Frieder Klein

Magnetite in seafloor serpentinite—Some like it hot

Serpentinization of mantle peridotite generates molecular hydrogen that can be exploited by microorganisms to gain metabolic energy; however, the mechanisms that control hydrogen generation and magnetite formation during serpentinization remain poorly understood. We have examined partly to completely serpentinized peridotites recovered during the Ocean Drilling Program and find a remarkable variation in the abundance of magnetite. Some completely serpentinized peridotites have as much as 6.15 wt% magnetite, whereas others are nearly magnetite free (

Experimental constraints on fluid-rock reactions during incipient serpentinization of harzburgite

Abstract The exposure of mantle peridotite to water at crustal levels leads to a cascade of interconnected dissolution-precipitation and reduction-oxidation reactions-a process referred to as serpentinization. These reactions have major implications for microbial life through the provision of hydrogen (H2). To simulate incipient serpentinization under well-constrained conditions, we reacted centimeter-sized pieces of uncrushed harzburgite with chemically modified seawater at 300 °C and 35 MPa for ca. 1.5 yr (13 441 h), monitored changes in fluid chemistry over time, and examined the secondary mineralogy at the termination of the experiment. Approximately 4 mol% of the protolith underwent alteration forming serpentine, accessory magnetite, chlorite, and traces of calcite and heazlewoodite. Alteration textures bear remarkable similarities to those found in partially serpentinized abyssal peridotites. Neither brucite nor talc precipitated during the experiment. Given that the starting material contained ~4 times more olivine than orthopyroxene on a molar basis, mass balance requires that dissolution of orthopyroxene was significantly faster than dissolution of olivine. Coupled mass transfer of dissolved Si, Mg, and H+ between olivine and orthopyroxene reaction fronts was driven by steep activity gradients and facilitated the precipitation of serpentine. Hydrogen was released in significant amounts throughout the entire experiment; however, the H2 release rate decreased with time. Serpentinization consumed water but did not release significant amounts of dissolved species (other than H2) suggesting that incipient hydration reactions involved a volume increase of ~40%. The reduced access of water to fresh olivine surfaces due to filling of fractures and coating of primary minerals with alteration products led to decreased rates of serpentinization and H2 release. While this concept might seem at odds with completely serpentinized seafloor peridotites, reaction-driven fracturing offers an intriguing solution to the seemingly self-limiting nature of serpentinization. Indeed, the reacted sample revealed several textural features diagnostic of incipient reaction-driven fracturing. We conclude that fracturing must have far reaching impacts on the rates of serpentinization and H2 release in peridotite-hosted hydrothermal systems.

Fluid mixing and the deep biosphere of a fossil Lost City-type hydrothermal system at the Iberia Margin

Significance We provide biogeochemical, micropaleontological, and petrological constraints on a subseafloor habitat at the passive Iberia Margin, where mixing of reduced hydrothermal serpentinization fluids with oxic seawater provided the energy and substrates for metabolic reactions. This mixing zone was inhabited by bacteria and archaea and is comparable to the active Lost City hydrothermal field at the Mid-Atlantic Ridge. Our results highlight the potential of magma-poor passive margins to host Lost City-type hydrothermal systems that support microbial activity in subseafloor environments. Because equivalent systems have likely existed throughout most of Earths history in a wide range of oceanic environments, fluid mixing may have provided the substrates and energy to support a unique subseafloor community of microorganisms over geological timescales. Subseafloor mixing of reduced hydrothermal fluids with seawater is believed to provide the energy and substrates needed to support deep chemolithoautotrophic life in the hydrated oceanic mantle (i.e., serpentinite). However, geosphere-biosphere interactions in serpentinite-hosted subseafloor mixing zones remain poorly constrained. Here we examine fossil microbial communities and fluid mixing processes in the subseafloor of a Cretaceous Lost City-type hydrothermal system at the magma-poor passive Iberia Margin (Ocean Drilling Program Leg 149, Hole 897D). Brucite−calcite mineral assemblages precipitated from mixed fluids ca. 65 m below the Cretaceous paleo-seafloor at temperatures of 31.7 ± 4.3 °C within steep chemical gradients between weathered, carbonate-rich serpentinite breccia and serpentinite. Mixing of oxidized seawater and strongly reducing hydrothermal fluid at moderate temperatures created conditions capable of supporting microbial activity. Dense microbial colonies are fossilized in brucite−calcite veins that are strongly enriched in organic carbon (up to 0.5 wt.% of the total carbon) but depleted in 13C (δ13CTOC = −19.4‰). We detected a combination of bacterial diether lipid biomarkers, archaeol, and archaeal tetraethers analogous to those found in carbonate chimneys at the active Lost City hydrothermal field. The exposure of mantle rocks to seawater during the breakup of Pangaea fueled chemolithoautotrophic microbial communities at the Iberia Margin, possibly before the onset of seafloor spreading. Lost City-type serpentinization systems have been discovered at midocean ridges, in forearc settings of subduction zones, and at continental margins. It appears that, wherever they occur, they can support microbial life, even in deep subseafloor environments.

