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Dissolution rates of porous crystalline materials reflect the superposition of transport and surface control, mainly via the parameters saturation of the ambient fluid and distribution of surface energy. As a result, reacting surfaces evolve over time showing a heterogeneous distribution of surface rates. The spatiotemporal heterogeneity of surface reaction rates is analyzed using the rate map and rate spectra concept. Here, we quantify the dissolution rate variability covering the nm- to mm-scale of dissolving single-crystal and polycrystalline calcite samples, using a combined approach of X-ray micro-computed tomography (µ-CT) and vertical scanning interferometry (VSI). The dissolution experiments cover reaction periods from 15 minutes up to 54 days. The observed rate ranges are remarkably consistent over the entire reaction period but include a variability of about two orders of magnitude (10-9 - 3 * 10-7 mol m-2 s-1). The rate map data underscore the concurrent and superimposing impact of surface- vs. fluid flow controlled rate portions. The impact of fluid flow on reactivity at the mm-scale in the transport-controlled system is confirmed by 2-D reactive transport modeling. The sub-mm spatial heterogeneity of low vs. high reactivity surface portions of polycrystalline calcite is clearly below the mean crystal size. This suggests the dominant impact of highly reactive surface portions irrespective of the orientation of larger crystals on the overall surface reactivity. Correspondingly, the overall range of intrinsic reactivity heterogeneity as observed using singly crystal material is not further expanded for polycrystalline material. As a general conclusion, numerical reactive transport concepts would benefit from the implementation of a reactivity term resembling the experimentally observed existence of multiple rate components.

Crystal morphologies are essential for deciphering the reaction history of igneous and metamorphic rocks because they often record the interplay between nucleation and growth rates controlled by the departure from equilibrium. Here, we report an exceptional record of the morphological transition of olivine formed during subduction metamorphism and high-pressure dehydration of antigorite-serpentinite to prograde chlorite-harzburgite in the Almirez ultramafic massif (Nevado–Filabride Complex, Betic Cordillera, SE Spain). In this massif, rare varied-textured chlorite-harzburgite (olivine+enstantite+chlorite+oxides) —formed after high–P dehydration of antigorite-serpentinite— exhibits large olivine porphyroblasts made up of rounded cores mantled by coronas of tabular olivine grains, similar to single tabular olivines occurring in the matrix. The correlative X-ray μ-CT and EBSD study of two varied-textured chlorite-harzburgite samples show that tabular olivine in coronas is tabular on (100)Ol with c > b >> a, and grew in nearly the same crystallographic orientation as the rounded olivine cores of the porphyroblast. Quantitative textural analysis and mass balance indicate that varied-textured chlorite-harzburgite is the result of a two-stage nucleation and growth of olivine during the progress of the high–P dehydration of antigorite-serpentinite to chlorite-harzburgite reaction. The first stage occurred under a low affinity (ΔGr) and affinity rate (ΔGr/dt) of the antigorite dehydration reaction that resulted in a low time-integrated nucleation rate and isotropic growth of olivine, forming rounded olivine porphyroblasts. With further progress of the dehydration reaction, a second stage of relatively higher affinity and affinity rate resulted in a higher time-integrated nucleation rate of olivine coeval with a shift from isotropic to anisotropic olivine growth, leading to tabular olivines. The two-stage evolution resulted in olivine porphyroblasts made up of rounded cores mantled by coronas of tabular olivine grains characteristic of varied-texture chlorite-harzburgite. Although a switch to anisotropic tabular olivine in the second stage is consistent with the relative increase in the affinity and affinity rate, these changes cannot solely account for the growth of Almirez olivine tabular on (100). Tabular olivines in komatiites and other igneous rocks are tabular on (010)Ol with either a > c >> b, or a ≈ c > > b, in agreement with experimentally determined growth rates of olivine phenocrysts under moderate to high undercooling and cooling rates. On the other hand, olivine tabular on (100) is expected in the presence of highly polymerized fluids where inhibited growth of the olivine (100) and (010) interfaces occurs, respectively, due to dissociative and molecular adsorption of water monolayers. Rounded and tabular olivines in Almirez varied-textured chlorite-harzburgite show differing trace element compositions that we interpret as due to the infiltration of external fluids during antigorite dehydration. Isothermal infiltration of highly polymerized fluids would explain the shift in the affinity and affinity rate of the antigorite dehydration reaction, as well as the olivine morphology tabular on (100) due to the inhibited growth on the (100) and, to a lesser extent, (010). Our study shows that surface-active molecules may play an essential role in shaping the morphology of growing crystals during fluid-present metamorphic crystallization.

