Bacteriohopanepolyols in tropical soils and sediments from the Congo River catchment area

The Congo River basin drains the second largest area of tropical rainforest in the world, including a large proportion of pristine wetlands. We present the bacteriohopanepolyol (BHP) inventory of a suite of tropical soils and, from comparison with published data, propose some initial ideas on BHP distribution controls. Strong taxonomic controls on BHP production are evident in wetland sediments. Dominant within the suite were 35-aminobacteriohopane-31,32,33,34-tetrol (aminotetrol) and 35-aminobacteriohopane-30,31,32,33,34-pentol (aminopentol), indicating aerobic methanotrophy. A narrow range and low mean relative abundance of 30-(5′-adenosyl)hopane (adenosylhopane) and related compounds, collectively termed “soil marker” BHPs, were observed in Congo soils (mean 17%, range 7.9–36% of total BHPs, n = 22) compared with literature data from temperate surface soils and Arctic surface soils (mean 36%, range 0–66% of total BHPs, n = 28) suggesting a greater rate of conversion of these BHP precursors to other structures.     

Bacteriohopanepolyol biomarker composition of organic matter exported to the Arctic Ocean by seven of the major Arctic rivers

Bacteriohopanepolyols (BHPs) are a diverse group of membrane lipids produced by a wide variety of bacteria and can be used as molecular biomarkers for bacterial processes and populations in both modern and ancient environments. A group of BHPs, including adenosylhopane and structurally related compounds, have been identified as being specific to soils, enabling the transport of terrestrial organic matter (terrOM) to the marine realm to be monitored. Estuary surface sediment samples were obtained from the five Great Russian Arctic Rivers (GRARs; Ob, Yenisey, Lena, Indigirka and Kolyma) and river sediments were obtained from two North American Rivers (Yukon and Mackenzie). Analysis of the BHP signatures, using high performance liquid chromatography–tandem mass spectrometry (HPLC–MSⁿ), indicated the presence of 15 different BHPs originating from a variety of different bacteria, as well as a significant presence of terrestrially derived OM. Total BHP abundance and the contribution of the “soil-marker” BHPs to the total BHP pool increased eastwards among the GRAR sediments. This suggests increasing terrestrial OM or increased preservation of OM as a result of shorter periods of permafrost thawing. The North American rivers showed greatly differing BHP levels between the Yukon and Mackenzie rivers, with a greater BHP input and thus a relatively higher soil OM contribution from the Yukon. The Indigirka River basin in the eastern Siberian Arctic appeared to be the epicentre in the pan-Arctic BHP distribution trend, with the highest “soil-marker” BHPs but the lowest tetrafunctionalised BHPs. Aminobacteriohopanepentol, an indicator of aerobic methane oxidation, was observed in all the sediments, with the source being either the marine environment or methane producing terrestrial environments.     

Euphotic zone bacterioplankton sources major sedimentary bacteriohopanepolyols in the Holocene Black Sea

