Subduction metamorphism of serpentinite‐hosted carbonates beyond antigorite‐serpentinite dehydration (Nevado‐Filábride Complex,Spain)

At sub‐arc depths, the release of carbon from subducting slab lithologies is mostly controlled by fluid released by devolatilization reactions such as dehydration of antigorite (Atg‐) serpentinite to prograde peridotite. Here we investigate carbonate–silicate rocks hosted in Atg‐serpentinite and prograde chlorite (Chl‐) harzburgite in the Milagrosa and Almirez ultramafic massifs of the palaeo‐subducted Nevado‐Filábride Complex (NFC, Betic Cordillera, S. Spain). These massifs provide a unique opportunity to study the stability of carbonate during subduction metamorphism at P–T conditions before and after the dehydration of Atg‐serpentinite in a warm subduction setting. In the Milagrosa massif, carbonate–silicate rocks occur as lenses of Ti‐clinohumite–diopside–calcite marbles, diopside–dolomite marbles and antigorite–diopside–dolomite rocks hosted in clinopyroxene‐bearing Atg‐serpentinite. In Almirez, carbonate–silicate rocks are hosted in Chl‐harzburgite and show a high‐grade assemblage composed of olivine, Ti‐clinohumite, diopside, chlorite, dolomite, calcite, Cr‐bearing magnetite, pentlandite and rare aragonite inclusions. These NFC carbonate–silicate rocks have variable CaO and CO₂ contents at nearly constant Mg/Si ratio and high Ni and Cr contents, indicating that their protoliths were variable mixtures of serpentine and Ca‐carbonate (i.e., ophicarbonates). Thermodynamic modelling shows that the carbonate–silicate rocks attained peak metamorphic conditions similar to those of their host serpentinite (Milagrosa massif; 550–600°C and 1.0–1.4 GPa) and Chl‐harzburgite (Almirez massif; 1.7–1.9 GPa and 680°C). Microstructures, mineral chemistry and phase relations indicate that the hybrid carbonate–silicate bulk rock compositions formed before prograde metamorphism, likely during seawater hydrothermal alteration, and subsequently underwent subduction metamorphism. In the CaO–MgO–SiO₂ ternary, these processes resulted in a compositional variability of NFC serpentinite‐hosted carbonate–silicate rocks along the serpentine‐calcite mixing trend, similar to that observed in serpentinite‐hosted carbonate‐rocks in other palaeo‐subducted metamorphic terranes. Thermodynamic modelling using classical models of binary H₂O–CO₂ fluids shows that the compositional variability along this binary determines the temperature of the main devolatilization reactions, the fluid composition and the mineral assemblages of reaction products during prograde subduction metamorphism. Thermodynamic modelling considering electrolytic fluids reveals that H₂O and molecular CO₂ are the main fluid species and charged carbon‐bearing species occur only in minor amounts in equilibrium with carbonate–silicate rocks in warm subduction settings. Consequently, accounting for electrolytic fluids at these conditions slightly increases the solubility of carbon in the fluids compared with predictions by classical binary H₂O–CO₂ fluids, but does not affect the topology of phase relations in serpentinite‐hosted carbonate‐rocks. Phase relations, mineral composition and assemblages of Milagrosa and Almirez (meta)‐serpentinite‐hosted carbonate–silicate rocks are consistent with local equilibrium between an infiltrating fluid and the bulk rock composition and indicate a limited role of infiltration‐driven decarbonation. Our study shows natural evidence for the preservation of carbonates in serpentinite‐hosted carbonate–silicate rocks beyond the Atg‐serpentinite breakdown at sub‐arc depths, demonstrating that carbon can be recycled into the deep mantle.     

蛇绿岩套中超基性岩体的岩石组合:蛇纹岩、异剥钙榴岩和蛇绿碳酸岩——以西阿尔卑斯Zermatt-Saas蛇绿岩为例

蛇纹岩、异剥钙榴岩和蛇绿碳酸岩是蛇绿岩套中超基性单元特有的3类岩石组合,该套岩石组合的形成过程复杂,经历了从地幔岩浆结晶分异、洋脊变质作用改造和俯冲-仰冲构造过程,记录了从地幔岩浆侵位到造山带形成、演化的全程信息。蛇纹岩由方辉橄榄岩、二辉橄榄岩和纯橄岩通过水化和氧化过程而形成;异剥钙榴岩由含水石榴石、符山石、绿帘石族矿物、透辉石和绿泥石等含水和含钙的硅酸盐矿物组成,是由基性岩经历钙交代和水化作用而形成;蛇绿碳酸岩则由高度破碎变形的蛇纹岩角砾和碳酸岩基质(方解石、白云石或菱镁矿)共同组成,碳酸钙主要来自海水参与蛇纹岩化过程产生的富钙热液。阿尔卑斯西部的Zermatt-Saas蛇绿岩体中这3种岩石的组合研究表明:蛇纹岩化过程发生在大洋变质时期,超基性岩体在海水的作用下形成蛇纹岩。蛇纹岩化过程中释放出主要来自斜方辉石和单斜辉石的钙,与水共同作用交代超基性岩体中的基性岩脉,从而形成异剥钙榴岩。蛇绿碳酸岩形成于俯冲变质之前或俯冲变质的早期。这3类岩石一经形成,都经历了其后的叠加变质作用,进而表明Zermatt-Saas蛇绿岩经历了大洋变质、与俯冲、折返和抬升有关的高压变质和区域变质、绿片岩相变质和晚期热液变质作用的pT轨迹演化,代表着西阿尔卑斯从洋脊变质作用到俯?