During the last decades, X-ray (micro-)computed tomography has gained increasing attention for the description of porous skeletal and shell structures of various organism groups. However, their quantitative analysis is often hampered by the difficulty to discriminate cavities and pores within the object from the surrounding region. Herein, we test the ambient occlusion (AO) algorithm and newly implemented optimisations for the segmentation of cavities (implemented in the software Amira). The segmentation accuracy is evaluated as a function of (i) changes in the ray length input variable, and (ii) the usage of AO (scalar) field and other AO-derived (scalar) fields. The results clearly indicate that the AO field itself outperforms all other AO-derived fields in terms of segmentation accuracy and robustness against variations in the ray length input variable. The newly implemented optimisations improved the AO field-based segmentation only slightly, while the segmentations based on the AO-derived fields improved considerably. Additionally, we evaluated the potential of the AO field and AO-derived fields for the separation and classification of cavities as well as skeletal structures by comparing them with commonly used distance-map-based segmentations. For this, we tested the zooid separation within a bryozoan colony, the stereom classification of an ophiuroid tooth, the separation of bioerosion traces within a marble block and the calice (central cavity)-pore separation within a dendrophyllid coral. The obtained results clearly indicate that the ideal input field depends on the three-dimensional morphology of the object of interest. The segmentations based on the AO-derived fields often provided cavity separations and skeleton classifications that were superior to or impossible to obtain with commonly used distance-map-based segmentations. The combined usage of various AO-derived fields by supervised or unsupervised segmentation algorithms might provide a promising target for future research to further improve the results for this kind of high-end data segmentation and classification. Furthermore, the application of the developed segmentation algorithm is not restricted to X-ray (micro-)computed tomographic data but may potentially be useful for the segmentation of 3D volume data from other sources.

We reconstruct the 3-D microstructure of centimetre-sized olivine crystals in rocks from the Almirez ultramafic massif (SE Spain) using combined X-ray micro computed tomography (μ-CT) and electron backscatter diffraction (EBSD). The semidestructive sample treatment involves geographically oriented drill pressing of rocks and preparation of oriented thin sections for EBSD from the μ-CT scanned cores. The μ-CT results show that the mean intercept length (MIL) analyses provide reliable information on the shape preferred orientation (SPO) of texturally different olivine groups. We show that statistical interpretation of crystal preferred orientation (CPO) and SPO of olivine becomes feasible because the highest densities of the distribution of main olivine crystal axes from EBSD are aligned with the three axes of the 3-D ellipsoid calculated from the MIL analyses from μ-CT. From EBSD data we distinguish multiple CPO groups and by locating the thin sections within the μ-CT volume, we assign SPO to the corresponding olivine crystal aggregates, which confirm the results of statistical comparison. We demonstrate that the limitations of both methods (i.e. no crystal orientation data in μ-CT and no spatial information in EBSD) can be overcome, and the 3-D orientation of the crystallographic axes of olivines from different orientation groups can be successfully correlated with the crystal shapes of representative olivine grains. Through this approach one can establish the link among geological structures, macrostructure, fabric and 3-D SPO-CPO relationship at the hand specimen scale even in complex, coarse-grained geomaterials.

In a drillcore sample of serpentinized harzburgite from the uppermost oceanic crust (Mid-Atlantic Ridge, ODP Leg 209, Site 1270), we demonstrate using high-resolution 3D-microtomography that micron-sized open cavities are present. The development of porosity is interpreted to result from dissolution of brucite and/or olivine. Petrographic observations indicate that voids are integrated in a network of carbonate veins, the formation of which is linked to changing alkalinity in conjunction with dissolution reactions. Partial carbonate filling of pore spaces indicates that under static conditions low-temperature carbonation leads to clogging of fluid pathways and thus to a reduction in permeability. Electron microprobe analyses show that the inner walls of open voids are lined with Fe-rich precipitates. We propose that the iron in those phases was released by brucite or olivine dissolution and was subsequently oxidized and precipitated as ferric hydroxide. Thermodynamic computations show that this process may be a potential source of catabolic energy for microorganisms inhabiting serpentinites. The proposed carbonation mechanism implies that carbonate precipitation may start soon after exposure of the abyssal peridotites, when dissolution of brucite and weathering of olivine begin, and continue until the phases become inaccessible to seawater. Predicting carbonation rates of abyssal peridotites will hence require understanding of permeability reactions.