Bacteriohopanepolyols (BHPs) are lipid constituents of many bacterial groups. Geohopanoids, the diagenetic products, are therefore ubiquitous in organic matter of the geosphere. To examine the potential of BHPs as environmental markers in marine sediments, we investigated a Holocene sediment core from the Black Sea. The concentrations of BHPs mirror the environmental shift from a well-mixed lake to a stratified marine environment by a strong and gradual increase from low values (∼30 μg g⁻¹ TOC) in the oldest sediments to ∼170 μg g⁻¹ TOC in sediments representing the onset of a permanently anoxic water body at about 7500 years before present (BP). This increase in BHP concentrations was most likely caused by a strong increase in bacterioplanktonic paleoproductivity brought about by several ingressions of Mediterranean Sea waters at the end of the lacustrine stage (∼9500 years BP). δ¹⁵N values coevally decreasing with increasing BHP concentrations may indicate a shift from a phosphorus- to a nitrogen-limited setting supporting growth of N₂-fixing, BHP-producing bacteria. In sediments of the last ∼3000 years BHP concentrations have remained relatively stable at about 50 μg g⁻¹ TOC.The distributions of major BHPs did not change significantly during the shift from lacustrine (or oligohaline) to marine conditions. Tetrafunctionalized BHPs prevailed throughout the entire sediment core, with the common bacteriohopanetetrol and 35-aminobacteriohopanetriol and the rare 35-aminobacteriohopenetriol, so far only known from a purple non-sulfur α-proteobacterium, being the main components. Other BHPs specific to cyanobacteria and pelagic methanotrophic bacteria were also found but only in much smaller amounts.Our results demonstrate that BHPs from microorganisms living in deeper biogeochemical zones of marine water columns are underrepresented or even absent in the sediment compared to the BHPs of bacteria present in the euphotic zone. Obviously, the assemblage of molecular fossils in the sediments does not represent an integrated image of the entire community living in the water column. Remnants of organisms living in zones where effective transport mechanisms - such as the fecal pellet express - exist are accumulated while those of others are underrepresented. Our work shows a high stability of BHPs over geological time scales. Largely uniform distributions and only minor changes in structures like an increasing prevalence of saturated over unsaturated BHPs with time were observed. Consequently, sedimentary BHP distributions are less suitable as markers for in situ living bacteria but are useful for paleoreconstructions of bacterioplanktonic communities and productivity changes.     

Variation in methanotroph-related proxies in peat deposits from Misten Bog,Hautes-Fagnes,Belgium

Methane emissions from peat bogs are strongly reduced by aerobic methane oxidising bacteria (methanotrophs) living in association with Sphagnum spp. Field studies and laboratory experiments have revealed that, with increasing water level and temperature, methanotrophic activity increases. To gain a better understanding of how longer term changes in methanotrophic activity are reflected in methanotroph biomarkers, a peat record (0–100 cm) from the Hautes-Fagnes (Belgium) encompassing the past 1500 years, was analysed for methanotroph-specific intact bacteriohopanepolyols (BHPs) and the carbon isotopic composition of diploptene. A predominance of aminobacteriohopanetetrol (aminotetrol) over aminobacteriohopanepentol (aminopentol) indicated the prevalence of type II methanotrophs. Relatively high methanotrophic activity was indicated by all methanotroph markers between 20 and 45 cm depth, around the present oxic–anoxic boundary, most likely representing the currently active methanotrophic community. Comparing methanotrophic markers in the deeper part of the peat profile with environmental variables afforded, however, no clear correlation between change in water level and methanotrophic activity. This is potentially caused by a predominance of type II methanotrophs, a combination of sources for methanotrophic biomarkers or insufficient variation in climatic changes. A proposed way forward would include a study of a core covering a longer timescale, thereby involving greater variability.     

New constraints on the provenance of hopanoids in the marine geologic record: Bacteriohopanepolyols in marine suboxic and anoxic environments

The abundance and structural diversity of bacteriohopanepolyols (BHPs) was examined in three marine pelagic environments that are characterized by strong vertical redox gradients and water column suboxia or anoxia. The abundance and, in most instances, structural diversity of BHPs was highest at depths where conditions were suboxic or anoxic. However, the majority of the BHP structures that were identified are environmentally cosmopolitan and their biological sources are presently not well constrained. An isomer of bacteriohopanetetrol (denoted BHT II) was observed at all three study sites in association with anoxic and suboxic conditions within the water column. Based on the absence of BHT II from terrigenous and oxic marine environments studied to date, and its strong association with suboxic and anoxic marine pelagic environments, we propose that BHT II is a promising candidate biomarker for water column suboxia and anoxia in the marine geologic record. The molecular fingerprint of BHPs in suspended and sinking particles and core-top sediments indicates that hopanoids produced within the water column are exported to marine sediments and that their biological source is most likely associated with settling particles and not the free-water phase. Based on our observations, BHPs likely represent an important input to the sedimentary hopanoid inventory, particularly in upwelling environments characterized by pelagic oxygen minimum zones (OMZ) and anoxic marine basins.     

