Description: Due to the strong interest in geochemical CO2-fluid-rock interaction in the context of geological storage of CO2 a growing number of research groups have used a variety of different experimental ways to identify important geochemical dissolution or precipitation reactions and – if possible – quantify the rates and extent of mineral or rock alteration. In this inter-laboratory comparison the gas-fluid-mineral reactions of three samples of rock-forming minerals have been investigated by 11 experimental labs. The reported results point to robust identification of the major processes in the experiments by most groups. The dissolution rates derived from the changes in composition of the aqueous phase are consistent overall, but the variation could be reduced by using similar corrections for changing parameters in the reaction cells over time. The comparison of experimental setups and procedures as well as of data corrections identified potential improvements for future gas-fluid-rock studies.

Description: The formation of mud volcanoes in the Gulf of Cadiz is closely linked to diapirism in the deep subsurface. The Mercator mud volcano (MMV) is a rare example where diapiric emplacement, in addition to being key for upward fluid migration, is also an important zone for fluid and mineral diagenesis. The most intriguing findings in the near-surface muds of the MMV are extremely high salinities of up to 5.2 M of NaCl from diapiric and evaporitic halite dissolution and the occurrence of authigenic gypsum and anhydrite crystals, both of which have not been observed to date in the Gulf of Cadiz. Employing a thermodynamic model we elucidate how the interplay of temperature pulses, strong salinity gradients, and fluid flow dynamically drive mineral dissolution and re-formation. The strong increase in salinity in the pore fluids has important implications for thermodynamic equilibria by significantly lowering the activity of water, thereby raising the gypsum–anhydrite transition zone from 〉1 km to about 400 m sediment depth at the MMV. This transition is further shifted to immediately below the seafloor during intervals of active mud and fluid expulsion when the MV surface temperature is heated up to at least 30 °C. As a consequence, precipitation of authigenic gypsum near the sediment surface (1–2 mbsf) has been linked to the dissolution of evaporites below the MMV. More precisely, the mechanisms generating supersaturation in the ascending gypsum-saturated MMV fluids are (1) the slow and constant cooling of these fluids along the geothermal gradient during their ascent leading to formation of ubiquitous micro-crystals and (2) the more rapid cooling after a heat pulse or transport from greater and warmer depth during an active mud volcano phase leading to the precipitation of cm-scale gypsum crystals or even fist-size concretions. The MMV fluids approaching the salt diapir from farther below have experienced a genesis similar to those of other mud volcanoes in the Gulf of Cadiz located above deep-rooted faults. These processes include clay mineral dewatering, thermogenic degradation of organic matter and deep high-temperature leaching of terrigenous sediments or continental crust.

Description: Hydrocarbon-rich fluids expelled at mud volcanoes (MVs) may contribute significantly to the carbon budget of the oceans, but little is known about the long-term variation in fluid fluxes at MVs. The Darwin MV is one of more than 40 MVs located in the Gulf of Cadiz, but it is unique in that its summit is covered by a thick carbonate crust that has the potential to provide a temporal record of seepage activity. In order to test this idea, we have conducted petrographic, chemical and isotopic analyses of the carbonate crust. In addition a 1-D transport-reaction model was applied to pore fluid data to assess fluid flow and carbonate precipitation at present. The carbonate crusts mainly comprise of aragonite, with a chaotic fabric exhibiting different generations of cementation and brecciation. The crusts consist of bioclasts and lithoclasts (peloids, intraclasts and extraclasts) immersed in a micrite matrix and in a variety of cement types (microsparite, botryoidal, isopachous acicular, radial and splayed fibrous). The carbonates are moderately depleted in 13C (δ13C = − 8.1 to − 27.9‰) as are the pore fluids (δ13C = − 19.1 to − 28.7‰), which suggests that their carbon originated from the oxidation of methane and higher hydrocarbons, like the gases that seep from the MV today. The carbonate δ18O values are as high as 5.1‰, and it is most likely that the crusts formed from 18O-rich fluids derived from dehydration of clay minerals at depth. Pore fluid modelling results indicate that the Darwin MV is currently in a nearly dormant phase (seepage velocities are 〈 0.09 cm yr− 1). Thus, the thick carbonate crust must have formed during past episodes of high fluid flow, alternating with phases of mud extrusion and uplift. Highlights ► Results of pore fluid modelling indicate low seepage activity at localised sites. ► Pore fluids are supersaturated with respect to hydrocarbons of thermogenic origin. ► AOM supports vent fauna and results in the formation of authigenic carbonates. ► The carbonate crust has a brecciated appearance and mainly consists of aragonite. ► The crust formation seems to be regulated by changes in fluid and mudflow activity.

