Molecular and isotopic partitioning of low-molecular-weight hydrocarbons during migration and gas hydrate precipitation in deposits of a high-flux seepage site

Detailed knowledge of the extent of post-genetic modifications affecting shallow submarine hydrocarbons fueled from the deep subsurface is fundamental for evaluating source and reservoir properties. We investigated gases from a submarine high-flux seepage site in the anoxic Eastern Black Sea in order to elucidate molecular and isotopic alterations of low-molecular-weight hydrocarbons (LMWHC) associated with upward migration through the sediment and precipitation of shallow gas hydrates. For this, near-surface sediment pressure cores and free gas venting from the seafloor were collected using autoclave technology at the Batumi seep area at 845 m water depth within the gas hydrate stability zone.Vent gas, gas from pressure core degassing, and from hydrate dissociation were strongly dominated by methane (> 99.85 mol.% of ∑[C₁–C₄, CO₂]). Molecular ratios of LMWHC (C₁/[C₂ + C₃] > 1000) and stable isotopic compositions of methane (δ¹³C = ? 53.5‰ V-PDB; D/H around ? 175‰ SMOW) indicated predominant microbial methane formation. C₁/C₂₊ ratios and stable isotopic compositions of LMWHC distinguished three gas types prevailing in the seepage area. Vent gas discharged into bottom waters was depleted in methane by > 0.03 mol.% (∑[C₁–C₄, CO₂]) relative to the other gas types and the virtual lack of ¹⁴C–CH₄ indicated a negligible input of methane from degradation of fresh organic matter. Of all gas types analyzed, vent gas was least affected by molecular fractionation, thus, its origin from the deep subsurface rather than from decomposing hydrates in near-surface sediments is likely.As a result of the anaerobic oxidation of methane, LMWHC in pressure cores in top sediments included smaller methane fractions [0.03 mol.% ∑(C₁–C₄, CO₂)] than gas released from pressure cores of more deeply buried sediments, where the fraction of methane was maximal due to its preferential incorporation in hydrate lattices. No indications for stable carbon isotopic fractionations of methane during hydrate crystallization from vent gas were found. Enrichments of ¹⁴C–CH₄ (1.4 pMC) in short cores relative to lower abundances (max. 0.6 pMC) in gas from long cores and gas hydrates substantiates recent methanogenesis utilizing modern organic matter deposited in top sediments of this high-flux hydrocarbon seep area.     

Redistribution of HFSE elements during rutile replacement by titanite

Titanite growth at the expense of rutile during retrograde hydration of eclogite into amphibolite is a common phenomenon. We investigated an amphibolite sample from the Tromsø eclogite facies terrain in Northern Norway to gain insight into the trace element distribution between rutile and titanite during incomplete resorption of the rutile by titanite. Patchy compositional zoning of Al, Ti, and F in titanite relates to the presence of a fluid with variable Ti/Al and/or F during its growth. Laser ablation ICP–MS and electron microprobe data for high field strength elements (HFSE: Nb, Zr, Ta, and Hf) of rutile resorbed by titanite indicate a pronounced enrichment of these elements in the rim of a large single rutile crystal (~8 mm) and a systematic decrease towards uniform HFSE contents in the large core. HFSE contents of smaller rutile grains (~0.5 mm) and rutile inclusions (<100 μm) in the titanite overgrowth are similar or higher than in the rims of large rutile crystals. Element profiles from the rim inward demonstrate that HFSE enrichment in rutile is controlled by diffusion. HFSE ratios in diffusion-altered rutile show systematic variations compared with the uniform core composition of the large rutile. Modelling of Zr and Nb diffusion in rutile indicates that diffusion coefficients in rutile in fluid-dominated natural systems must be considerably higher than those determined experimentally at 1 bar in dry systems. Variations of HFSE contents in the newly formed titanite show no systematic spatial distribution. HFSE ratios in titanite and the rims of rutile are different, indicating different solid/fluid distribution coefficients in these minerals. Element fractionation by diffusion into the relict rutile and during fluid-mediated growth of new titanite could substantially change the HFSE budget of these minerals and could affect their use for geochemical tracing and other applications, such as Zr-based geothermobarometry.     