Publisher's version (útgefin grein), Surtsey, the youngest of the islands of Vestmannaeyjar, is an oceanic volcano created by explosive basaltic eruptions during 1963-1967 off the southern coast of Iceland. The subsurface deposits of the volcano were first sampled by a cored borehole in 1979. In summer 2017, three cored boreholes were drilled through the active hydrothermal system of the volcano by the International Continental Scientific Drilling Program (ICDP) SUSTAIN Expedition 5059. These cores are expected to provide the first glimpse of microbial life in very young and native basaltic tuff of the oceanic crust. To reduce the contamination of the subsurface environment, seawater circulating fluid was filtered and passed through two UV-sterilizing treatments. One of the boreholes has been equipped with a subsurface observatory dedicated in situ experiments for monitoring water-rock interactions and microbial processes in sterile, artificial basaltic glass and in olivine granules. With temperatures ranging from 25 to 125 °C, the subsurface observatory provides a precise geothermal window into an active hydrothermal system and thus represents an exceptional natural laboratory for studying fluid-rock-microbe interactions at different temperature regimes and facilitates experimental validation of active submarine microbial processes at the limit of functional life, about 121 °C. Comparisons with the 1979 and 2019 drill cores will provide time-lapse observations of hydrothermal processes over a 50-year timescale. Here, we present the technical design of the observatory and the incubation chamber experiments deployed from September 2017 to summer 2019., We thank all members of the SUSTAIN onsite and science teams and the Surtsey Research Society for their contributions to the drilling project. Bernd Zimanowski, at the University of Würzburg, produced the sterile basaltic glass for the current in situ experiments. The SUSTAIN project was funded by the International Continental Scientific Drilling Program (ICDP; led by Marie D. Jackson), the Icelandic Science Fund, ICF-RANNÍS (the IceSUSTAIN consortium led by Magnús T. Guðmundsson), the Bergen Research Foundation and K. G. Jebsen Centre for Deep Sea Research at the University of Bergen, Norway (led by Steffen Leth Jørgensen), the German Research Foundation (DFG; led by Wolfgang Bach and Bernd Zimanowski), and DiSTAR, University of Naples, Federico II, Italy (led by Piergiulio Cappelletti). The University of Utah, USA (Marie D. Jackson) and the two Icelandic power companies, Reykjavík Energy and Landsvirkjun, contributed additional funds. Anonymous reviewers made valuable improvements to the report.

Serpentinite mud volcanism in the Mariana forearc provides a window into the shallow portions of an active subduction zone. Fluid–rock interactions and related mass transfers into the mantle wedge can be assessed by studying the trace element compositions of slab-derived fluids and serpentinized mantle wedge materials brought to the seafloor by the serpentinite mud volcanoes. We investigated variably serpentinized ultramafic clasts from the Yinazao, Fantangisna, and Asut Tesoru mud volcanoes recovered on International Ocean Discovery Program Expedition 366 to examine the transfer of fluid-mobile elements (FMEs) from the slab to the wedge. These mud volcanoes sample the slab–wedge interface at depths of ~13–18 km and estimated temperatures of 80–250 °C. Our samples represent the serpentinized forearc and exhibit a multi-phase serpentinization history, as apparent from microfabrics, mineralogy, and in situ major and trace elemental analyses of distinct generations of serpentine. Initial hydration of the forearc mantle occurred under reducing conditions by Si-rich fluids. Early serpentine is characterized by generally high concentrations of Li, Sr, Rb, Cs, and Ba. Subsequent fluid–rock interactions were driven by Si-rich and FME-poor fluids and at later stages by Si- and FME-poor fluids in the mud volcano conduits, the latter of which resulted in the abundant formation of Fe-rich brucite. Iowaite and hematite indicate that less reducing conditions prevailed during the alteration of clasts after their emplacement at the seafloor. Concentrations of B are generally high but our dataset does not allow distinguishing slab- from seawater-derived B. Serpentine from the shallow-sourced Yinazao exhibits high Rb/Cs ratios of ≤37, highest concentrations of Li, but lowest Rb, Sr, Ba, and Cs contents. The serpentinizing fluids were derived from expulsion of sedimentary pore waters and by the breakdown of opal in the subducted sediments. Serpentine at the intermediate-sourced Fantangisna has Rb/Cs ratios of Including data from the South Chamorro serpentinite mud volcano (18 km slab depth; Kahl et al., 2015, Lithos), we provide a detailed record of slab dehydration reactions at shallow forearc depths and the related mobilization of FMEs as well as their transport into the mantle wedge. Our study demonstrates that slab-derived fluids undergo extensive alteration during the interaction with mantle wedge peridotite. Pore waters from the serpentinite mud volcanoes hence provide incomplete insight into the processes at depth; fluid signatures at the slab–wedge interface as well as their across-forearc changes are best recorded in early hydration products such as serpentine.

