Origin of light volatile hydrocarbon gases in mud volcano fluids, Gulf of Cadiz — Evidence for multiple sources and transport mechanisms in active sedimentary wedges

Widespread mud volcanism across the thick (≤ 14 km) seismically active sedimentary prism of the Gulf of Cadiz is driven by tectonic activity along extensive strike–slip faults and thrusts associated with the accommodation of the Africa–Eurasia convergence and building of the Arc of Gibraltar, respectively. An investigation of eleven active sites located on the Moroccan Margin and in deeper waters across the wedge showed that light volatile hydrocarbon gases vented at the mud volcanoes (MVs) have distinct, mainly thermogenic, origins. Gases of higher and lower thermal maturities are mixed at Ginsburg and Mercator MVs on the Moroccan Margin, probably because high maturity gases that are trapped beneath evaporite deposits are transported upwards at the MVs and mixed with shallower, less mature, thermogenic gases during migration. At all other sites except for the westernmost Porto MV, δ¹³C–CH₄ and δ²H–CH₄ values of ~ − 50‰ and − 200‰, respectively, suggest a common origin for methane; however, the ratio of CH₄/(C₂H₆ + C₃H₈) varies from ~ 10 to > 7000 between sites. Mixing of shallow biogenic and deep thermogenic gases cannot account for the observed compositions which instead result mainly from extensive migration of thermogenic gases in the deeply-buried sediments, possibly associated with biodegradation of C₂₊ homologues and secondary methane production at Captain Arutyunov and Carlos Ribeiro MVs. At the deep-water Bonjardim, Olenin and Carlos Ribeiro MVs, generation of C₂₊-enriched gases is probably promoted by high heat flux anomalies which have been measured in the western area of the wedge. At Porto MV, gases are highly enriched in CH₄ having δ¹³C–CH₄ ~ − 50‰, as at most sites, but markedly lower δ²H–CH₄ values < − 250‰, suggesting that it is not generated by thermal cracking of n-alkanes but rather that it has a deep Archaeal origin. The presence of petroleum-type hydrocarbons is consistent with a thermogenic origin, and at sites where CH₄ is predominant support the suggestion that gases have experienced extensive transport during which they mobilized oil from sediments ~ 2–4 km deep. These fluids then migrate into shallower, thermally immature muds, driving their mobilization and extrusion at the seafloor. At Porto MV, the limited presence of petroleum in mud breccia sediments further supports the hypothesis of a predominantly deep microbial origin of CH₄.     

Composition and origin of lipid biomarkers in the surface sediments from the southern Challenger Deep,Mariana Trench

The surface sediments collected from the southern Mariana Trench at water depths between ca. 4900 m and 7068 m were studied using lipid biomarker analyses to reveal the origin and distribution of organic matters. For all samples, an unresolved complex mixture (UCM) was present in the hydrocarbon fractions, wherein resistant component tricyclic terpanes were detected but C₂₇–C₂₉ regular steranes and hopanes indicative of a higher molecular weight range of petroleum were almost absent. This biomarker distribution patterns suggested that the UCM and tricyclic terpanes may be introduced by contamination of diesel fuels or shipping activities and oil seepage elsewhere. The well-developed faults and strike-slip faults in the Mariana subduction zone may serve as passages for the petroleum hydrocarbons. In addition, the relative high contents of even n-alkanes and low Carbon Preference Indices indicated that the n-alkanes were mainly derived from bacteria or algae. For GDGTs, the predominance of GDGT-0 and crenarchaeol, together with low GDGT-0/Crenarchaeol ratios (ranging from 0.86 to 1.64), suggests that the GDGTs in samples from the southern Mariana Trench were mainly derived from planktic Thaumarchaeota. However, the high GDGT-0/crenarchaeol ratio (10.5) in sample BC07 suggests that the GDGTs probably were introduced by methanogens in a more anoxic environment. Furthermore, the n-alkanes C₁₉–C₂₂ and the n-fatty acids C_20:0–C_22:0 were depleted in ¹³C by 3‰ compared to n-alkanes C₁₆–C₁₈ and the n-fatty acids C_14:0–C_18:0, respectively, which was interpreted to result from the preferential reaction of fatty acid fragments with carbon “lighter” terminal carboxyl groups during carbon chain elongation from the precursors to products. The abundance of total alkanes, carboxylic acids, alcohols and total lipids were generally increased along the down-going seaward plate, suggesting the lateral organic matter inputs play an important role in organic matter accumulation in hadal trenches. The extremely high contents of biomarkers in sample BC11 were most likely related to trench topography and current dynamics, since the lower steepness caused by graben texture and proximity to the trench axis may result in higher sedimentation rate. This paper, for the first time, showed the biomarker patterns in surface sediments of the Mariana Trench and shed light on biogeochemistry of the hardly reached trench environment.     