Bacteriohopanepolyol signatures of bacterial populations in Western Canadian soils

Bacteriohopanepolyols (BHPs) are naturally occurring compounds derived from bacteria. Their quantity and diversity in five Western Canadian soils, which vary mostly in vegetative cover, were examined using high performance liquid chromatography – atmospheric pressure chemical ionization – mass spectrometry (HPLC–APCI–MS). Eighteen BHP compounds including tetra-, penta- and hexa-functionalised components, as well as composite components, were identified. Concentrations were highest in the forest-grassland transition soil [515 μg/g organic carbon (OC)], followed by the forest soil (431 μg/g OC) and the grassland soils (333–306 μg/g OC). The distribution trends measured using HPLC–ACPI–MS agree with hopanoid measurements using gas chromatography–mass spectrometry (GC–MS) but intact BHPs were detected at a concentration that was an order of magnitude higher using HPLC–APCI–MS. Adenosylhopane was the most abundant BHP in all the samples and comprised on average 27% of total BHPs, supporting earlier work indicating that adenosylhopane is an excellent soil-specific biomarker. The soil samples vary in vegetative cover and this is likely one of the main reasons for observing variation in BHP composition, suggesting that BHP biomarkers may be a valuable tool for assessing bacterial community structure in soil when used in cooperation with other molecular microbial ecology methods (such as DNA genotyping).     

Bacteriohopanoid inventory of Geobacter sulfurreducens and Geobacter metallireducens

Geobacter spp. are ubiquitous prokaryotes in diverse sedimentary environments, coupling the oxidation of various carbon compounds with the reduction of metals, such as ferric iron. One specific attribute of such species, namely Geobacter metallireducens and Geobacter sulfurreducens, is their ability to synthesize hopanoids. Hopanoids are among the most specific and abundant molecular fossils in the sedimentary record and are commonly used to trace bacterial activity in recent to sub-recent sediments. The production of polyfunctionalized bacteriohopanepolyols (BHPs) by G. sulfurreducens and G. metallireducens is known, but the intact BHPs were not identified. In this study, the complete hopanoid inventory of both species was investigated. Among the hopanoids, bacteriohopanetetrol cyclitol ether was the major compound in both, while guanidine-substituted bacteriohopanetetrol cyclitol ether and bacteriohopanetetrol glucosamine were also found in high abundance in G. sulfurreducens, but only in trace amounts in G. metallireducens. Interestingly, the BHP inventories are similar to those of some aerobic or facultative anaerobic methylotrophic bacteria, but have been identified in anaerobic cultures of Geobacter for the first time. The ubiquity of Geobacter spp. in anoxic sediments provokes us to speculate that such species may be among the predominant sources of composite BHPs in many sedimentary environments.     

Microbial carbon cycling in oligotrophic regional aquifers near the Tono Uranium Mine, Japan as inferred from δC and ΔC values of in situ phospholipid fatty acids and carbon sources

