培养、快速和普适性等特点.综述了海洋沉积物中细菌和古菌的细胞膜完整极性膜脂的组成特点及其在生物地球化学和微生物生态学等研究中的应用,重点评述了在生物地球化学循环中有特殊作用的微生物,如厌氧氨氧化细菌、甲烷氧化古菌、氨氧化古菌、具有四醚膜脂结构的海洋泉古菌等,或者是一些特殊生态系统,如冷泉、海底深部生物圈等研究中完整极性膜脂应用的进展.还简要介绍了完整极性膜脂的分析方法,并对其应用前景进行了展望.     

Applications of Intact Polar Lipids for Tracing the Marine Microbial Activity and Their Limitations

Intact Polar Lipids (IPLs) are synthesized predominately or uniquely by specific organisms and would degrade rapidly after cell death. Such biomarker IPLs can be used to indicate the microbial distribution and activity in marine environment. Here the progress of the aforementioned studies made over the last decade was reviewed. With the development of chromatography and mass spectrometry, the discovery of new IPLs compounds and the application of stable carbon isotope composition (δ¹³C) of IPLs, our understanding of the composition and transformation of IPLs in suspended particulate matter in the water column and of the applicability of the TEX₈₆ proxy are greatly improved. Besides, IPLs are widely applied in the study of marine eukaryotes-bacteria symbiosis, aerobic and anaerobic ammonia oxidation, anaerobic methane oxidation and microbial metabolic states. Meanwhile, it is suggested by recent studies that different IPLs often exhibit differential degradation. Some IPLs, especially glycolipids, have the potential to be preserved as fossil molecules for very long time upon dead cells, and therefore, they can not specifically indicate living biomass. Furthermore, the IPLs degradation rate and completeness would be affected by such factors as oxygen concentration and organic matter content. It is also suggested that the composition of IPLs might be affected by microbial metabolism. Therefore, it is essential to take these factors into account when IPLs are used as proxies to trace marine microbial activities and reconstruct the palaeoenvironment.     

Distributions of uronic acids and O-methyl sugars in sinking and sedimentary particles in two coastal marine environments

Although recent research has indicated that bacteria may contribute an important fraction of biochemical residues in terrestrial and marine environments, it is difficult for geochemists to identify contributions from these ubiquitous and biochemically diverse organisms. Previous studies have suggested uronic acids and O-methyl sugars may be useful indicators of microbial abundance and activity, but have been limited primarily to analyses of a small number of isolated samples. We report here comparative distributions of O-methyl sugars, uronic acids, and aldoses in sediment trap material and sediments from Dabob Bay, WA and nearby Saanich Inlet, BC, where temporal and spatial trends may be used together with well-established patterns in other biochemicals to identify bacterial contributions against the background of other carbohydrate sources.O-methyl sugars and uronic acids were important contributors to the overall flux and burial of polysaccharide material in Dabob Bay and Saanich Inlet, composing ≤12 wt% of the total carbohydrate yields from sediment trap and sediment samples. O-methyl sugars accounted for an average of 5% of the carbohydrate yields from sediment trap materials and sediments, but were found rarely and only in low abundance in vascular plant tissues, phytoplankton, and kelp. In contrast, uronic acids were abundant products of sediment trap material and sediments, as well as vascular plant tissues, where in some cases they predominated among all carbohydrates. Uronic acid abundance in sediment trap material averaged 3% and ranged to >6% of total carbohydrate yields.The persistence of total minor sugar yields in water column collections from Dabob Bay throughout the seasonal cycle indicated they had a primary source that was not directly related to plankton bloom cycles nor pulsed inputs of vascular plant remains. Subsurface maxima in total minor sugar yields (and several individual components) within sediment cores from both sites indicate in situ sedimentary sources. Taken together, the observed environmental distributions strongly suggest that the minor sugar abundances in Dabob Bay and Saanich Inlet were controlled by in situ microbial production.     

