Influence of oxygen fugacity on mineral compositions in peralkaline melts: The Katzenbuckel volcano, Southwest Germany

The igneous rocks of the Katzenbuckel, Southwest Germany, represent a unique and unusual alkaline to peralkaline association within the European Volcanic Province. The magmatic activity can be subdivided into two main phases. Phase I comprises the main rock bodies of phonolite and nepheline syenite, which were later intruded by different peralkaline dyke rocks (tinguaites and alkali feldspar syenite dykes) of phase II. The dyke assemblage was accompanied by magnetite and apatite veins and was followed by a late-stage pneumatolytic activity causing autometasomatic alterations.

As is typical for alkaline to peralkaline igneous rocks, early mafic minerals of phase I rocks comprise olivine, augite and Fe–Ti oxides, which are substituted in the course of fractionation by Na-amphibole and Na-pyroxene. For the early magmatic stage, calculated temperatures range between 880 and 780 °C with low silica activities (0.4 to 0.6) but high relative oxygen fugacities between 0.5 and 1.9 log units above the FMQ buffer. Even higher oxygen fugacities (above the HM buffer) are indicated for the autometasomatic alteration, which occurred at temperatures between 585 and 780 °C and resulted in the formation of pseudobrookite and hematite.

The unusually high oxygen fugacities (even during the early magmatic stage) are recorded by the major element compositions of the mafic minerals (forsterite content in olivine between 68 and 78 mol%, up to 6.2 wt.% ZrO₂ and 8.5 wt.% TiO₂ in clinopyroxene), the unusual mineral assemblages (pseudobrookite, freudenbergite) and by the enrichment of Fe³⁺ in the felsic minerals (up to 2.8 wt.% Fe₂O₃ in alkali feldspar and up to 2.6 wt.% Fe₂O₃ in nepheline). These observations point to a metasomatically enriched and highly oxidized lithospheric mantle as a major source for the Katzenbuckel melts.     

Kimberlite metasomatism at Murowa and Sese pipes, Zimbabwe

Metasomatism accompanying kimberlite emplacement is a worldwide phenomenon, although infrequently described or recognised. At the Cambrian-aged Murowa and Sese kimberlite clusters located within the Archean Zimbabwe Craton just north of the boundary with the Limpopo Mobile Zone in southern central Zimbabwe, the metasomatism is intense and well exposed and the processes can be readily studied. Dykes, sills and the root zones of pipes are exposed at the current erosion level. Kimberlite lithologies present are hypabyssal macrocrystic kimberlite (“HMK”), HMK breccia, and tuffisitic kimberlite breccia (“TKB”) including minor lithic tuffisitic kimberlite breccia (“LTKB”). Country rocks are 2.6 Ga Chibi and Zimbabwe granite batholiths emplaced into 2.6–2.9 Ga or earlier Archean tonalitic gneiss and greenstones. During initial metasomatism, the granites become spotted with green chlorite, needles of alkaline amphiboles (winchite, riebeckite, arfvedsonite) and pyroxenes (aegirine–augite) with minor carbonate and felts of talc. Oligoclase feldspar becomes converted to albite, extensively altered, dusted and reddened with hematite, whereas K-feldspar remains unaffected. The granites become converted to syenite through removal of quartz. More intense metasomatism at Murowa and Sese results in veins of green metasomatite which cut and disrupt the granite. Progressive disruption entrains granite blocks, breaking down the granite still further, spalling off needle-like granite slivers, and so giving rise to LTKB. This process of disruption and entrainment appears to be the manner of initial development of the pipe structure. The chemistry of the metasomatite is intermediate between granite and kimberlite. Compared to granite country rock it has markedly higher Mg, Cr, Ni, CO₂ and H₂O+, higher Ca, Mn, Nb, Sr, P, Fe³⁺/Fe²⁺ ratio, U, Co, and Cu, approximately equal TiO₂, K₂O, Na₂O, La, Ta, Rb, Zr, Zn and resultant lower SiO₂, Al₂O₃, Ga and Y. The metasomatite Na₂O/K₂O ratio is slightly higher than that of the granite. The metasomatic process is broadly analogous to fenitisation of granitic wall rock accompanying carbonatite complex emplacement. The metasomatism at Murowa and Sese was caused by fluids from the rising but confined proto-kimberlite melt penetrating into cracks and matrix of granite country rock and reacting with it. These fluids were CO₂-rich, hydrous, oxidising, enhanced in ultramafic elements and carried low levels of Na.     