Sedimentary evolution of a late Pleistocene wetland indicating extreme coastal uplift in southern Tanzania

Facies analyses of Pleistocene deposits from southern coastal Tanzania (Lindi District) document that sediments formed in a wetland evolving on a coastal terrace in the Lindi Fracture Zone foreland. The exposed succession shows a marked sedimentary change from tidal to terrestrial facies. ¹⁴C analyses on gastropod shells indicate the emergence of the Lindi coast at ∼ 44 ¹⁴C ka BP. Emergence and subsequent elevation of terraces to 21 m above present-day sea level was linked to the falling eustatic sea level prior to the last glacial maximum, and to a periodic elevation due to extensional tectonic episodes in the eastern branch of the East African Rift System (EARS). Since ∼ 44 ¹⁴C ka BP tectonic uplift at the coast was 80-110 m, comparable to that in the extreme uplift areas of the EARS.     

Complete recycling of a magmatic arc: evidence from chemical and isotopic composition of Quaternary trench sediments in Chile (36°–40°S)

Marine Quaternary trench and slope sediments were sampled along the margin of the Southern Andes, Chile between 36° and 40°S. Major and trace element contents indicate only minor influence of weathering and transport fractionation. The whole rock composition of the sediments is similar to the average rock of the Cretaceous to Holocene magmatic arc of this section of the southern volcanic zone. Sr, Nd, and Pb isotope composition of the sediments also resembles closely the average composition of the magmatic arc. The contribution of compositionally distinct Palaeozoic crust, which makes up most of the volume of the forearc, is ~0–20% crustal Sr, Nd, and Pb according to the isotope record of the trench and slope sediments. Input of sediments from the continent into the subduction system was dominated by detritus from the magmatic arc at least for the last 20 My on the basis of the Oligocene to Holocene exhumation history of the margin.     

Construction of three-phase data to model multiphase flow in porous media: Comparing an optimization approach to the finite element approach

Multiphase flow modelling is a major issue in the assessment of groundwater pollution. Three-phase flows are commonly governed by mathematical models that associate a pressure equation with two saturation equations. These equations involve a number of secondary variables that reflect the fluid behaviour in a porous medium. To improve the computational efficiency of multiphase flow simulators, several simplified reformulations of three-phase flow equations have been proposed. However, they require the construction of new secondary variables adapted to the reformulated flow equations. In this article, two different approaches are compared to quantify these variables. A numerical example is given for a typical fine sand.     

Distribution and temporal variation of mega‐fauna at the Regab pockmark (Northern Congo Fan), based on a comparison of videomosaics and geographic information systems analyses

The Regab pockmark is a large cold seep area located 10 km north of the Congo deep sea channel at about 3160 m water depth. The associated ecosystem hosts abundant fauna, dominated by chemosynthetic species such as the mussel Bathymodiolus aff. boomerang, vestimentiferan tubeworm Escarpia southwardae, and vesicomyid clams Laubiericoncha chuni and Christineconcha regab. The pockmark was visited during the West African Cold Seeps (WACS) cruise with RV Pourquoi Pas? in February 2011, and a 14,000‐m² high‐resolution videomosaic was constructed to map the most populated area and to describe the distribution of the dominant megafauna (mussels, tubeworms and clams). The results are compared with previous published works, which also included a videomosaic in the same area of the pockmark, based on images of the BIOZAIRE cruise in 2001. The 10‐year variation of the faunal distribution is described and reveals that the visible abundance and distribution of the dominant megafaunal populations at Regab have not changed significantly, suggesting that the overall methane and sulfide fluxes that reach the faunal communities have been stable. Nevertheless, small and localized distribution changes in the clam community indicate that it is exposed to more transient fluxes than the other communities. Observations suggest that the main megafaunal aggregations at Regab are distributed around focused zones of high flux of methane‐enriched fluids likely related to distinct smaller pockmark structures that compose the larger Regab pockmark. Although most results are consistent with the existing successional models for seep communities, some observations in the distribution of the Regab mussel population do not entirely fit into these models. This is likely due to the high heterogeneity of this site formed by the coalescence of several pockmarks. We hypothesize that the mussel distribution at Regab could also be controlled by the occurrence of zones of both intense methane fluxes and reduced efficiency of the anaerobic oxidation of methane possibly limiting tubeworm colonization.     