Microorganisms are ubiquitous in deep subsurface environments, but their role in the global carbon cycle is not well-understood. The natural abundance δ¹³C and Δ¹⁴C values of microbial membrane phospholipid fatty acids (PLFAs) were measured and used to assess the carbon sources of bacteria in sedimentary and granitic groundwaters sampled from three boreholes in the vicinity of the Tono Uranium Mine, Gifu, Japan. Sample storage experiments were performed and drill waters analyzed to characterize potential sources of microbial contamination. The most abundant PLFA structures in all waters sampled were 16:0, 16:1ω7c, cy17:0, and 18:1ω7c. A PLFA biomarker for type II methanotrophs, 18:1ω8c, comprised 3% and 18% of total PLFAs in anoxic sedimentary and granitic waters, respectively, sampled from the KNA-6 borehole. The presence of this biomarker was unexpected given that type II methanotrophs are considered obligate aerobes. However, a bacterium that grows aerobically with CH₄ as the sole energy source and which also produces 56% of its total PLFAs as 18:1ω8c was isolated from both waters, providing additional evidence for the presence of type II methanotrophs. The Δ¹⁴C values determined for type II methanotroph PLFAs in the sedimentary (−861‰) and granite (−867‰) waters were very similar to the Δ¹⁴C values of dissolved inorganic carbon (DIC) in each water (∼−850‰). This suggests that type II methanotrophs ultimately derive all their carbon from inorganic sources, whether directly from DIC and/or from CH₄ produced by the reduction of DIC. In contrast, δ¹³C values of type II PLFAs in the sedimentary (−93‰) and granite (−60‰) waters indicate that these organisms use different carbon assimilation schemes in each environment despite very similar δ¹³C_CH4 values (∼−95‰) for each water. The δ¹³C_PLFA values (−28‰ to −45‰) of non-methanotrophic bacteria in the KNA-6 LTL water do not clearly distinguish between heterotrophic and autotrophic metabolisms, but Δ¹⁴C_PLFA values indicate that >65% of total bacteria filtered from the KNA-6 LTL water are heterotrophs. Ancient Δ¹⁴C values (∼−1000‰) of some PLFAs suggest that many heterotrophs utilize ancient organic matter, perhaps from lignite seams within the sedimentary rocks. The more negative range of δ¹³C_PLFA values determined for the KNA-6 granitic water (−42‰ to −66‰) are likely the result of a microbial ecosystem dominated by chemolithoautotrophy, perhaps fuelled by abiogenic H₂. Results of sample storage experiments showed substantial shifts in microbial community composition and δ¹³C_PLFA values (as much as 5‰) during 2-4 days of dark, refrigerated, aseptic storage. However, water samples collected and immediately filtered back in the lab from freshly drilled MSB-2 borehole appeared to maintain the same relative relationships between δ¹³C_PLFA values for sedimentary and granitic host rocks as observed for samples directly filtered under artesian flow from the KNA-6 borehole of the Tono Uranium Mine.     

Prediction of Flowing Bottomhole Pressures for Two-Phase Coalbed Methane Wells

A method is proposed to predict the flowing bottomhole pressures(FBHPs)for two-phase coalbed methane(CBM)wells.The mathematical models for both gas column pressure and two-phase fluid column pressure were developed based on the well liquid flow equation.FBHPs during the production were predicted by considering the effect of entrained liquid on gravitational gradients.Comparison of calculated BHPs by Cullender-Smith and proposed method was also studied.The results show that the proposed algorithm gives the desired accuracy of calculating BHPs in the lowproductivity and low-pressure CBM wells.FBHP is resulted from the combined action of wellhead pressure,gas column pressure and fluid column pressure.Variation of kinetic energy term,compressibility and friction factors with depth increments and liquid holdup with velocity should be considered to simulate the real BHPs adequately.BHP is a function of depth of each column segment.The small errors of less than 1.5%between the calculated and measured values are obtained with each segment within 25 m.Adjusting BHPs can effectively increase production pressure drop,which is beneficial to CBM desorption and enhances reservoir productivity.The increment of pressure drop from 5.37 MPa2 to 8.66 MPa2 leads to an increase of CBM production from 3270 m3/d to 6700 m3/d and is attributed to a decrease in BHP from 2.25 MPa to 1.33 MPa.     

Distribution of glycerol dialkyl glycerol tetraether lipids in the water column of Lake Tanganyika

We studied the distribution of glycerol dialkyl glycerol tetraethers (GDGTs) in suspended particulate matter from the water column of Lake Tanganyika (East Africa), where sediment studies had shown the applicability of the TEX₈₆ proxy for reconstructing surface lake water temperature. GDGTs, in particular crenarchaeol, showed maximum abundance within the suboxic zone (100–180 m), suggesting that this is the preferred niche of ammonia-oxidizing Thaumarchaeota. Despite evidence for anaerobic methane oxidation in deep anoxic water (300–1200 m) no unambiguous evidence for an imprint of methanotrophic archaea on GDGT distribution was found. Comparison of TEX₈₆ and BIT indices with those of surface sediments suggests that the sedimentary GDGTs are derived predominantly from the oxic zone and suboxic zone of the lake.     