Corundum formation by metasomatic reactions in Archean metapelite,SW Greenland:Exploration vectors for ruby deposits within high-grade greenstone belts

Corundum (ruby-sapphire) is known to have formed in situ within Archean metamorphic rocks at several localities in the North Atlantic Craton of Greenland. Here we present two case studies for such occurrences: (1) Maniitsoq region (Kangerdluarssuk), where kyanite paragneiss hosts ruby corundum, and (2) Nuuk region (Storø), where sillimanite gneiss hosts ruby corundum. At both occurrences, ultramafic rocks (amphibole-peridotite) are in direct contact with the ruby-bearing zones, which have been transformed to mica schist by metasomatic reactions. The bulk-rock geochemistry of the ruby-bearing rocks is consistent with significant depletion of SiO₂ in combination with addition of Al₂O₃, MgO, K₂O, Th and Sr relative to an assumed aluminous precursor metapelite. Phase equilibria modelling supports ruby genesis from the breakdown of sillimanite and kyanite at elevated temperatures due to the removal of SiO₂. The juxtaposition of relatively silica- and aluminum-rich metasedimentary rocks with low silica ultramafic rocks established a chemical potential gradient that leached/mobilized SiO₂ allowing corundum to stabilize in the former rocks. Furthermore, addition of Al₂O₃ via a metasomatic reaction is required, because Al/Ti is fractionated between the aluminous precursor metapelites and the resulting corundum-bearing mica schist. We propose that Al was mobilized either by complexation with hydroxide at alkaline conditions, or that Al was transported as K-Al-Si-O polymers at deep crustal levels. The three main exploration vectors for corundum within Archean greenstone belts are: (1) amphibolite- to granulite-facies metamorphic conditions, (2) the juxtaposition of ultramafic rocks and aluminous metapelite, and (3) mica-rich reactions zones at their interface.     

Metasomatism and the formation of greisen in Grainsgill,Cumbria, England

A section of hornfelsed Skiddaw Slate adjacent to the margin of the Grainsgill Greisen is described and chemical analyses of the various rock types presented. The results confirm that hydrothermal fluids liberated K and Na from the granite to produce the greisen. This gave rise to K metasomatism of the adjacent hornfels and to retrogressive metamorphism over a radius of 200m from the intrusion. Na leached from the hornfels near the intrusion and that liberated during the formation of the greisen are probably the sources of the Na in the brines recorded in fluid inclusions within the nearby quartz-tungsten veins.     

Depleted lithosphere from the mantle wedge beneath Tres Lagos, southern Patagonia, Argentina

Anhydrous spinel lherzolite and harzburgite xenoliths from Tres Lagos, situated inboard of the Volcanic Arc Gap (VAG) in southernmost Patagonia, are samples of a depleted lithospheric mantle and can be divided into two major groups: metasomatized and non-metasomatized. Metasomatized samples, which are the minority, are partly mylonitized and their metasomatism is related to this tectonic process. A group of non-metasomatized samples have enriched whole rock LREE-abundances that are not consistent with the depleted LREE-abundances in their clinopyroxenes. Intergranular host basalt infiltration could be responsible for the whole rock LREE enrichments. Their Sr- and Nd-isotopic ratios have also been affected by host basalt infiltration, whereas their high Sr-isotopic ratios point to subsequent contamination by ground-water and/or Ca-rich surface solutions. Similar contamination is thought to cause the decoupling of Sr- and Nd-isotopes (high Sr- and Nd-isotopic ratios) observed in the non-metasomatized samples with depleted whole rock LREE. A two-stage partial melting process could be responsible for the origin of the Tres Lagos xenoliths. Model calculations have shown that in the first stage, 2% of batch melting took place in the garnet peridotite field and subsequently the residue experienced 2–8% batch melting in the spinel peridotite field. The Tres Lagos peridotites have not been affected by subduction-related metasomatic processes and they could represent an old lithospheric mantle.     