Distribution and characteristics of marine habitats in a subpolar bay based on hydroacoustics and bed shear stress estimates—Potter Cove,King George Island,Antarctica

Marine habitats worldwide are increasingly pressurized by climate change, especially along the Antarctic Peninsula. Well-studied areas in front of rapidly retreating tidewater glaciers like Potter Cove are representative for similar coastal environments and, therefore, shed light on habitat formation and development on not only a local but also regional scale. The objective of this study was to provide insights into habitat distribution in Potter Cove, King George Island, Antarctica, and to evaluate the associated environmental processes. Furthermore, an assessment concerning the future development of the habitats is provided. To describe the seafloor habitats in Potter Cove, an acoustic seabed discrimination system (RoxAnn) was used in combination with underwater video images and sediment samples. Due to the absence of wave and current measurements in the study area, bed shear stress estimates served to delineate zones prone to sediment erosion. On the basis of the investigations, two habitat classes were identified in Potter Cove, namely soft-sediment and stone habitats that, besides influences from sediment supply and coastal morphology, are controlled by sediment erosion. A future expansion of the stone habitat is predicted if recent environmental change trends continue. Possible implications for the Potter Cove environment, and other coastal ecosystems under similar pressure, include changes in biomass and species composition.     

The Allende multicompound chondrule (ACC)—Chondrule formation in a local super‐dense region of the early solar system

In Allende, a very complex compound chondrule (Allende compound chondrule; ACC) was found consisting of at least 16 subchondrules (14 siblings and 2 independents). Its overall texture can roughly be described as a barred olivine object (BO). The BO texture is similar in all siblings, but does not exist in the two independents, which appear as relatively compact olivine‐rich units. Because of secondary alteration of pristine Allende components and the ACC in particular, only limited predictions can be made concerning the original compositions of the colliding melt droplets. Based on textural and mineralogical characteristics, the siblings must have been formed on a very short time scale in a dense, local environment. This is also supported by oxygen isotope systematics showing similar compositions for all 16 subchondrules. Furthermore, the ACC subchondrules are isotopically distinct from typical Allende chondrules, indicating formation in or reaction with a more ¹⁶O‐poor reservoir. We modeled constraints on the particle density required at the ACC formation location, using textural, mineral‐chemical, and isotopic observations on this multicompound chondrule to define melt droplet collision conditions. In this context, we discuss the possible relationship between the formation of complex chondrules and the formation of macrochondrules and cluster chondrites. While macrochondrules may have formed under similar or related conditions as complex chondrules, cluster chondrites certainly require different formation conditions. Cluster chondrites represent a mixture of viscously deformed, seemingly young chondrules of different chemical and textural types and a population of older chondrules. Concerning the formation of ACC calculations suggest the existence of very local, kilometer‐sized, and super‐dense chondrule‐forming regions with extremely high solid‐to‐gas mass ratios of 1000 or more.     

Benthic foraminiferal distribution and sedimentary structures suggest tectonic erosion at the Costa Rica convergent plate margin

ABSTRACT Distribution patterns of benthic foraminiferal faunas from ODP Leg 170 Sites 1041 and 1042 show that the Costa Rican convergent margin subsided from coastal to abyssal depth from Middle Miocene to Present. This favours the model of a margin undergoing active subduction erosion. We propose that subduction erosion leads to the removal of material from the base of the forearc wedge and, as a consequence, to progressive subsidence of the forearc. A mean subsidence rate is estimated to be approximately 0.4 mm yr⁻¹.