Metasomatism Within the Ocean Crust

From ridge to trench, the ocean crust undergoes extensive chemical exchange with seawater, which is critical in setting the chemical and isotopic composition of the oceans and their rocky foundation. Although the overall exchange fluxes are great, the first-order metasomatic changes of crustal rocks are generally minor (usually <10% relative change in major element concentrations). Drastic fluid-induced metasomatic mass transfers are limited to areas of very high fluid flux such as hydrothermal upflow zones. Epidotization, chloritization, and serizitization are common in these upflow zones, and they often feature replacive sulfide mineralization, forming significant metal accumulations below hydrothermal vent areas. Diffusional metasomatism is subordinate in layered (gabbroic-doleritic-basaltic) crust, because the chemical potential differences between the different lithologies are minor. In heterogeneous crust (mixed mafic-ultramafic lithologies), however, diffusional mass transfers between basaltic lithologies and peridotite are very common. These processes include rodingitization of gabbroic dikes in the lithospheric mantle and steatitization of serpentinites in contact to gabbroic intrusions. Drivers of these metasomatic changes are strong across-contact differences in the activities of major solutes in the intergranular fluids. Most of these processes take place under greenschist-facies conditions, where the differences in silica and proton activities in the fluids are most pronounced. Simple geochemical reaction path models provide a powerful tool for investigating these processes. Because the oceanic crust is hydrologically active throughout much of its lifetime, the diffusional metasomatic zones are commonly also affected by fluid flow, so that a clear distinction between fluid-induced and lithology-driven metasomatism is not always possible. Heterogeneous crust is common along slow and ultraslow spreading ridges, were much of the extension is accommodated by faulting (normal faults and detachment faults). Mafic-ultramafic contacts hydrate to greater extents and at higher temperatures than uniform mafic or ultramafic masses of rock. Hence, these lithologic contacts turn mechanically weak at great lithopheric depth and are prone to capture much of the strain during exhumation and uplift of oceanic core complexes. Metasomatism therefore plays a critical role in setting rheological properties of oceanic lithosphere along slow oceanic spreading centers, which – by length – comprise half of the global mid-ocean ridge system.

Calcite-accumulating large sulfur bacteria of the genus Achromatium in Sippewissett Salt Marsh

Large sulfur bacteria of the genus Achromatium are exceptional among Bacteria and Archaea as they can accumulate high amounts of internal calcite. Although known for more than 100 years, they remain uncultured, and only freshwater populations have been studied so far. Here we investigate a marine population of calcite-accumulating bacteria that is primarily found at the sediment surface of tide pools in a salt marsh, where high sulfide concentrations meet oversaturated oxygen concentrations during the day. Dynamic sulfur cycling by phototrophic sulfide-oxidizing and heterotrophic sulfate-reducing bacteria co-occurring in these sediments creates a highly sulfidic environment that we propose induces behavioral differences in the Achromatium population compared with reported migration patterns in a low-sulfide environment. Fluctuating intracellular calcium/sulfur ratios at different depths and times of day indicate a biochemical reaction of the salt marsh Achromatium to diurnal changes in sedimentary redox conditions. We correlate this calcite dynamic with new evidence regarding its formation/mobilization and suggest general implications as well as a possible biological function of calcite accumulation in large bacteria in the sediment environment that is governed by gradients. Finally, we propose a new taxonomic classification of the salt marsh Achromatium based on their adaptation to a significantly different habitat than their freshwater relatives, as indicated by their differential behavior as well as phylogenetic distance on 16S ribosomal RNA gene level. In future studies, whole-genome characterization and additional ecophysiological factors could further support the distinctive position of salt marsh Achromatium.