The Almirez ultramafic massif (SE Spain) preserves the transformation of high-P antigorite (Atg-) serpentinite to chlorite (Chl-) harzburgite (1.6–1.9 GPa; 680–710 °C), a metamorphic reaction that is the primary source of water at the intermediate depth of subducting slabs. We present a detailed μ-CT and EBSD study of oriented samples across the Atg-serpentinite dehydration isograd to investigate the textural evolution during serpentinite dehydration to peridotite and its relation to stress orientations and the kinematics of subducting slabs. Above the Atg-out isograd, Atg-serpentinite shows a prograde mylonitic foliation and a weak Shape Preferred Orientation (SPO) of oxide aggregates defining a N—S stretching lineation. The antigorite Crystal Preferred Orientation (CPO) is characterized by [001]Atg perpendicular to the foliation, and the poles to (100)Atg and (010)Atg distributed in a girdle-like symmetry with [100]Atg nearly parallel to the stretching lineation. The antigorite microstructure and CPO are consistent with deformation by dislocation creep, twinning, and dissolution-precipitation creep. These textures record the long-term shear deformation near the slab interface where the main compressive stress, σ1, was at an acute angle to the foliation. Below the Atg-out isograd, Atg-serpentinite dehydrated to unfoliated, coarse-grainedChl-harzburgite with granofels or spinifex textures distributed in alternating decameter-sized lenses. Crystallization of granofels and spinifex Chl-harzburgite records, respectively, a sequence of slow and fast fluid draining events during serpentinite dehydration under the same orientation of the principal stresses that resulted in the shear deformation of the Atg-serpentinite. Both textural types exhibit coarse-grained textures with systematic mineral CPOs and SPOs and microstructures without evidence of major ductile deformation. The texture of the granofels Chl-harzburgite formed by a topotactic dehydration reaction after Atg-serpentinite coupled to compaction leading to an olivine layering subparallel to the Atg-serpentinite foliation. The olivines of granofels Chl-harzburgite are rounded and display a weak CPO that can be accounted for by the topotactic reaction 〈100〉Atg||〈100〉Ol and (001)Atg||(010)Ol after Atg-serpentinite. Similarly, orthopyroxene shows a marked CPO consistent with the topotactic reaction (100)Opx||(001)Atg and [001]Opx||[100]Atg. Spinifex Chl-harzburgite displays systematic mineral SPO and CPO. Spinifex olivines are tabular on (100)Ol and elongated along [001]Ol (c > b >> a), and define a ESE–WNW platelet lineation. The average texture is characterized by [001]Ol,Opx subparallel to a strong ESE–WNW oxide aggregate lineation, and [100]Ol,Opx and [001]Ol,Opx within a plane of similar orientation to the Atg-serpentinite foliation. The SPOs and CPOs of spinifex Chl-harzburgites are composed of up to four orientation populations of tabular olivines, where one population is volumetrically dominant in all samples. Relative to the main orientation population, the CPO of olivine shows clustered distribution of [100]Ol and [010]Ol maxima rotated at systematic angles around [001]Ol. These clustered CPOs and SPOs show a remarkable correlation with the orientation of the principal paleostresses. The preponderant orientation population of tabular olivines lies on the plane of maximum compression (σ2–σ3 plane) and has [010]Ol and its (100)Ol tabular faces nearly perpendicular to the Atg-serpentinite foliation. This population can be accounted for by oriented growth of platy crystals perpendicular to σ1. The other populations lie in the plane perpendicular to the least compressive stress (σ3) and the planes of maximum shear. The driving force and causes for the oriented crystallization of tabular olivine in these planes is uncertain, but their correlation with paleostresses suggests a cause-effect relationship. Spinifex and granofels Chl-harzburgites show a marked ESE–WNW oxide aggregate lineation that differs in orientation from that of Atg-serpentinite and is approximately parallel to the intermediate compressive stress (σ2). These lineations and the platelet lineation of spinifex Chl-harzburgite may be due to along-strike fluid flow below the permeability barrier that constituted the Atg-out dehydration isograd. Our study shows that the kinematics of the slab, paleostresses, and fluid flow exert a dynamic control on the textures of Atg-serpentinite dehydrating to peridotite in subducting slabs.

