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Copper slag (CS) remains a challenging industrial by-product with a relatively small utilization fraction. The present study investigated the development of one-part alkali-activated cements based on CS, ground granulated blast furnace slag (GGBS) and a mixture of the two as a precursor. We investigated 5 to 15 wt% solid sodium metasilicate (Na2SiO3) and disilicate (Na2Si2O5) as alkaline reagents. Isothermal calorimetry showed that the reactivity of the system was higher for the metasilicate based samples, with early reaction and higher cumulative heat released. Metasilicate based samples also presented a more densified microstructure, lower porosity and higher strength. Better performances were observed with 10 wt% metasilicate/disilicate with respect to the 5 and 15 wt%. The 28-day compressive strength and elastic modulus of 10 wt% metasilicate samples reached 75 MPa and 25 GPa, respectively, and, for paste samples, ranged from 100 wt% GGBS to 50/50 wt% CS/GGBS. The microstructure and calorimetry of the pastes showed that GGBS actively participated in the binding process, whereas CS played a smaller role and acted as a filler and catalyst. The substitution of commercial GGBS by CS up to 50 wt% did not affect the overall performance, thus, bringing CS forward as an economically interesting precursor.

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.

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.