U-Th stratigraphy of a cold seep carbonate crust

International audienceOn continental margins, oxidation of methane-rich fluids from the sediment often leads to formation of authigenic carbonate pavements on the seafloor. The biogeochemical processes involved during this carbonate precipitation are increasingly understood, but little is known about the duration or mode of carbonate crust formation. Here, we report uranium and thorium concentrations and isotope compositions for a set of 14 samples drilled across an authigenic carbonate pavement, which provide the first stratigraphy for a cold-seep carbonate crust. The 5.5-cm thick crust (NL7-CC2) was collected by submersible on the Nile deep-sea fan in an area of active fluid venting. U-Th analyses must be corrected for initial Th and measurement of co-existing sediments indicates the presence of both scavenged and detrital initial 230Th, which must be considered during this correction. The calculated 230Th/U age-depth profile for NL7-CC2 provides evidence for continuous downward carbonate precipitation at the studied location over the last ~ 5000 years. Three distinct phases can be distinguished from top to bottom with average growth rates of ~ 0.4, 5 and 0.8 cm/kyr, respectively, corresponding to carbonate precipitation rates ranging from ~ 7 to 92 µmol m2 h− 1 (rates consistent with previous estimates). High-resolution δ13C profiles [Gontharet, S., Pierre, C., Blanc-Valleron, M.-M., Rouchy, J.M., Fouquet, Y., Bayon, G., Foucher, J.P., Woodside, J., Mascle, J., The Nautinil Scientific Party, 2007. Nature and origin of diagenetic carbonate crusts and concretions from mud volcanoes and pockmarks of the Nile deep-sea fan (eastern Mediterranean Sea). Deep Sea Res. II 54, 1292-1311] and major elements across NL7-CC2 show that the variations in carbonate precipitation rates were also accompanied by changes in carbonate mineralogy and fluid composition. We suggest that these changes primarily reflect modification of the diagenetic environment, i.e. a progressive depletion of dissolved sulphate through anaerobic oxidation of methane, caused by the initial carbonate crust formation and the resulting reduction in bioirrigation. Overall, U-Th dating of cold seep carbonates offers a promising tool to bring new insights into biogeochemical processes at cold seeps and to assess the timing and duration of fluid venting on continental margins

Controls on authigenic carbonate precipitation at cold seeps along the convergent margin off Costa Rica

Five sediment cores from cold seeps at the forearc off Costa Rica were used to explore the relationship between fluid advection, dissolved Ca concentrations in upward migrating fluids, and authigenic CaCO3 precipitation. A numerical transport-reaction model was used to determine rates of anaerobic oxidation of methane (AOM), CaCO3 precipitation, and benthic fluxes of solutes. Production of carbonate alkalinity and formation of authigenic carbonates is most intense at intermediate flow rates (3–40 cm a−1) and reduced under low and high flux conditions (0.1 and 200 cm a−1). Dissolved Ca concentrations observed in the vent fluids off Costa Rica cover a wide range between 4 and 31 mM, clearly exceeding seawater concentrations at two locations. Systematic model runs showed that high Ca concentrations in ascending fluids enhance the rate of authigenic carbonate production at moderate flow rates leading to an almost quantitative fixation of deeply derived Ca in authigenic carbonates. Hence, CaCO3 precipitation is not only controlled by Ca diffusing into the sediment from bottom water, but also by the Ca concentration in ascending fluids. Thus, Ca enriched fluids offer a reason for enhanced subsurface CaCO3 precipitation and the occurrence of carbonate caps on dewatering structures in the Central American fore-arc. Based on average precipitation rates deduced from the systematic model runs it is possible to give a rough estimate of the global Ca-fixation at cold seeps (∼2·1010 mol Ca a−1), which suggests that cold seeps are most likely not of key importance with respect to Ca cycling in the ocean

Boron concentrations and isotopic compositions in methane-derived authigenic carbonates : constraints and limitations in reconstructing formation conditions