The effect of organic matter and oxygen on the degradation of bacterial membrane lipids in marine sediments

The biodegradation of purified radiolabelled membrane lipids from a methanogenic bacterium and a pseudomonad were investigated in mangrove, beach and high marsh marine sediments under aerobic and anaerobic conditions. The effect of organic matter on the amount and rate of degradation was also examined by supplementing beach sediments with humic acids. In aerobic sediments, CO₂ was the major product of lipid degradation while under anaerobic conditions both CO₂ and CH₄ were major end products and the overall rates were reduced (up to 40%) relative to aerobic conditions. Total bacterial numbers increased during all incubations with the largest increases occurring in anaerobic sediments supplemented with humic acids. No lipid degradation occurred in aerobic or anaerobic sediments treated with formaldehyde or autoclaving. In low organic beach sediments, the ester-linked phospholipid of the pseudomonad was degraded much more rapidly than the diphytanyl glycerol diether of the methanogen with 69% of the phospholipid degraded in 96 hours versus only 4% of the methanogen lipid. Lipid degradation in both aerobic and anaerobic sediments was highly correlated to organic matter content with increasing amounts of organic matter inhibiting degradation. Long incubations (75 days) of the diphytanyl glycerol ether resulted in 51% degraded to CO₂ in low (0.5%) organic mangrove sediments while only 9% was mineralized in high (10.8%) organic marsh sediments. Physicochemical sorption of membrane lipids to the organic matrix is proposed as a mechanism which protects membrane lipids from microbial attack and degradation.     

Further insights into how sediment redox status controls the preservation and composition of sedimentary biomarkers

Sedimentary biomarker distributions can record ocean productivity and community structure, but their interpretation must consider alteration during organic matter (OM) export and burial. Large changes in the water column redox state are known to impact on the preservation of biomarkers, but more subtle variation in sediment redox conditions, characteristic of major modern ocean basins, have been less thoroughly investigated. Here we evaluate changes in biomarker distributions during sinking and burial across a nearshore to offshore transect in the southwestern Cape Basin (South East Atlantic), which includes a range of sedimentary environments. Biomarker concentrations and distributions in suspended particulate matter from the upper water column were determined and compared with underlying sedimentary biomarker accumulation rates and distributions. Biomarker distributions were similar in surface and subsurface waters, indicating that the OM signature is exported from the ocean mixed layer with minimal alteration. We show that, while export production (100 m) is similar along this transect, ²³⁰Th_xs-corrected biomarker accumulation rate varies by over an order of magnitude in sediments and is directly associated with sedimentary redox conditions, ranging from oxic to nitrogenous–ferruginous. Biomarker distributions were dominated by sterols in surface water, and by alkenones in underlying sediments, which we propose to be primarily the result of selective preservation. Notably, the difference in sediment O₂ penetration depth was associated with relative biomarker preservation. Subtle variation in sedimentary redox conditions has a dramatic impact on the distribution of preserved biomarkers. We discuss mechanisms for preferential degradation of specific biomarkers within this setting.     

Electron flow in acidic subsurface sediments co-contaminated with nitrate and uranium

The combination of low pH and high concentrations of nitrate and radionuclides in the subsurface is representative of many sites within the U.S. nuclear weapons complex managed by the Department of Energy (DOE), including the DOE’s Environmental Remediation Sciences Program Field Research Center (ORFRC), in Oak Ridge, Tennessee. In order to provide a further understanding of the coupled microbiological and geochemical processes limiting radionuclide bioremediation, we determined the rates and pathways of terminal-electron accepting processes (TEAPs) in microcosm experiments using close to in situ conditions with ORFRC subsurface materials. At the in situ pH range of 4-5, carbon substrate utilization and TEAP rates were diminished, such that nitrate was not depleted and metal reduction was prevented. Upon biostimulation by pH neutralization and carbon substrate addition, TEAPs were stimulated to rates that rival those measured in organic-rich surficial sediments of aquatic environments, and extremely high nitrate concentrations (0.4-0.5 M) were not found to be toxic to microbial metabolism. Metal reduction under neutral pH conditions started once nitrate was depleted to low levels in response to biostimulation. Acidity controlled not only the rates but also the pathways of microbial activity. Denitrification predominated in sediments originating from neutral pH zones, while dissimilatory nitrate reduction to ammonium occurred in neutralized acidic microcosms amended with glucose. Electron donors were determined to stimulate microbial metabolism leading to metal reduction in the following order: glucose > ethanol > lactate > hydrogen. In microcosms of neutralized acidic sediments, 80-90% of C equivalents were recovered as fermentation products, mainly as acetate. Due to the stress imposed by low pH on microbial metabolism, our results indicate that the TEAPs of acidic subsurface sediment are inherently different from those of neutral pH environments and neutralization will be necessary to achieve sufficient metabolic rates for radionuclide remediation.     