Effects of Oxygen Loss on Carbon Processing and Heterotrophic Prokaryotes from an Estuarine Ecosystem: Results from Stable Isotope Probing and Cytometry Analyses

Many aquatic ecosystems are experiencing a decline in their oxygen (O₂) content and this is predicted to continue. Implications of this change on several properties of bacterioplankton (heterotrophic prokaryotes) remain however are poorly known. In this study, oxic samples (～170 μM O₂?=?controls) from an oligohaline region of the Scheldt Estuary were purged with N₂ to yield low-O₂ samples (～69 μM O₂?=?treatments); all were amended with ¹³C-glucose and incubated in dark to examine carbon incorporation and cell size of heterotrophic prokaryotes, and relationships between organic matter (OM) degradation and phosphate (P) availability in waters following O₂ loss. Stable isotope (¹³C) probing of phospholipid fatty acids (PLFA) and flow cytometry were used. In samples that have experienced O₂ loss, PLFA biomass became higher, prokaryotic cells had significantly larger size and higher nucleic acid content, but P concentrations was lower, compared to controls. P concentration and OM degradation were positively related in controls, but uncoupled in low-O₂ samples. Moreover, the dominant PLFA 16:1ω7c (likely mainly from Gram-negative bacteria) and the nucleic acid content of heterotrophic prokaryotic cells in low-O₂ samples explained (62–72 %) differences between controls and low-O₂ samples in P amounts. Shortly after incubations began, low-O₂ samples had consistently lower bacterial PLFA ¹³C-enrichments, suggesting involvement of facultatively anaerobic metabolism in carbon incorporation, and supporting the view that this metabolic pathway is widespread among pelagic bacteria in coastal nutrient-rich ecosystems. Estimates based on ¹³C-enrichment of PLFAs indicated that grazing by protozoa on some bacteria was stronger in low-O₂ samples than in controls, suggesting that the grazing pressure on some heterotrophic prokaryotes may increase at the onset of O₂ deficiency in nutrient-rich aquatic systems. These findings also suggest that physiological responses of heterotrophic prokaryotes to O₂ loss in such ecosystems include increases in cell activity, high carbon incorporation, and possibly phosphorus retention by cells that may contribute to reduce phosphate availability in waters.     

Palaeoenvironmental conditions during deposition of the Upper Cretaceous oil shale sequences in the Songliao Basin (NE China): Implications from geochemical analysis

Excellent hydrocarbon source rocks (oil shales), containing Type I organic matter (OM), were deposited in the continental Songliao rift basin during the Late Cretaceous. A major contribution of aquatic organisms (dinoflagellates, green algae, botryococcus) and minor input from macrophytes and land plants to OM accumulation is indicated by n-alkane distribution, steroid composition and δ¹³C values of individual biomarkers. Microbial communities included heterotrophic bacteria, cyanobacteria and chemoautotrophic bacteria, as well as purple and green sulfur bacteria. The presence of methanotrophic bacteria is indicated by ¹³C-depleted methyl hopane. The sediments were deposited in a eutrophic, alkaline palaeolake. Highly reducing (saline) bottom water conditions and a stratified water column existed during OM accumulation of the Qingshankou Formation and Member 1 of the Nenjiang Formation. This is indicated by low pristane/phytane, gammacerane index and MTTC ratios, and the presence of β-carotane and aryl isoprenoids. However, an abrupt change in environmental conditions during deposition of Member 2 of the Nenjiang Formation is indicated by significant changes in salinity and redox-sensitive biomarker ratios. A freshwater environment and suboxic conditions in the deep water prevailed during this period. Higher input of terrigenous OM occurred during deposition of the upper Nenjiang Formation.Good oil-to-source rock correlation was obtained using biomarker fingerprints of oil-stained sandstone from the Quantou Formation and oil shales from the Qingshankou Formation. Based on the extent of isomerisation of C₃₁ hopanes, the oil was most probably derived from oil shales of the Qingshankou Formation in deeper parts of the basin.     

