Quantifying the concurrent changes in rock volume and fluid composition during serpentinization remains a major challenge in assessing its physicochemical effects during continental rifting, seafloor spreading, and subduction. Here we conducted a series of 11 hydrothermal laboratory experiments where cylindrical cores of natural dunite, harzburgite, and pyroxenite were reacted with an aqueous solution at 300 °C and 35 MPa for up to 18 months. Using three-dimensional microcomputed tomography and thermogravimetry, we show that rock volume systematically increased with time and extent of reaction, leading to a volume increase of 44% (±8%) in altered rock domains after 10–18 months of serpentinization. The volume expansion was accompanied by Mg-Ca exchange between fluid and rock, while Fe and Si were largely conserved. We find that the protolith composition (olivine/orthopyroxene ratio) plays a significant role in controlling the fluid chemistry and the proportions of hydrous secondary minerals during serpentinization. Agreement between alteration mineralogy, composition of reacting fluids, and measured volume changes suggests that serpentinization under static conditions is a volume-increasing process in spite of demonstrable mass transfer. Volume expansion implies an increased water carrying capacity and buoyancy force of serpentinite per unit mass of protolith, while Mg-Ca exchange during serpentinization may affect the Mg/Ca ratio of seawater on Earth and possibly other ocean worlds.
more »
« less
Quantifying the volume increase and chemical exchange during serpentinization
Quantifying the concurrent changes in rock volume and fluid composition during serpentinization remains a major challenge in assessing its physicochemical effects during continental rifting, seafloor spreading, and subduction. Here we conducted a series of 11 hydrothermal laboratory experiments where cylindrical cores of natural dunite, harzburgite, and pyroxenite were reacted with an aqueous solution at 300 °C and 35 MPa for up to 18 months. Using three-dimensional microcomputed tomography and thermogravimetry, we show that rock volume systematically increased with time and extent of reaction, leading to a volume increase of 44% (±8%) in altered rock domains after 10–18 months of serpentinization. The volume expansion was accompanied by Mg-Ca exchange between fluid and rock, while Fe and Si were largely conserved. We find that the protolith composition (olivine/orthopyroxene ratio) plays a significant role in controlling the fluid chemistry and the proportions of hydrous secondary minerals during serpentinization. Agreement between alteration mineralogy, composition of reacting fluids, and measured volume changes suggests that serpentinization under static conditions is a volume-increasing process in spite of demonstrable mass transfer. Volume expansion implies an increased water carrying capacity and buoyancy force of serpentinite per unit mass of protolith, while Mg-Ca exchange during serpentinization may affect the Mg/Ca ratio of seawater on Earth and possibly other ocean worlds.
more »
« less
- Award ID(s):
- 1551431
- NSF-PAR ID:
- 10149538
- Date Published:
- Journal Name:
- Geology
- Volume:
- 48
- ISSN:
- 1943-2682
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
more » « less
Abstract A cave‐monitoring study in Hatchet Bay Cave on the island of Eleuthera, Bahamas, has examined the origins of variations in oxygen and carbon isotopic and minor element composition in cave calcites. Every 3 to 8 months, between 2012 and 2016, temperature, humidity, cave air (δ13CCO2), dripwaters (δ18O and δ2H values, and Ca, Sr, and Mg concentrations), and the chemical composition of precipitating calcite (δ18O and δ13C values, and Ca, Sr, and Mg concentrations) were analyzed in two rooms in the cave. Results from the elemental analyses show that throughout the cave prior calcite precipitation was a driver of the elemental chemistry of the precipitated calcites. In addition, cave calcites show that δ13C and δ18O values were positively correlated with Mg/Ca ratios. The Mg/Ca ratios were also positively correlated with lower calcite precipitation rates. Therefore, water/rock interactions may also influence δ13C and δ18O values and Mg/Ca ratios of the calcite. Differences were observed between the two rooms, with the Main Room of the cave exhibiting increased prior calcite precipitation, more ventilation, lower calcite precipitation rates, and δ18O values, which were farther from equilibrium when compared to the more isolated portion of the cave. These results also validated previous interpretations from Pleistocene stalagmites collected from a nearby Bahamian cave suggesting that a positive covariation between Mg/Ca and δ13C values reflects water/rock interactions.
