ALBERT

Description: This study presents new secondary ion mass spectrometry (SIMS) reference materials (RMs) for measuring water contents in nominally anhydrous orthopyroxenes from upper mantle peridotites. The enstatitic reference orthopyroxenes from spinel peridotite xenoliths have Mg#s between 0.83 and 0.86, Al2O3 ranges between 4.02 and 5.56 wt%, and Cr2O3 ranges between 0.21 and 0.69 wt%. Based on Fourier-transform infrared spectroscopy (FTIR) characterizations, the water contents of the eleven reference orthopyroxenes vary from dry to 249 ± 6 µg/g H2O. Using these reference grains, a set of orthopyroxene samples obtained from variably altered abyssal spinel peridotites from the Atlantic and Arctic Ridges as well as from the Izu-Bonin-Mariana forearc region was analyzed by SIMS and FTIR regarding their incorporation of water. The major element composition of the sample orthopyroxenes is typical of spinel peridotites from the upper mantle, characterized by Mg#s between 0.90 and 0.92, Al2O3 between 1.66 and 5.34 wt%, and Cr2O3 between 0.62 and 0.96 wt%. Water contents as measured by SIMS range from 68 ± 7 to 261 ± 11 µg/g H2O and correlate well with Al2O3 contents (r = 0.80) and Cr#s (r. = -0.89). We also describe in detail an optimized strategy, employing both SIMS and FTIR, for quantifying structural water in highly altered samples such as abyssal peridotite. This approach first analyzes individual oriented grains by polarized FTIR, which provides an overview of alteration. Subsequently, the same grain along with others of the same sample is measured using SIMS, thereby gaining information about homogeneity at the hand sample scale, which is key for understanding the geological history of these rocks.

Description: Deutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659

Description: Bavarian Equal Opportunities Sponsorship - Realization Equal Opportunities for Women in Research and Teaching

Description: Friedrich-Alexander-Universität Erlangen-Nürnberg (1041)

Description: 〈title xmlns:mml="http://www.w3.org/1998/Math/MathML"〉Abstract〈/title〉〈p xmlns:mml="http://www.w3.org/1998/Math/MathML" xml:lang="en"〉Erzgebirge ultrahigh‐pressure (UHP) garnet peridotite includes scarce layers of garnet pyroxenite, nodules of garnetite and, very rarely, of eclogite. Peridotite‐hosted eclogite shows the same subalkali‐basaltic bulk rock composition, mineral assemblage and peak conditions as gneiss‐hosted eclogite present in the same UHP unit. Garnetite has considerably more Mg, moderately enhanced Ca and Fe and significantly lower contents of Na, Ti, P, K and Si than eclogite, whereas Al is very similar. In addition, the compatible trace elements (Ni, Co, Cr, V) are elevated and most incompatible elements (Zr, Hf, Y, Sr, Rb and rare Earth elements [REE]) are depleted in garnetite relative to eclogite. In contrast to other large ion lithophile elements (LILEs), Pb (+121%) and Ba (+83%) are strongly enriched. The REE patterns of garnetite are characterized by depletion of light and heavy REE and a medium REE hump indicative of metasomatism, features being absent in eclogite. An exceptional garnetite sample shows an REE distribution similar to that of eclogite. Garnetite is interpreted to have formed from the same, but metasomatically altered, igneous protolith as eclogite. Except for Ba and Pb, the chemical signature of garnetite is explained best by metasomatic changes of its basaltic protolith caused by serpentinization of the host peridotite. Garnetite is chemically similar to basaltic rodingite/metarodingite. Although rodingite is commonly more enriched in Ca, there are also examples with moderately enhanced Ca matching the composition of Erzgebirge garnetite. Limited Ca metasomatism is attributed to the preservation of Ca in peridotite during hydrous alteration. This can be explained by incomplete serpentinization favouring metastable survival of the original clinopyroxene. In this case, most Ca is retained in peridotite and not available for infiltration and metasomatism of the garnetite protolith. This inescapable consequence is supported by the fact that clinopyroxene is part of the garnet peridotite UHP assemblage, which would not be the case if Ca had been removed from the protolith prior to high‐pressure metamorphism. The enrichment of compatible elements in garnetite is attributed to decomposition of peridotitic olivine (Ni, Co) and spinel (Cr, V) during serpentinization. Enrichment of Ba and Pb contrasts the behaviour of other LILEs and is ascribed to dehydration of the serpentinized peridotite (deserpentinization). This requires two separate stages of metasomatism: (1) intense chemical alteration of the basaltic garnetite precursor, together with serpentinization of peridotite at the ocean floor or during incipient subduction; and (2) prograde metamorphism and dehydration of serpentinite during continued subduction, thereby releasing Pb–Ba‐rich fluids that reacted with associated metabasalt. Finally, subduction to >100 km and UHP metamorphism of all lithologies led to formation of garnetite, eclogite and garnet pyroxenite hosted by co‐facial garnet peridotite as observed in the Erzgebirge.〈/p〉