The work is supported by Norwegian Research Council through the schemes PETROMAKS2-NORCRUST (grant number 255150 ) and Centre for Arctic Gas Hydrate, Environment and Climate (CAGE grant number 223259 ) as well as Lundin Norway AS. Cruise MSM57-1/-2 was funded by the German Research Foundation (DFG), the Research Center/Excellence Cluster “The Ocean in the Earth System” at MARUM–Center for Marine and Environmental Sciences, University of Bremen and funds from CAGE.The boron content and isotopic composition (δ11B), of marine carbonates have the potential to constrain CO2 chemistry during carbonate growth conditions. However, obtaining and interpreting boron compositions from authigenic carbonates in geological archives present several challenges that may substantially limit their application. In particular, contamination from non-carbonate phases during sample preparation must be carefully avoided, and a variety of controls on boron composition during authigenic growth conditions must be evaluated. To advance understanding of the use and limitations of boron in authigenic carbonates, we present data and modelling results on methane-derived authigenic carbonate (MDAC), a by-product of microbially mediated anaerobic oxidation of methane, taken from three cold seep sites along the Norwegian margin. We present a novel sequential leaching method to isolate the boron signals from the micritic (Mg-calcite) and cavity-filling (aragonitic) MDAC cements in these complex multi-phase samples. This method successfully minimizes contamination from non-carbonate phases. To investigate the factors that could potentially contribute to the observed boron signals, we construct a numerical model to simulate the evolution of MDAC δ11B and B/Ca ratios over its growth history. We show that diagenetic fluid composition, depths of precipitation, the physical properties of sediments (such as porosity), and mineral surface kinetics all contribute to the observed boron compositions in the different carbonate cements. While broad constraints may be placed on fluid composition, the multiple competing controls on boron in these diagenetic settings limit the ability to place unique solutions on fluid CO2 chemistry using boron in these authigenic carbonates.Publisher PDFPeer reviewe

South China Sea Seeps

This open access book presents an overview on seep systems in South China Sea. It includes numerous illustrations and photographs of the seeps that never seen before. It also introduces multidisciplinary research results to stimulate further research interest

Modeling the Mutualistic Interactions between Tubeworms and Microbial Consortia

The deep-sea vestimentiferan tubeworm Lamellibrachia luymesi forms large aggregations at hydrocarbon seeps in the Gulf of Mexico that may persist for over 250 y. Here, we present the results of a diagenetic model in which tubeworm aggregation persistence is achieved through augmentation of the supply of sulfate to hydrocarbon seep sediments. In the model, L. luymesi releases the sulfate generated by its internal, chemoautotrophic, sulfide-oxidizing symbionts through posterior root-like extensions of its body. The sulfate fuels sulfate reduction, commonly coupled to anaerobic methane oxidation and hydrocarbon degradation by bacterial–archaeal consortia. If sulfate is released by the tubeworms, sulfide generation mainly by hydrocarbon degradation is sufficient to support moderate-sized aggregations of L. luymesi for hundreds of years. The results of this model expand our concept of the potential benefits derived from complex interspecific relationships, in this case involving members of all three domains of life

Gas bubble emissions at continental margins: Detection, mapping, and quantification

The significance of gas bubble emissions at deep-water hydrocarbon seeps on the global carbon cycle is poorly constrained. Methane is, however, an important component regarding past and future climate change scenarios. One of the main motivations of this study was to obtain a better understanding of the sources and transport pathways of gas bubbles in order to evaluate their input to the atmospheric methane inventory. Three areas were investigated, which are located in different geological settings. Gas emissions were found in all three areas, indicating that this is a common phenomenon at different types of hydrocarbon seeps also in deep-water environments. The case studies show that the gas bubble emissions represent an effective pathway to transport methane into the water column. The fate of the gas bubbles while rising through the water column is strongly influenced by hydrate formation around the bubbles. Nevertheless, it was generally observed that the emitted gas bubbles ultimately remain in the ocean interior and thus do not contribute to the atmospheric methane inventory