-
null (Ed.)Geologic processes at convergent plate margins control geochemical cycling, seismicity, and deep biosphere activity in subduction zones and suprasubduction zone lithosphere. International Ocean Discovery Program (IODP) Expedition 366 was designed to address the nature of these processes in the shallow to intermediate depth of the Mariana subduction channel. Although no technology is available to permit direct sampling of the subduction channel of an intraoceanic convergent margin at depths up to 18 km, the Mariana forearc region (between the trench and the active volcanic arc) provides a means to access this zone. Active conduits, resulting from fractures in the forearc, are prompted by along- and across-strike extension that allows slab-derived fluids and materials to ascend to the seafloor along associated faults, resulting in the formation of serpentinite mud volcanoes. Serpentinite mud volcanoes of the Mariana forearc are the largest mud volcanoes on Earth. Their positions adjacent to or atop fault scarps on the forearc are likely related to the regional extension and vertical tectonic deformation in the forearc. Serpentinite mudflows at these volcanoes include serpentinized forearc mantle clasts, crustal and subducted Pacific plate materials, a matrix of serpentinite muds, and deep-sourced formation fluid. Mud volcanism on the Mariana forearc occurs within 100 km of the trench, representing a range of depths and temperatures to the downgoing plate and the subduction channel. These processes have likely been active for tens of millions of years at this site and for billions of years on Earth. At least 10 active serpentinite mud volcanoes have been located in the Mariana forearc. Two of these mud volcanoes are Conical and South Chamorro Seamounts, which are the furthest from the Mariana Trench at 86 and 78 km, respectively. Both seamounts were cored during Ocean Drilling Program (ODP) Legs 125 and 195, respectively. Data from these two seamounts represent deeper, warmer examples of the continuum of slab-derived materials as the Pacific plate subducts, providing a snapshot of how slab subduction affects fluid release, the composition of ascending fluids, mantle hydration, and the metamorphic paragenesis of subducted oceanic lithosphere. Data from the study of these two mud volcanoes constrain the pressure, temperature, and composition of fluids and materials within the subduction channel at depths of about 18 to 19 km. Understanding such processes is necessary for elucidating factors that control seismicity in convergent margins, tectonic and magma genesis processes in the forearc and volcanic arc, fluid and material fluxes, and the nature and variability of environmental conditions that impact subseafloor microbial communities. Expedition 366 centered on data collection from cores recovered from three serpentinite mud volcanoes that define a continuum of subduction-channel processes defined by the two previously cored serpentinite mud volcanoes and the trench. Three serpentinite mud volcanoes (Yinazao, Fantangisña, and Asùt Tesoro) were chosen at distances 55 to 72 km from the Mariana Trench. Cores were recovered from active sites of eruption on their summit regions and on the flanks where ancient flows are overlain by more recent ones. Recovered materials show the effects of dynamic processes that are active at these sites, bringing a range of materials to the seafloor, including materials from the lithosphere of the Pacific plate and from subducted seamounts (including corals). Most of the recovered material consists of serpentinite mud containing lithic clasts, which are derived from the underlying forearc crust and mantle and the subducting Pacific plate. Cores from each of the three seamounts drilled during Expedition 366, as well as those from Legs 125 and 195, include material from the underlying Pacific plate. A thin cover of pelagic sediment was recovered at many Expedition 366 sites, and at Site U1498 we cored through serpentinite flows to the underlying pelagic sediment and volcanic ash deposits. Recovered serpentinites are largely uniform in major element composition, with serpentinized ultramafic rocks and serpentinite muds spanning a limited range in SiO2 , MgO, and Fe2 O3 compositions. However, variation in trace element composition reflects pore fluid composition, which differs as a function of the temperature and pressure of the underlying subduction channel. Dissolved gases H2 , CH4 , and C2 H6 are highest at the site furthest from the trench, which also has the most active fluid discharge of the Expedition 366 serpentinite mud volcanoes. These dissolved gases and their active discharge from depth likely support active microbial communities, which were the focus of in-depth subsampling and preservation for shore-based analytical and culturing procedures. The effects of fluid discharge were also registered in the porosity and GRA density data indicated by higher than expected values at some of the summit sites. These higher values are consistent with overpressured fluids that minimize compaction of serpentinite mud deposits. In contrast, flank sites have significantly greater decreases in porosity with depth, suggesting that processes in addition to compaction are required to achieve the observed data. Thermal measurements reveal higher heat flow values on the flanks (~31 mW/m2) than on the summits (~17 mW/m2) of the seamounts. The new 2G Enterprises superconducting rock magnetometer (liquid helium free) revealed relatively high values of both magnetization and bulk magnetic susceptibility of discrete samples related to