Description: Lithium concentration and isotope data (δ7Li) are reported for pore fluids from 18 cold seep locations together with reference fluids from shallow marine environments, a sediment-hosted hydrothermal system and two Mediterranean brine basins. The new reference data and literature data of hydrothermal fluids and pore fluids from the Ocean Drilling Program follow an empirical relationship between Li concentration and δ7Li (δ7Li = −6.0(±0.3) · ln[Li] + 51(±1.2)) reflecting Li release from sediment or rocks and/or uptake of Li during mineral authigenesis. Cold seep fluids display δ7Li values between +7.5‰ and +45.7‰, mostly in agreement with this general relationship. Ubiquitous diagenetic signals of clay dehydration in all cold seep fluids indicate that authigenic smectite–illite is the major sink for light pore water Li in deeply buried continental margin sediments. Deviations from the general relationship are attributed to the varying provenance and composition of sediments or to transport-related fractionation trends. Pore fluids on passive margins receive disproportionally high amounts of Li from intensely weathered and transported terrigenous matter. By contrast, on convergent margins and in other settings with strong volcanogenic input, Li concentrations in pore water are lower because of intense Li uptake by alteration minerals and, most notably, adsorption of Li onto smectite. The latter process is not accompanied by isotope fractionation, as revealed from a separate study on shallow sediments. A numerical transport-reaction model was applied to simulate Li isotope fractionation during upwelling of pore fluids. It is demonstrated that slow pore water advection (order of mm a−1) suffices to convey much of the deep-seated diagenetic Li signal into shallow sediments. If carefully applied, Li isotope systematics may, thus, provide a valuable record of fluid/mineral interaction that has been inherited several hundreds or thousands of meters below the actual seafloor fluid escape structure.

Description: Several known gas seep sites along the Hikurangi Margin off the east coast of New Zealand were surveyed by marine controlled source electromagnetic (CSEM) experiments. A bottom-towed electric dipole–dipole system was used to reveal the occurrence of gas hydrate and methane related to the seeps. The experiments were part of the international multidisciplinary research program “New Vents” carried out on German R/V Sonne in 2007 (cruise SO191) to study key parameters controlling the release and transformation of methane from marine cold vents and shallow gas hydrate deposits. Two CSEM lines have been surveyed over known seep sites on Opouawe Bank in the Wairarapa region off the SE corner of the North Island. The data have been inverted to sub-seafloor apparent resistivity profiles and one-dimensional layered models. Clearly anomalous resistivities are coincident with the location of two gas seep sites, North Tower and South Tower on Opouawe Bank. A layer of concentrated gas hydrate within the uppermost 100 m below the seafloor is likely to cause the anomalous resistivities, but free gas and thick carbonate crusts may also play a role. Seismic data show evidence of fault related venting which may also indicate the distribution of gas hydrates and/or authigenic carbonate. Geochemical profiles indicate an increase of methane flux and the formation of gas hydrate in the shallow sediment section around the seep sites. Takahe is another seep site in the area where active venting, higher heat flow, shallow gas hydrate recovered from cores, and seismic fault planes, but only moderately elevated resistivities have been observed. The reasons could be a) the gas hydrate concentration is too low, even though methane venting is evident, b) strong temporal or spatial variation of the seep activity, and c) the thermal anomaly indicates rather temperature driven fluid expulsion that hampers the formation of gas hydrate beneath the vent.

Description: The production of natural gas via injection of fossil-fuel derived CO2 into submarine gas hydrate reservoirs can be an example of tapping a hydrocarbon energy source in a CO2-neutral manner. However, the industrial application of this method is technically challenging. Thus, prior to feasibility testing in the field, multi-scale laboratory experiments and adapted reaction-modeling are needed. To this end, high-pressure flow-through reactors of 15 and 2000 mL sample volume were constructed and tested. Process parameters (P, T, Q, fluid composition) are defined by a fluid supply and conditioning unit to enable simulation of natural fluid-flow scenarios for a broad range of sedimentary settings. Additional Raman- and NMR-spectroscopy aid in identifying the most efficient pathway for CH4 extraction from hydrates via CO2 injection on both microscopic and macroscopic level. In this study we present experimental set-up and design of the highpressure flow-through reactors as well as CH4 yields from H4-hydrate decomposition experiments using CO2-rich brines and pure liquefied CO2.