Effect of water activity on rates of serpentinization of olivine

The hydrothermal alteration of mantle rocks (referred to as serpentinization) occurs in submarine environments extending from mid-ocean ridges to subduction zones. Serpentinization affects the physical and chemical properties of oceanic lithosphere, represents one of the major mechanisms driving mass exchange between the mantle and the Earth’s surface, and is central to current origin of life hypotheses as well as the search for microbial life on the icy moons of Jupiter and Saturn. In spite of increasing interest in the serpentinization process by researchers in diverse fields, the rates of serpentinization and the controlling factors are poorly understood. Here we use a novel in situ experimental method involving olivine micro-reactors and show that the rate of serpentinization is strongly controlled by the salinity (water activity) of the reacting fluid and demonstrate that the rate of serpentinization of olivine slows down as salinity increases and H2O activity decreases.

Mid-ocean Ridge Serpentinite in the Puerto Rico Trench: from Seafloor Spreading to Subduction

In this study we investigate the origin and alteration history of serpentinites in two dredge hauls from the North Wall of the Puerto Rico Trench, where the North American plate subducts beneath the Greater Antilles island arc. Faulting of the North American plate at the North Wall of the Puerto Rico Trench exposes oceanic basement in a nearly spreading-parallel direction, offering a unique perspective on crustal accretion and alteration processes in the Cretaceous Quiet Zone. U–Pb age dating of porous zircon in an altered mafic vein in serpentinite from 20 00’00”N, 66 31’57”W yields an age of 114 8 Ma, suggesting that it originated at the Cretaceous Mid-Atlantic Ridge, c. 2200 km east of its current location. After localized high-temperature (>380 C) hydrothermal alteration to chlorite, antigorite, talc and tremolite, peridotites underwent pervasive serpentinization at lower temperatures ( 310–240 C). In addition to lizardite-rich serpentinite, which is prevalent in dredge D10, dredge D2 contains serpentinite dominated by antigorite. Pervasive serpentinization was followed by extensive talc alteration of several antigorite-rich serpentinites from dredge D2, which was accompanied by Fe loss. As the newly formed crust moved off-axis, open-system alteration at low temperatures by seawater (i.e. weathering) modified the mineralogy, chemical composition, and physical properties of the serpentinite. Where present, brucite dissolved and magnetite oxidized to hematite and goethite, which caused a decrease in magnetic susceptibility and an increase in porosity. Weathering led to complete oxidation of several lizardite-serpentinites in dredge D10, whereas talc-altered antigorite serpentinites in dredge D2 were less affected by oxidation. Rare earth element concentrations of lizardite-rich serpentinite in dredge D10 decreased steadily with increasing Fe(III)/Fetot, reflecting simultaneous leaching and oxidation by seawater. These results have implications for our understanding of several processes, including hydrothermal alteration of peridotite at the Cretaceous Mid-Atlantic Ridge, mass transfer and redox reactions between serpentinite and seawater during off-axis weathering, and the introduction of volatiles, oxidizing agents, and antigorite beneath the Greater Antilles Arc.

Progress in Deciphering the Controls on the Geochemistry of Fluids in Seafloor Hydrothermal Systems

Over the last four decades, more than 500 sites of seafloor hydrothermal venting have been identified in a range of tectonic environments. These vents represent the seafloor manifestation of hydrothermal convection of seawater through the permeable oceanic basement that is driven by a subsurface heat source. Hydrothermal circulation has fundamental effects on the transfer of heat and mass from the lithosphere to the hydrosphere, the composition of seawater, the physical and chemical properties of the oceanic basement, and vent ecosystems at and below the seafloor. In this review, we compare and contrast the vent fluid chemistry from hydrothermal fields in a range of tectonic settings to assess the relative roles of fluid-mineral equilibria, phase separation, magmatic input, seawater entrainment, and sediment cover in producing the observed range of fluid compositions. We focus particularly on hydrothermal activity in those tectonic environments (e.g., mid-ocean ridge detachment faults, back-arc basins, and island arc volcanoes) where significant progress has been made in the last decade in documenting the variations in vent fluid composition.