Description: Deutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659

Description: Little is known about water in nominally anhydrous minerals of orogenic garnet peridotite and enclosed metabasic rocks. This study is focused on peridotite-hosted eclogite and garnetite (metarodingite) from the Erzgebirge (EG), Germany, and the Lepontine Alps (LA), Switzerland. Newly discovered, peridotite-hosted eclogite in the Erzgebirge occurs in the same ultra-high pressure (UHP) unit as gneiss-hosted coesite eclogite, from which it is petrologically indistinguishable. Garnet is present in all mafic and ultramafic high pressure (HP) rocks providing for an ideal proxy to compare the H2O content of the different rock types. Garnet composition is very similar in EG and LA samples and depends on the rock type. Garnet from garnetite, compared to eclogite, contains more CaO (garnetite: 10.5–16.5 wt%; eclogite: 5–11 wt%) and is also characterized by an anomalous REE distribution. In contrast, the infrared (IR) spectra of garnet from both rock types reveal the same OH absorption bands that are also identical to those of previously studied peridotitic garnet from the same locations. Two groups of IR bands, SW I (3,650 ± 10 cm−1) and SW II (3,570–3,630 cm−1) are ascribed to structural hydroxyl (colloquially ‘water’). A third, broad band is present in about half of the analysed garnet domains and related to molecular water (MW) in submicroscopic fluid inclusions. The primary content of structural H2O, preserved in garnet domains without fluid inclusions (and MW bands), varies systematically—depending on both the location and the rock type. Garnet from EG rocks contains more water compared to LA samples, and garnet from garnetite (EG: 121–241 wt.ppm H2O; LA: 23–46 wt.ppm) hosts more water than eclogitic garnet (EG: 84 wt.ppm; LA: 4–11 wt.ppm). Higher contents of structural water (SW) are observed in domains with molecular water, in which the SW II band (being not restricted to HP conditions) is simultaneously enhanced. This implies that fluid influx during decompression not only led to fluid inclusions but also favoured the uptake of secondary SW. The results signify that garnet from all EG and LA samples was originally H2O-undersaturated. Combining the data from eclogite, garnetite and previously studied peridotite, H2O and CaO are positively correlated, pointing to the same degree of H2O-undersaturation at peak metamorphism in all rock types. This ubiquitous water-deficiency cannot be reconciled with the derivation of any of these rocks from the lowermost part of the mantle wedge that was in contact with the subducting plate. This agrees with the previously inferred abyssal origin for part of the rocks from the LA (Cima di Gagnone). A similar origin has to be invoked for the Erzgebirge UHP unit. We suggest that all mafic and ultramafic rocks of this unit not only shared the same metamorphic evolution but also a common protolith origin, most probably on the ocean floor. This inference is supported by the presence of peridotite-hosted garnetite, representing metamorphosed rodingite.

Description: Major and trace elements in omphacite, including hydrogen, were determined in eclogites from two Variscan basement complexes in Germany: Erzgebirge (EG) and Fichtelgebirge (FG). Erzgebirge eclogite is derived from three units, showing different peak pressure (P) and temperature (T) conditions (Unit 1: 840–920°C/≥30 kbar, Unit 2: 670–730°C/24–26 kbar, Unit 3: 600–650°C/20–22 kbar). The peak conditions of FG eclogite (690–750°C/25–28 kbar) resemble those of EG Unit 2. Coesite eclogite occurs in EG Unit 1, and quartz eclogite in all other units. Omphacite from all samples shows four infrared (IR) absorption bands. Two prominent, sharp bands occur at 3,455 ± 10 cm−1 (band II) and 3,522 ± 10 cm−1 (band III). Band II is usually more prominent than band III, except for few samples with low jadeite content. A further, broad band is centred between 3,270 and 3,370 cm−1 (band I) and a fourth, minor band at 3,611–3,635 cm−1 (band IV). Bands II and III are due to hydrogen bound as structural OH− ions in omphacite. In most cases, this also applies to band IV. However, some spectra with extremely large type IV bands reflect phengite inclusions. The ambiguous band I may be due to different H2O species (molecular water, structural OH, and water in phengite). Omphacite of quartz eclogite has lower contents of TiO2, Zr, Hf, and REE, compared with that from coesite eclogite. By contrast, omphacite in quartz eclogite from both EG (H2O sample averages: 465–852 ppm) and FG (546–1,089 ppm) contains the same amount of structural OH (concentrations given in wt.‐ppm H2O) as omphacite in coesite eclogite (492–1,140 ppm). The obtained difference in the garnet‐omphacite H2O partition coefficient between quartz (0.01–0.03) and coesite eclogite (0.08–0.11) results from different H2O contents in garnet (coesite eclogite: 50–150 ppm; quartz eclogite: 〈2–50 ppm; Gose & Schmädicke, 2018). The total content of structural OH in omphacite is unrelated to its major and trace element composition. However, treating the individual IR bands separately, a relation between OH and mineral composition is observed. The OH amount defined by band II is positively correlated to Ti and tetrahedral Al, and that of band III shows a positive correlation with Ca and a negative one with Na (and jadeite). Both the total OH content of omphacite and the partial contents deduced from individual IR bands are unrelated to PT conditions. This implies that omphacite incorporated its structural H2O mainly in the quartz stability field, presumably during initial omphacite growth. Conversely, most OH in garnet was derived from the final breakdown of the last remaining calcic amphibole close to or within the coesite stability field. Our data suggest that coesite eclogite is able to transport a significant amount of H2O (average 550 ppm, maximum 730 ppm), corresponding to that in 3–4 vol.% calcic amphibole, via subduction to depths beyond 100 km. However, the majority of water liberated by dehydration reactions during subduction, including the breakdown of 5–10 vol.% eclogite facies and 〉10 vol.% pre‐eclogitic hydrous minerals, is not preserved in eclogite but liberated to the mantle wedge.

Description: Deutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659