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.     

Application of pyrolysis–GC/MS for the characterisation of suspended particulate organic matter in the Mediterranean Sea: a comparison with the Black Sea

Suspended particulate organic matter (SPOM) both from the oligotrophic Mediterranean and from the more productive Black Sea has been analysed by pyrolysis–gas chromatography/mass spectrometry (Py–GC/MS) and by such conventional techniques as elemental analysis and fluorometry. The data achieved by the two approaches generally confirmed and complemented each other. The relative concentrations of pyrolysis products (termed markers) characteristic of chlorophyll (CHL), lipid, carbohydrate (CBH), and protein (PROT) components of SPOM have been determined. The vertical distribution of lipid markers was more uniform in the Mediterranean surface waters. Their relative abundance increased rapidly in the oxycline of the Black Sea, reaching their highest levels in the suboxic zone, where the protein composition of the SPOM changed significantly. In both seas, the relative concentrations of CHL markers increased consistently within the CHL maximum zone where the CBH markers were less abundant. No lignin markers from terrestrial vegetation were detected at significant levels in the pyrograms.     

溶藻弧菌对三疣梭子蟹抗氧化酶系统的影响

从患乳化病的养殖三疣梭子蟹(Portunus trituberculatus)体组织内分离出痛原菌--溶藻弧菌(Vibrioalginglyticus),通过肌肉注射的方式对三疣梭子蟹进行感染实验,对照组注射等量的生理盐水,在感染后O、24、48和72 h分别采集不同处理组三疣梭子蟹的血淋巴、肌肉和肝胰腺组织,测定溶藻弧菌对其各组织抗氧化相关酶活的影响.结果表明:注射生理盐水的对照组三疣梭子蟹体组织中抗氧化酶和MDA含量在不同的采样时间变化不显著(P>0.05).与对照组比较,三疣梭子蟹感染溶藻弧菌后血淋巴、肌肉和肝胰腺组织中SOD活性随着感染时间的延长显著降低(P<0.05).在感染溶藻弧菌24 h时血淋巴和肝胰腺组织中GSH-px活性有增强的趋势(P>0.05),随后在感染48 h后GSH-px活性显著降低(P<0.05);感染组各体组织中的MDA含量均随着感染时间的延长而显著上升(P<0.05).结果显示梭子蟹感染溶藻弧菌后机体消除氧化过程自由基的抗氧化酶活降低,脂质过氧化物水平升高,使得抗氧化防御能力下降.     

Lipid analysis of a ground sloth coprolite

Coprolites can provide detailed information about the nutritional habits and digestive processes of the animals that produced them and may also yield information about the palaeoenvironment in which the animal existed. To test the utility of the lipid biomarker approach to coprolite analysis, lipids were extracted from a coprolite of the Pleistocene ground sloth Nothrotheriops shastensis. Gas chromatography/mass spectrometry results revealed a dominant spiroketal sapogenin component identified, using nuclear magnetic resonance spectroscopy, as epismilagenin. The dominance of epismilagenin is probably due to ingestion of Yucca spp. and Agave spp., which is consistent with previous studies on the diet of this species.     