The range of substrates that the bone-eating marine worm Osedax is able to consume has important implications for its evolutionary history, especially its potential link to the rise of whales. Once considered a whale specialist, recent work indicates that Osedax consumes a wide range of vertebrate remains, including whale soft tissue and the bones of mammals, birds and fishes. Traces resembling those produced by living Osedax have now been recognized for the first time in Oligocene whale teeth and fish bones from deep-water strata of the Makah, Pysht and Lincoln Creek formations in western Washington State, USA. The specimens were acid etched from concretions, and details of the borehole morphology were investigated using micro-computed tomography. Together with previously published Osedax traces from this area, our results show that by Oligocene time Osedax was able to colonize the same range of vertebrate remains that it consumes today and had a similar diversity of root morphologies. This supports the view that a generalist ability to exploit vertebrate bones may be an ancestral trait of Osedax. peerReviewed

Iron arsenates, either well or poorly crystalline, are the usual phases of choice for arsenic immobilization in waste forms of variable origin. Among these phases, scorodite (FeAsO 4 ·2H 2 O) is used very often because of its favorable properties. The thermodynamic properties of this phase, necessary for the prediction of its dissolution or precipitation, have been usually constrained by solubility experiments. Here, we measured the thermodynamic properties of scorodite, its polymorph parascorodite, the mineral kaňkite (FeAsO 4 ·3.5H 2 O), and the anhydrous FeAsO 4 by a combination of calorimetric techniques, thus avoiding the inherent uncertainties of the solubility experiments. The enthalpies of formation from elements at standard temperature and pressure for scorodite, parascorodite, kaňkite, and FeAsO 4 are − 1508.9 ± 2.9, − 1506.6 ± 2.9, − 1940.2 ± 2.8, and − 899.0 ± 3.0 kJ·mol − 1 , respectively. The measured standard entropies for scorodite and kaňkite are 188.0 ± 2.1 and 247.6 ± 2.8 J·mol − 1 ·K − 1 , respectively; entropies of FeAsO 4 and parascorodite were estimated. The resulting Gibbs free energies of formation for scorodite, parascorodite, kaňkite,\ and FeAsO 4 are − 1284.8 ± 2.9, − 1282.5, − 1629.6 ± 2.9, and − 786.7 kJ·mol − 1 , respectively. The solubility product for scorodite of − 25.83 ± 0.52 is in an excellent agreement with a previously selected best value of − 25.83 ± 0.07 from Langmuir et al. (2006) . As expected, scorodite is stable under a wide range of conditions applicable to terrestrial surface environments. The anhydrous FeAsO 4 , parascorodite, and kaňkite are either metastable or stable under restricted conditions which are unlikely for the terrestrial surface environments. Using the thermodynamic data for scorodite and for a suite of ferric oxides, we can predict the aqueous As concentrations in systems in which scorodite dissolves and ferric oxides precipitate. These models show that the As concentration can vary widely as function of the nature, chemical composition, and crystallinity of these ferric oxides.

The bone-eating marine annelid Osedax consumes mainly whale bones on the deep-sea floor, but recent colonization experiments with cow bones and molecular age estimates suggesting a possible Cretaceous origin of Osedax indicate that this worm might be able grow on a wider range of substrates. The suggested Cretaceous origin was thought to imply that Osedax could colonize marine reptile or fish bones, but there is currently no evidence that Osedax consumes bones other than those of mammals. We provide the first evidence that Osedax was, and most likely still is, able to consume non-mammalian bones, namely bird bones. Borings resembling those produced by living Osedax were found in bones of early Oligocene marine flightless diving birds (family Plotopteridae). The species that produced these boreholes had a branching filiform root that grew to a length of at least 3 mm, and lived in densities of up to 40 individuals per square centimeter. The inclusion of bird bones into the diet of Osedax has interesting implications for the recent suggestion of a Cretaceous origin of this worm because marine birds have existed continuously since the Cretaceous. Bird bones could have enabled this worm to survive times in the Earth’s history when large marine vertebrates other than fish were rare, specifically after the disappearance of large marine reptiles at the end-Cretaceous mass extinction event and before the rise of whales in the Eocene. peerReviewed