Compositional signatures of SSZ-type peridotites from the northern Vourinos ultra-depleted upper mantle suite,NW Greece

The northern Vourinos massif, located in the Dinarides-Hellenides mountain belt in the Balkan Peninsula, forms a section of the so-called Neotethyan ophiolitic belt in the Alpine-Himalayan orogenic system. It is comprised mainly of a well-preserved mantle sequence, dominated by voluminous massive harzburgite with variable clinopyroxene and olivine modal abundances, accompanied by subordinate coarse- and fine-grained dunite. The harzburgite rock varieties are characterized by high Cr# [Cr/(Cr + Al)] values in Cr-spinel (0.47–0.74), elevated Mg# [Mg/(Mg + Fe²⁺)] in olivine (0.90–0.93), low Al₂O₃ content in clinopyroxene (≤1.82 wt.%) and low average bulk-rock concentrations of CaO (0.52 wt.%) and Al₂O₃ (0.40 wt.%), which are indicative of their refractory nature. In addition, dunite-type rocks display even more depleted compositions, containing Cr-spinel and olivine with higher Cr# (0.76–0.84) and Mg# (0.91–0.94), respectively. They also display extremely low average abundances of CaO (0.13 wt.%) and Al₂O₃ (0.15 wt.%). The vast majority of the studied peridotites are also strongly depleted in REE. Simple batch and fractional melting models are not sufficient to explain their ultra-depleted composition. Whole-rock trace element abundances of the northern Vourinos mantle rocks can be modeled by up to 22–31% closed-system non-modal dynamic melting of an assumed primitive mantle (PM) source having spinel lherzolite composition. The highly depleted compositional signatures of the investigated peridotites indicate that they have experienced hydrous melting in the fore-arc mantle region above a SSZ. This intense melting event was responsible for the release of arc-related melts from the mantle. These melts reacted with the studied peridotites causing incongruent melting of pyroxenes followed by considerable olivine and Cr-spinel addition in terms of cryptic metasomatism. This later metasomatic episode has obscured any geochemical fingerprints indicative of an early mantle melting event in a MOR setting. The lack of any MOR-type peridotites in the northern Vourinos depleted mantle suite is quite uncommon for SSZ-type Neotethyan ophiolites.     

Geochemical and O-isotope constraints on the evolution of lithospheric mantle in the Ross Sea rift area (Antarctica)

Peridotite xenoliths found in Cenozoic alkali basalts of northern Victoria Land, Antarctica, vary from fertile spinel-lherzolite to harzburgite. They often contain glass-bearing pockets formed after primary pyroxenes and spinel. Few samples are composite and consist of depleted spinel lherzolite crosscut by amphibole veins and/or lherzolite in contact with poikilitic wehrlite. Peridotite xenoliths are characterized by negative Al₂O₃–Mg# and TiO₂–Mg# covariations of clino- and orthopyroxenes, low to intermediate HREE concentrations in clinopyroxene, negative Cr–Al trend in spinel, suggesting variable degrees of partial melting. Metasomatic overprint is evidenced by trace element enrichment in clinopyroxene and sporadic increase of Ti–Fe_tot. Preferential Nb, Zr, Sr enrichments in clinopyroxene associated with high Ti–Fe_tot contents constrain the metasomatic agent to be an alkaline basic melt. In composite xenoliths, clinopyroxene REE contents increase next to the veins suggesting metasomatic diffusion of incompatible element. Oxygen isotope data indicate disequilibrium conditions among clinopyroxene, olivine and orthopyroxene. The highest δ¹⁸O values are observed in minerals of the amphibole-bearing xenolith. The δ¹⁸O_cpx correlations with clinopyroxene modal abundance and geochemical parameters (e.g. Mg# and Cr#) suggest a possible influence of partial melting on oxygen isotope composition. Thermobarometric estimates define a geotherm of 80°C/GPa for the refractory lithosphere of NVL, in a pressure range between 1 and 2.5 GPa. Clinopyroxene microlites of melt pockets provide P–T data close to the anhydrous peridotite solidus and confirm that they originated from heating and decompression during transport in the host magma. All these geothermometric data constrain the mantle potential temperature to values of 1250–1350°C, consistent with the occurrence of mantle decompressional melting in a transtensive tectonic regime for the Ross Sea region.     