ultramafic rocks, particularly in dunite. Magnetite, a product of serpentinization, and authigenic carbonates were observed in the mudflow matrix materials. In addition to coring operations, Expedition 366 focused on the deployment and remediation of borehole casings for future observatories and set the framework for in situ experimentation. Borehole work commenced at South Chamorro Seamount, where the original-style CORK was partially removed. Work then continued at each of the three summit sites following coring operations. Cased boreholes with at least three joints of screened casing were deployed, and a plug of cement was placed at the bottom of each hole. Water samples were collected from two of the three boreholes, revealing significant inputs of formation fluids. This suggests that each of the boreholes tapped a hydrologic zone, making these boreholes suitable for experimentation with the future deployment of a CORK-lite. An active education and outreach program connected with many classrooms on shore and with the general public through social media.more » « less
-
more » « less
Abstract We address in situ serpentinization and mineral carbonation processes in oceanic lithosphere using integrated field magnetic measurements, rock magnetic analyses, superconducting quantum interference device (SQUID) microscopy, microtextural observations, and energy dispersive spectroscopy phase mapping. A representative suite of ultramafic rock samples were collected, within the Atlin ophiolite, along a 100‐m long transect across a continuous outcrop of mantle harzburgite with several alteration fronts: serpentinite, soapstone (magnesite + talc), and listvenite (magnesite + quartz). Strong correlations between changes in magnetic signal strengths and amount of alteration are shown with distinctive contrasts between serpentinite, transitional soapstone, and listvenite that are linked to the formation and breakdown of magnetite. While previous observations of the Linnajavri ultramafic complex indicated that the breakdown of magnetite occurred during listvenite formation from the precursor soapstone (Tominaga et al., 2017,
https://doi.org/10.1038/s41467-017-01610-4 ), results from our study suggest that magnetite destabilization already occurred during the replacement of serpentinite by soapstone (i.e., at lower fluid CO2concentrations). This difference is attributed to fracture‐controlled flow of sulfur‐bearing alteration fluid at Atlin, causing reductive magnetite dissolution in thin soapstone zones separating serpentinite from sulfide‐mineralized listvenite. We argue that magnetite growth or breakdown in soapstone provides insight into the mode of fluid flow and the composition, which control the scale and extent of carbonation. This conclusion enables us to use magnetometry as a viable tool for monitoring the reaction progress from serpentinite to carbonate‐bearing assemblages in space and time with a caution that the three‐dimensionality of magnetic sources impacts the scalability of measurements. -
more » « less
Abstract The distribution of the short‐lived radionuclide26Al in the early solar system remains a major topic of investigation in planetary science. Thousands of analyses are now available but grossite‐bearing Ca‐, Al‐rich inclusions (
CAI s) are underrepresented in the database. Recently found grossite‐bearing inclusions inCO 3 chondrites provide an opportunity to address this matter. We determined the oxygen and magnesium isotopic compositions of individual phases of 10 grossite‐bearingCAI s in the Dominion Range (DOM ) 08006 (CO 3.0) andDOM 08004 (CO 3.1) chondrites. All minerals inDOM 08006CAI s as well as hibonite, spinel, and pyroxene inDOM 08004 are uniformly16O‐rich (Δ17O = −25 to −20‰) but grossite and melilite inDOM 08004CAI s are not; Δ17O of grossite and melilite range from ~ −11 to ~0‰ and from ~ −23 up to ~0‰, respectively. Even within this small suite, in the two chondrites a bimodal distribution of the inferred initial26Al/27Al ratios (26Al/27Al)0is seen, with four having (26Al/27Al)0≤1.1 × 10−5and six having (26Al/27Al)0≥3.7 × 10−5. Five of the26Al‐richCAI s have (26Al/27Al)0within error of 4.5 × 10−5; these values can probably be considered indistinguishable from the “canonical” value of 5.2 × 10−5given the uncertainty in the relative sensitivity factor for grossite measured by secondary ion mass spectrometry. We infer that the26Al‐poorCAI s probably formed before the radionuclide was fully mixed into the solar nebula. All minerals in theDOM 08006CAI s, as well as spinel, hibonite, and Al‐diopside in theDOM 08004CAI s retained their initial oxygen isotopic compositions, indicating homogeneity of oxygen isotopic compositions in the nebular region where theCO grossite‐bearingCAI s originated. Oxygen isotopic heterogeneity inCAI s fromDOM 08004 resulted from exchange between the initially16O‐rich (Δ17O ~−24‰) melilite and grossite and16O‐poor (Δ17O ~0‰) fluid during hydrothermal alteration on theCO chondrite parent body; hibonite, spinel, and Al‐diopside avoided oxygen isotopic exchange during the alteration. Grossite and melilite that underwent oxygen isotopic exchange avoided redistribution of radiogenic26Mg and preserved undisturbed internal Al‐Mg isochrons. The Δ17O of the fluid can be inferred from O‐isotopic compositions of aqueously formed fayalite and magnetite that precipitated from the fluid on theCO parent asteroid. This and previous studies suggest that O‐isotope exchange during fluid–rock interaction affected mostCAI s in CO ≥3.1 chondrites.
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/https://doi.org/10.1130/G47289.1