海洋沉积物中色素生物标志物研究进展

海洋沉积物中的光合色素包含着水体、沉积物中浮游和底栖植物以及微生物群落的丰富信息,能表征特定生物来源,在埋藏到沉积物甚至发生某些改变之后仍然保留其源信息,是一类重要的化学生物标志物.结合总有机碳、总氮等其他海洋地球化学参数,沉积色素可用来研究海洋浮游植物和光合细菌的群落组成和丰度,反演海洋初级生产、水体富营养化水平及其历史趋势,指示水体和沉积物氧化还原条件,揭示海域气候条件等现状及其历史变化.沉积色素的研究,对于掌握海洋中碳的生物地球化学循环过程,回溯古环境、古海洋、古生态以及古气候记录,制定合理的海洋管理政策具有十分重要的意义.阐述了沉积物中色素的分类、来源、性质和分析方法,分析了色素在沉积物中的保存和变化规律,探讨总结了沉积色素作为化学生物标志物在海洋学研究中的应用.     

Modification of sediment geochemistry by the hydrocarbon seep tubeworm Lamellibrachia luymesi: A combined empirical and modeling approach

The sulfide-oxidizing symbiotic tubeworm Lamellibrachia luymesi is a dominant member of deep-sea hydrocarbon seep ecosystems on the Gulf of Mexico seafloor. This tubeworm forms large aggregations that can live for centuries and provide habitat for an assortment of associated fauna. Previous studies have suggested that persistence of these tubeworms for such long time periods is contingent upon their ability to supply sediments with sulfate. To examine this hypothesis, we characterized the tubeworm’s geochemical environment using pore water peepers and compared the measured depth profiles with those predicted by a sulfur diffusion-reaction-supply model. We found a large range of sulfide concentrations in the tubeworm habitat, indicating that this species can live under conditions of both high and low sulfide availability. In sediments rich in hydrocarbons, we found compelling evidence that tubeworms enhance microbial sulfide production, likely through a combination of sulfide uptake and sulfate release through their root-like structures buried in the sediment. Our in situ empirical data combined with the results of the geochemical model corroborate previous physiological studies that indicate that tubeworms release between 70% and 90% of the sulfate produced during sulfide oxidation by their symbionts across their roots into the surrounding sediment. In sediments low in hydrocarbon content, sulfide production is hydrocarbon-limited rather than sulfate-limited, and our model predicts that tubeworm growth could be limited by low sulfide availability.     

Early diagenesis of organic matter in the water column and sediments: Microbial degradation and resynthesis of lipids in Lake Haruna

Particulate matter, sediment trap, and surface sediment samples collected in freshwater Lake Haruna were studied to understand early diageesis of organic materials in the water column and in bottom sediments. The samples were analyzed for biomarkers, including aliphatic and aromatic hydrocarbons, fatty alcohols, saturated and unsaturated fatty acids, β- and ω-hydroxyacids, and α,ω-dicar☐ylic acids. Decreases in concentrations of autochthonous saturated C₁₂–C₁₉ fatty acids and polyunsaturated C₁₈ acids relative to TOC occured with the settling of organic matter ot the lake bottom, whereas the amounts of terrestial saturated C₂₀–C₃₀ acids remained almost constant. Conversely, the concentrations of monosaturated fatty acids, branched chain fatty acids, and β- and ω-hydroxyacids, which are probably produced by microbial activity, increased. These results indicate that preferential degradation of algal lipids accompanies microbial resynthesis of lipids during settling, however, terrigenous lipids are relatively stable.