A quantitative study of the degradation of whale bone lipids: Implications for the preservation of fatty acids in marine sediments

The degradation and preservation affecting the biomarker record of ancient metazoa are not fully understood. We report on a five month experiment on the fate of fatty acids (FAs) during the degradation of recent whale vertebrae (Phocoena phocoena). Whale bones were analysed for extractable FAs and macromolecularly bound n-acyl compounds. Fresh bone showed extractable FAs dominated by 16:1ω7c, 16:0, 18:1ω9c and 18:0. Calculated degradation rate constant (k) values showed a rapid decrease in FA concentration, with k values higher for unsaturated than for saturated compounds (0.08/day for 18:1ω9c, 0.05/day for 16:0). The appearance or increased abundance of distinctive methyl branched (e.g. i/ai-15:0 and -17:0, 10Me-16:0) and hydroxy FAs (e.g. 10OH-16:0 and 10OH-18:0) were observed, providing clear evidence for the microbial degradation of bone organic matter and an input of lipids from specialised bacteria. Catalytic hydropyrolysis (HyPy) of demineralised extraction residues released up to 0.13% of the total n-C₁₆ and n-C₁₈ moieties in the degraded bones. This revealed that only a small, yet sizeable, portion of bone-derived fatty acyl units was sequestered into (proto)kerogen during the earliest stages of degradation.     

Soil organic matter transport along an sub-Arctic river–sea transect

Bacteriohopanepolyols (BHPs) and glycerol dialkyl glycerol tetraethers (GDGTs) have potential as soil-tracing biomarkers for the extensive shelves of the Arctic Ocean. In this work these biomarkers were analysed in surface sediments along a well characterised sub-Arctic transect in the northernmost Baltic Sea from the Kalix River to the central Bothnian Bay to assess their environmental behaviour and potential for tracing the contribution of soil in this type of system. There was a high BHP diversity and enhanced total BHP concentration in the estuarine sediments, whereas a much less diverse pattern could be observed in the open bay with lower total BHP concentration. In addition, both soil marker BHPs (adenosylhopanes) and branched GDGTs were substantially more abundant in the estuarine than the open bay sediments.The $R_{\text{soil}}^{\prime }$ index, based on the R_soil index minus the contribution from the methylated soil marker BHPs, is suggested as a new approach for tracing soil derived organic matter (OM) in the (sub)-Arctic region. The index decreased along the transect in an off-river direction, correlating strongly with both the branched and isoprenoid tetraether (BIT) index and the stable carbon isotopic composition of the sedimentary organic carbon. These field results indicate that both the $R_{\text{soil}}^{\prime }$ and the BIT indices have potential for tracing soil derived OM in sub-Arctic to Arctic waters.     

Bacterial hopanoids as tracers of organic carbon sources and processing across the western Arctic continental shelf

Tracing the inputs of bacterial organic carbon to marine systems has been constrained by the lack of distinguishing geochemical tracers and limited contribution in sediments compared to other sources of organic matter. Bacteriohopanepolyols (BHPs) provide a direct means to identify bacterial inputs which also reflect potential bacterial groups and their activities in aquatic systems. We applied recent analytical approaches to identify and quantify bacterial derived carbon contributions to surface sediments from the western Arctic Ocean using BHPs. The abundance and distribution of BHPs resemble trends of water column primary production and suggest active heterotrophic recycling of in situ production with some component of long term preservation. BHPs proposed as terrestrial derived signatures (i.e. adenosylhopanes) were also abundant in western Arctic sediments and reflect offshore trends of other terrigenous lipid signatures with a fraction representing their degradative products. Analysis of BHPs in organic rich peat and surface sediments from two Arctic rivers showed the highest inputs of adenosylhopanes, implying active bacterial recycling of recalcitrant terrigenous material. BHPs observed in western Arctic surface sediments reveal significant contributions of bacteria associated with organic carbon from multiple sources.     