Micro-FTIR spectroscopic signatures of Bacterial lipids in Proterozoic microfossils

Precambrian microbial fossils show carbonaceous cellular structure, which often resemble in shape and size cyanobacteria and other prokaryotes. Morphological taxonomy of these minute, simple, and more or less degraded fossils is, however, often not enough to determine their precise phylogenetic positions. Here we report the results of micro-FTIR spectroscopic analyses of well-preserved microfossils in 850 Ma and 1900 Ma stromatolites, together with those of 8 species of extant prokaryotes and 5 of eukaryotes for comparison. These Proterozoic fossils have low CH₃/CH₂ absorbance ratios (R_3/2 < 0.5) of aliphatic CH moieties, suggesting selective preservation of long, straight, aliphatic carbon chains probably derived from bacterial membrane lipids. All the observed R_3/2 values of coccoids, filaments and amorphous organic matter resemble lipid fractions of extant Bacteria including cyanobacteria, but not Archaea. The results indicate that Proterozoic microfossils belong to Bacteria, which is consistent with the cyanobacterial origin inferred from morphology. Moreover, the R_3/2 value of fossilized cell would reflect chemical composition of its precursor membrane lipid, thus could be a useful new tracer for distinguishing Archaea, Bacteria and possibly Eucarya for fossilized and extant microorganisms.     

两株硅藻筒柱藻和纤细角毛藻的油脂生产

通过气泡柱光反应器评价了两株硅藻筒柱藻(Cylindrotheca fusiformis)和纤细角毛藻(Chaetoceros gracilis)的生物量、油脂及甘油三脂的积累.结果发现,其生物量与油脂产率相当,脂肪酸组成方面,也均以C16:0和C16:1为主,但是筒柱藻的油脂组成以甘油三酯为主,纤细角毛藻的油脂以单酰甘油酯、磷脂和糖脂为主.通过培养条件的优化,发现相比于降低初始氮元素与硅元素,降低培养液盐度,能够获得更高的生物量、油脂以及甘油三脂产率.通过筒柱藻批次培养最高获得了0.36 g/(L·d)的甘油三脂产率,且甘三酯占收获干物质的50%以上,具有相当好的应用潜力.     

Lipid and 13C signatures of submicron and suspended particulate organic matter in the Eastern Tropical North Pacific: Implications for the contribution of Bacteria

The contribution of bacterial biomass to total particulate organic matter (POM) in the ocean, including exported material, is poorly constrained. To examine potential signatures for the presence and export of bacterioplankton and their detrital remains, here we provide a detailed compound-specific ¹³C characterization of fatty acids from membrane polar lipids obtained from a water column profile in the Eastern Tropical North Pacific. POM of submicron size (0.2–0.7 μm; “X-POM”) was sampled and analyzed separately from the size class typically collected as “suspended” POM (0.7–53 μm; “L-POM”). The distributions of polar head group classes, specific fatty acid side chains, and natural ¹³C contents all vary, both between particle size classes and with depth in the water column. In general, the polar lipids in submicron material – and by inference, lipids of bacterial origin – have higher ¹³C content than polar lipids from larger POM and are equally abundant. Lipid signatures from the photic zone appear to be partially conserved in the suspended pool during transit down the water column. However, bacterial heterotrophy and possibly chemoautotrophy partially overprint these surface signatures. In addition, active metabolisms in the oxygen minimum zone (OMZ) appear to mediate the disaggregation of POM transported from the surface, thus adding complexity to the pathways of mid-water carbon flux and providing additional organic substrates to the OMZ and below. This “substrate injection” may provide important fuel for the denitrification and anammox reactions. Finally, examination of ¹³C content in polar lipids provides a basis for new interpretation of depth-related variations in δ¹³C values of bulk suspended POM.