The Role of Magmatism in Hydrocarbon Generation in Sedimented Rifts: a Nd Isotope Perspective from Mid-Cretaceous Methane-Seep Deposits of the Basque-Cantabrian Basin, Spain

Studies on the involvement of intrusive magmatism in hydrocarbon generation within sedimentary basins have gained momentum owing to increasing appraisal of the role that such processes may play in controlling global carbon cycle perturbations, and the exploration potential of the volcanic sedimentary basins. Nevertheless, for many areas the causal link between the intrusions and surrounding hydrocarbon systems remains disputed, encouraging a search for methods that could aid in identifying different hydrocarbon sources. Here, we have performed a multi-proxy geochemical study of the middle Cretaceous methane-seep deposits of the Basque-Cantabrian Basin, an early-stage, peri-cratonic rift marking the Mesozoic opening of the Bay of Biscay. Infilled by a thick sedimentary succession intruded by shallow-level igneous bodies, the basin shares analogies with modern young, sedimented rifts that sustain hydrocarbon seepage. We have applied a novel approach that uses the Nd isotope composition of the seep deposits to constrain the relationship between hydrocarbon seepage and igneous activity, and to explore the general potential of Nd isotopes to trace magmatic-influenced fluids in volcanic sedimentary basins. The Nd isotope data have been combined with rare earth element analyses and carbon and oxygen isotope measurements, providing broad insight into the former composition of the seeping fluids. For three out of four investigated seeps, the Nd isotope ratios observed in authigenic seep carbonates include signatures markedly more radiogenic than that reconstructed for background seawater-derived pore waters. The level of this Nd-143-enrichment varies both between and within individual deposits, reflecting spatial and temporal differences in fluid composition typical of seep-related environments. The radiogenic Nd isotope signals provide evidence of subseafloor interactions between the seeping fluids and mafic igneous materials, supporting the model of an igneous control on the mid-Cretaceous methane expulsion in the Basque-Cantabrian Basin. The thermogenic origin of the methane is in accord with the moderately negative delta C-13 values and paragenetic successions observed in the studied seep carbonates. For a single deposit, its relatively unradiogenic Nd isotope composition can be attributed to the smallest size and shallowest emplacement depth of the underlying intrusion, likely resulting in a short-lived character and limited hydrocarbon-generation potential of the associated contact metamorphism. The study demonstrates that Nd isotope analyses of seep carbonates offer a tool in disentangling methane fluxes from different organic matter alteration pathways for the numerous, both fossil and modern sedimented rifts for which the involvement of various methane sources remains insufficiently understood.This work was supported by the National Science Centre, Poland (grant No. 2016/23/D/ST10/00444; to MJ) , and the Eusko Jaurlaritza (Ikerketa Taldeak IT930-16) and the Spanish State Research Agency (project PID2019-105670GB-I00/AEI/10.13039/501100011033; both to LMA

Box Models of Volatile Cycles over the Entire Phanerozoic

Three stand-alone geochemical box models have been developed to simulate globally coupled biogeochemical cycles. These models reflect the evolution of the participating biotic and abiotic constituents in marine and terrestrial environments, including the lower atmosphere. The single models focus on the calculation of: 1) the chemical evolution of seawater, 2) the atmospheric methane concentration, and 3) the concentration of oxygen in surface and deep ocean water over the entire Phanerozoic (570 Ma). The models are driven by geological and evolutionary forcings and are controlled by proxy data. Internal feedback is provided by model outputs serving as input to other model components. The Phanerozoic biogeochemical evolution of seawater (dissolved inorganic carbon, alkalinity, nutrients, and oxygen), its isotope sulfur and carbon composition, as well as the atmospheric partial pressures of oxygen (pO2), carbon dioxide (pCO2), and methane (pCH4) are calculated by standard runs of the individual models