A new particulate Mn-Fe-P-shuttle at the redoxcline of anoxic basins

Pelagic redoxclines of anoxic basins and deeps form the suboxic transition between oxygenated surface and anoxic or even sulfidic bottom waters. Intense element cycling, favoured by elevated microbial activity, causes steep gradients of physico-chemical parameters, nutrients and redox-sensitive trace metals. This study presents a conceptual model for authigenic particle formation at pelagic redoxclines, which is based on the tight coupling of Mn, Fe, and P cycles. Besides the well-known occurrence of Mn-oxides, textural (SEM-EDX) and geochemical (ICP-OES, ICP-MS) analyses of particles from the redoxclines of the Black Sea and the Baltic Sea (Gotland Basin, Landsort Deep) evidence the existence of earlier postulated Fe-oxyhydroxo-phosphates and emphasize mixed phases consisting of Mn-oxides and Fe-oxyhydroxo-phosphates as a new solid species. Most of the analyzed particles are star-shaped, of about 5 μm in size, and occur as single particles or aggregates without any morphological differences between Mn-oxides, Fe-oxyhydroxo-phosphates, and mixed phases. Throughout the redoxcline, these minerals show a general succession with maximum abundance of Mn-oxides above the redoxcline followed by mixed phases and almost pure Fe-phosphates within and below the redoxcline, respectively. Molar Fe/P ratios of single particles argue against the formation of known pure Fe-phosphates like vivianite or strengite at the lower end of the redox transition zone, but are consistent with recent experimental findings for colloidal P-bearing hydrous ferric oxides. Moreover, morphological similarities suggest the formation of irregular Fe-oxyhydroxo coatings due to oxidation of upward diffusing Fe²⁺ by oxygen and stepwise replacement of Mn(IV) by Fe(III) on sinking MnO_x particles followed by immediate adsorption or even co-precipitation of phosphate. Batch-type experiments using biogenic MnO_x particles demonstrate the efficient potential of Fe²⁺ oxidation by sinking MnO_x particles. When entering sulfidic waters MnO_x particles are progressively reduced leading to an increasing relative abundance of Fe- and P-rich particles. In deeper parts of the water column these particles are also reductively dissolved, thereby releasing Fe²⁺ and phosphate to the water column. This Mn-Fe-P-shuttle likely affects phosphate transport throughout the water column and thus impacts primary production at least over longer time scales. Furthermore, the particulate Mn-Fe-P-shuttle must have played an important role for the cycling of P and certain trace metals in ancient ocean basins, e.g., during certain periods of Cretaceous black shale formation and should be considered in future mass balances and modeling approaches dealing with oxic/anoxic interfaces of aquatic ecosystems.     

大兴安岭多年冻土区不同林型土壤微生物群落特征

高纬度多年冻土区是全球变化的敏感区域,揭示不同林型土壤微生物群落的演变规律,对于理解气候变化对寒区生态系统的影响机制具有重要意义。以大兴安岭多年冻土区3种典型林型（落叶松林、樟子松林和白桦林）为研究对象,运用磷脂脂肪酸法（PLFA）系统研究土壤微生物群落结构间差异及与土壤因子的关系。结果表明：不同林型土壤中共检测到38种PLFA生物标记,含量较高的PLFA为16∶0、18∶0、19∶0和18∶2ω6c;各类群微生物中,细菌PLFA含量最高,占总磷脂脂肪酸的83.78%~90.55%,其次为真菌,放线菌最低;白桦林土壤总磷脂脂肪酸、革兰氏阴性菌、革兰氏阳性菌、真菌和放线菌的含量最高分别为22.03、5.13、4.90、1.88和0.77 nmol·g^-1,而樟子松林最低分别为14.25、2.75、2.75、1.34和0.51 nmol·g^-1。Shannon-Wiener多样性指数主要表现为白桦林 > 落叶松林 > 樟子松林。冗余分析结果为：土壤含水量、全氮、总有机碳与总磷脂脂肪酸、细菌、革兰氏阳性菌和革兰氏阴性菌呈显著正相关（P<0.05）;铵态氮、硝态氮、全磷与真菌和放线菌呈显著正相关（P<0.05）。大兴安岭多年冻土区不同林型间土壤微生物群落特征存在显著差异,土壤含水量、全氮和总有机碳是影响多年冻土微生物群落结构的主要因素。     