Formation and alteration of plagiogranites in an ultramafic-hosted detachment fault at the Mid-Atlantic Ridge (ODP Leg 209)

We examined small-scale shear zones in drillcore samples of abyssal peridotites from the Mid-Atlantic Ridge. These shear zones are associated with veins consisting of chlorite + actinolite/tremolite assemblages, with accessory phases zircon and apatite, and they are interpreted as altered plagiogranite melt impregnations, which originate from hydrous partial melting of gabbroic intrusion in an oceanic detachment fault. Ti-in-zircon thermometry yields temperatures around 820°C for the crystallization of the evolved melt. Reaction path modeling indicates that the alteration assemblage includes serpentine of the adjacent altered peridotites. Based on the model results, we propose that formation of chlorite occurred at higher temperatures than serpentinization, thus leading to strain localization around former plagiogranites during alteration. The detachment fault represents a major pathway for fluids through the oceanic crust, as evidenced by extremely low δ¹⁸O of altered plagiogranite veins (+3.0–4.2‰) and adjacent serpentinites (+ 2.6–3.7‰). The uniform oxygen isotope data indicate that fluid flow in the detachment fault system affected veins and adjacent host serpentinites likewise. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Subduction-zone peridotites and their records of crust-mantle interaction

Subduction is the core process of plate tectonics. The mantle wedge in subduction-zone systems represents a key tectonic unit, playing a significant role in material cycling and energy exchange between Earth's layers. This study summarizes research progresses in terms of subduction-related peridotite massifs, including supra-subduction zone(SSZ) ophiolites and mantle-wedge-type(MWT) orogenic peridotites. We also provide the relevant key scientific questions that need be solved in the future. The mantle sections of SSZ ophiolites and MWT orogenic peridotites represent the mantle fragments from oceanic and continental lithosphere in subduction zones, respectively. They are essential targets to study the crust-mantle interaction in subduction zones. The nature of this interaction is the complex chemical exchanges between the subducting slab and the mantle wedge under the major control of physical processes. The SSZ ophiolites can record melt/fluid-rock interaction, metamorphism,deformation, concentration of metallogenic elements and material exchange between crust and mantle, during the stages from the generation of oceanic lithosphere at spreading centers to the initiation, development, maturation and ending of oceanic subduction at continental margins. The MWT orogenic peridotites reveal the history of strong metamorphism and deformation during subduction, the multiple melt/fluid metasomatism(including silicatic melts, carbonatitic melts and silicate-bearing C-HO fluids/supercritical fluids), and the complex cycling of crust-mantle materials, during the subduction/collision and exhumation of continental plates. In order to further reveal the crust-mantle interaction using subduction-zone peridotites, it is necessary to utilize high-spatial-resolution and high-precision techniques to constrain the complex chemical metasomatism, metamorphism,deformation at micro scales, and to reveal their connections with spatial-temporal evolution in macro-scale tectonics.     

Chemical fluid transport (CFT): A window into Earth and its development

Gas phase transport according to chemical fluid transport (CFT) in Earth's crust as well as in the solar nebula is characterized by very high transport efficiency. Systematic investigations of mobilization, transport and deposition of gaseous MeX (Me = metal, X = F or Cl) compounds by solid gas equilibrium reactions are suitable to explain numerous extensive accumulations of minerals and ores. More than 40 of the considered chemical elements form volatile MeX compounds. Some elements tend to form MeF compounds, whereas others are more likely to form MeCl compounds. Silicon reacts with HF to form SiF₄ and replaces other elements to form MeF compounds at low temperature ranges. Accumulations caused by SiF₄ transport explain the formation of numerous quartz varieties and silicate minerals in Earth's crust. Iron most likely reacts with HCl to form FeCl₂ as well as FeCl₃ and explain the formation of iron or iron compounds. Thermodynamically directed transport from cool to hot areas in connection with cyclic processes increases the transport efficiency of MeX-species. Such species are SiF₄, Al₂F₆, POF₃, Cu₃Cl₃, SnCl₄, BF₃, GeF₄, GeCl₄, Ga₂Cl₆, ZrF₄, NbF₅ and TiF₄. The transport gases SiF₄ and POF₃ often react with environmental compounds forming pneumatolytic and metasomatical mineral accumulations. CFT is the “motor” of pneumatolytic and metasomatical processes.