Description: Within the German gas hydrate initiative SUGAR, we have developed a new tool for predicting the formation of sub-seafloor gas hydrate deposits. For this purpose, a new 2D/3D module simulating the biogenic generation of methane from organic material and the formation of gas hydrates has been added to the petroleum systems modeling software package PetroMod®. T ypically, PetroMod® simulates the thermogenic generation of multiple hydrocarbon components including oil and gas, their migration through geological strata, and finally predicts the oil and gas accumulation in suitable reservoir formations. We have extended PetroMod® to simulate gas hydrate accumulations in marine and permafrost environments by the implementation of algorithms describing (1) the physical, thermodynamic, and kinetic properties of gas hydrates; and (2) a kinetic continuum model for the microbially mediated, low temperature degradation of particulate organic carbon in sediments. Additionally, the temporal and spatial resolutions of PetroMod® were increased in order to simulate processes on time scales of hundreds of years and within decimeters of spatial extension. As a first test case for validating and improving the abilities of the new hydrate module, the petroleum systems model of the Alaska North Slope developed by IES (currently Shlumberger) and the USGS has been chosen. In this area, gas hydrates have been drilled in several wells, and a field test for hydrate production is planned for 2011/2012. The results of the simulation runs in PetroMod® predicting the thickness of the gas hydrate stability field, the generation and migration of biogenic and thermogenic methane gas, and its accumulation as gas hydrates will be shown during the conference. The predicted distribution of gas hydrates will be discussed in comparison to recent gas hydrate findings in the Alaska North Slope region.

Description: The accumulation of methane hydrate in marine sediments is basically controlled by the accumulation of particulate organic carbon at the seafloor, the kinetics of microbial organic matter degradation and methane generation in marine sediments, the thickness of the gas hydrate stability zone (GHSZ), the solubility of methane in pore fluids within the GHSZ and the ascent of deepseated pore fluids and methane gas into the GHSZ. Our present knowledge on these controlling factors is discussed and new estimates of global sediment and methane fluxes are presented. A new transport-reaction model is applied at a global grid defined by these up- dated parameter values. The model yields an improved and better constrained estimate of the global inventory of methane gas hydrates in marine sediments (3000 ± 2000 Gt of methane carbon).

Description: The production of natural gas via injection of fossil-fuel derived CO2 into submarine gas hydrate reservoirs can be an example of tapping a hydrocarbon energy source in a CO2-neutral manner. However, the industrial application of this method is technically challenging. Thus, prior to feasibility testing in the field, multi-scale laboratory experiments and adapted reaction-modeling are needed. To this end, high-pressure flow-through reactors of 15 and 2000 mL sample volume were constructed and tested. Process parameters (P, T, Q, fluid composition) are defined by a fluid supply and conditioning unit to enable simulation of natural fluid-flow scenarios for a broad range of sedimentary settings. Additional Raman- and NMR-spectroscopy aid in identifying the most efficient pathway for CH4 extraction from hydrates via CO2 injection on both microscopic and macroscopic level. In this study we present experimental set-up and design of the highpressure flow-through reactors as well as CH4 yields from H4-hydrate decomposition experiments using CO2-rich brines and pure liquefied CO2.

Description: Submarine mud volcanism is an important pathway for transfer of deep-sourced fluids enriched in hydrocarbons and other elements into the ocean. Numerous mud volcanoes (MVs) have been discovered along oceanic plate margins, and integrated elemental fluxes are potentially significant for oceanic chemical budgets. Here, we present the first detailed study of the spatial variation in fluid and chemical fluxes at the Carlos Ribeiro MV in the Gulf of Cadiz. To this end, we combine analyses of the chemical composition of pore fluids with a 1-D transport-reaction model to quantify fluid fluxes, and fluxes of boron, lithium and methane, across the sediment–seawater interface. The pore fluids are significantly depleted in chloride, but enriched in lithium, boron and hydrocarbons, relative to seawater. Pore water profiles of sulphate, hydrogen sulphide and total alkalinity indicate that anaerobic oxidation of methane occurs at 34–180 cm depth below seafloor. Clay mineral dehydration, and in particular the transformation of smectite to illite, produces pore fluids that are depleted in chloride and potassium. Profiles of boron, lithium and potassium are closely related, which suggests that lithium and boron are released from the sediments during this transformation. Pore fluids are expelled into the water column by advection; fluid flow velocities are 4 cm yr−1 at the apex of the MV but they rapidly decrease to 0.4 cm yr−1 at the periphery. The associated fluxes of boron, lithium and methane vary between 7–301, 0.5–6 and 0–806 mmol m−2 yr−1, respectively. We demonstrate that fluxes of Li and B due to mud volcanism may be important on a global scale, however, release of methane into the overlying water column is suppressed by microbial methanotrophy.