Aerobic methanotrophy at ancient marine methane seeps: A synthesis

The molecular fingerprints of the chemosynthesis based microbial communities at methane seeps tend to be extremely well preserved in authigenic carbonates. The key process at seeps is the anaerobic oxidation of methane (AOM), which is performed by consortia of methanotrophic archaea and sulphate reducing bacteria. Besides the occurrence of ¹³C depleted isoprenoids and n-alkyl chains derived from methanotrophic archaea and sulphate reducing bacteria, respectively, ¹³C depleted triterpenoids have been reported from a number of seep deposits. In order to evaluate the significance of these apparently non-AOM related molecular fossils, the biomarker inventories of one Campanian and two Miocene methane seep limestones are compared. These examples provide strong evidence that methane was not solely oxidized by an anaerobic process. Structural and carbon isotope data reveal that aerobic methanotrophy was common at some ancient methane seeps as well. The Miocene Marmorito limestone contains abundant 3β-methylated hopanoids (δ¹³C: −100‰). Most likely, 3β-methylated hopanepolyols, prevailing in aerobic methanotrophs, were the precursor lipids of these compounds. A series of isotopically depleted 4-methylated steranes (lanostanes; δ¹³C: −80‰ to −70‰) and similarly isotopically depleted 17β(H),21β(H)-32-hopanoic acid in the Miocene Pietralunga seep limestone also are derived probably from aerobic methanotrophs. Lanosterol, which is known to be produced by aerobic methanotrophs, is the most likely precursor of 4-methylated steranes. Less obvious is the origin of 8,14-secohexahydrobenzohopanes (δ¹³C: −110‰ to −107‰) in Late Cretaceous seep limestones. These hopanoids probably reflect early degradational products of precursor lipids locally produced by seep endemic aerobic methanotrophs.     

Rapid, oxygen-dependent microbial Mn(II) oxidation kinetics at sub-micromolar oxygen concentrations in the Black Sea suboxic zone

Microbial Mn(II) oxidation kinetics in response to oxygen concentration were assessed in suboxic zone water at six sites throughout the Black Sea. Mn(II) oxidation rates increased asymptotically with increasing oxygen concentration, consistent with Michaelis-Menten enzyme kinetics. The environmental half-saturation constant, K_E, of Mn(II) removal (oxidation) varied from 0.30 to 10.5 μM dissolved oxygen while the maximal environmental rate, V_E−max, ranged from 4 to 50 nM h⁻¹. These parameters varied spatially and temporally, consistent with a diverse population of enzymes catalyzing Mn oxide production in the Black Sea. Coastally-influenced sites produced lower K_E and higher V_E−max constants relative to the Western and Eastern Gyre sites. In the Bosporus Region, the Mn(II) residence time calculated using our K_E and V_E−max values with 0.1 μM oxygen was 4 days, 25-fold less than previous estimates. Our results (i) indicate that rapid Mn(II) oxidation to solid phase Mn oxides in the Black Sea’s suboxic zone is stimulated by oxygen concentrations well below the 3-5 μM concentration reliably detected by current oceanographic methods, (ii) suggest the existence of multiple, diverse Mn(II)-oxidizing enzymes, (iii) are consistent with shorter residence times than previously calculated for Mn(II) in the suboxic zone and (iv) cast further doubt on the existence of proposed reactions coupling solid phase Mn oxide production to electron acceptors other than oxygen.     

Microbial ecology of the stratified water column of the Black Sea as revealed by a comprehensive biomarker study

The stratified water column of the Black Sea is partitioned into oxic, suboxic, and euxinic zones, each characterized by different biogeochemical processes and by distinct microbial communities. In 2003, we collected particulate matter by large volume in situ filtration at the highest resolution to date for lipid biomarker analysis and bacterioplankton for enumeration of major prokaryotic groups. Abundances of several prokaryotic groups were estimated using CARD-FISH probes specific for Bacteria, Archaea (Crenarchaeota and Euryarchaeota), epsilonproteobacteria (mainly sulfide oxidizers) and sulfate reducing bacteria. We also measured a wide range of bacterial and archaeal lipid biomarkers. Depth distributions of diagnostic biomarkers are matched with zonation of microbial processes, including aerobic bacterial oxidation of methane, oxidation of ammonium by bacteria and archaea, metal reduction, and sulfide oxidation at the chemocline, and bacterial sulfate reduction and anaerobic oxidation of methane by archaea in the anoxic zone. Cell densities for archaea and sulfate reducing bacteria are estimated based on water column biomarker concentrations and compared with CARD-FISH results.