Sonja Aulbach

Evidence for a reducing Archean ambient mantle and its effects on the carbon cycle

Chemical reduction-oxidation mechanisms within mantle rocks link to the terrestrial carbon cycle by influencing the depth at which magmas can form, their composition, and ultimately the chemistry of gases released into the atmosphere. The oxidation state of the uppermost mantle has been widely accepted to be unchanged over the past 3800 m.y., based on the abundance of redox-sensitive elements in greenstone belt–associated samples of different ages. However, the redox signal in those rocks may have been obscured by their complex origins and emplacement on continental margins. In contrast, the source and processes occurring during decompression melting at spreading ridges are relatively well constrained. We retrieve primary redox conditions from metamorphosed mid-oceanic ridge basalts (MORBs) and picrites of various ages (ca. 3000–550 Ma), using V/Sc as a broad redox proxy. Average V/Sc values for Proterozoic suites (7.0 ± 1.4, 2σ, n = 6) are similar to those of modern MORB (6.8 ± 1.6), whereas Archean suites have lower V/Sc (5.2 ± 0.4, n = 5). The lower Archean V/Sc is interpreted to reflect both deeper melt extraction from the uppermost mantle, which becomes more reduced with depth, and an intrinsically lower redox state. The pressure-corrected oxygen fugacity (expressed relative to the fayalite-magnetite-quartz buffer, ΔFMQ, at 1 GPa) of Archean sample suites (ΔFMQ –1.19 ± 0.33, 2σ) is significantly lower than that of post-Archean sample suites, including MORB (ΔFMQ –0.26 ± 0.44). Our results imply that the reducing Archean atmosphere was in equilibrium with Earth’s mantle, and further suggest that magmatic gases crossed the threshold that allowed a build-up in atmospheric O2 levels ca. 3000 Ma, accompanied by the first “whiffs” of oxygen in sediments of that age.

Volatile-rich Metasomatism in the Cratonic Mantle beneath SW Greenland: Link to Kimberlites and Mid-lithospheric Discontinuities

The cratonic part of Greenland has been a hotspot of scientific investigation since the discovery of some of the oldest crust on Earth and of significant diamond potential in the underlying lithospheric mantle, the characterization of which remains, however, incomplete. We applied a detailed petrographic and in situ analytical approach to a new suite of fresh kimberlite-borne peridotite xenoliths, recovered from the North Atlantic craton in SW Greenland, to unravel the timing and nature of mantle metasomatism, and its link to the formation of low-volume melts (e.g. kimberlites) and to geophysically detectible discontinuities. Two types of mineralogies and metasomatic styles, occurring at two depth intervals, are recognized. The first type comprises lherzolites, harzburgites and dunites, some phlogopite-bearing, which occur from 100–170 km depth. They form continuous trends towards lower mineral Mg# at increasing TiO2, MnO and Na2O and decreasing NiO contents. These systematics are ascribed to metasomatism by a hydrous silicate melt precursor to c. 150 Ma kimberlites, in the course of rifting, decompression and lithosphere thinning. This metasomatism was accompanied by progressive garnet breakdown, texturally evident by pyroxene–spinel assemblages occupying former coarse grains and compositionally evident by increasing concentrations of elements that are compatible in garnet (Y, Sc, In, heavy rare earth elements) in newly formed clinopyroxene. Concomitant sulphide saturation is indicated by depletion in Cu, Ni and Co. The residual, more silica-undersaturated and potentially more oxidizing melts percolated upwards and metasomatized the shallower lithospheric mantle, which is composed of phlogopitebearing, texturally equilibrated peridotites, including wehrlites, showing evidence for recent pyroxene-breakdown. This is the second type of lithology, which occurs at 90–110 km depth and is inferred to have highly depleted protoliths. This type is compositionally distinct from lherzolites, with olivine having higher Ca/Al, but lower Al and V contents. Whereas low Al may in part reflect lower equilibration temperatures, low V is ascribed to a combination of intrinsically more oxidizing mantle at lower pressure and oxidative metasomatism. The intense metasomatism in the shallow cratonic mantle lithosphere contrasts with the strong depletion recorded in the northwestern part of the craton, which at 590–550 Ma extended to >210 km depth, and suggests loss of 40 km of lithospheric mantle, also recorded in the progressive shallowing of magma sources during the breakup of the North Atlantic craton. The concentration of phlogopite-rich lithologies in a narrow depth interval ( 90–110 km) overlaps with a negative seismic velocity gradient that is interpreted as a mid-lithospheric discontinuity beneath western Greenland. This is suggested to be a manifestation of small-volume volatile-rich magmatism, which paved the way for Mesozoic kimberlite, ultramafic lamprophyre, and carbonatite emplacement across the North Atlantic craton. VC The Author(s) 2018. Published by Oxford University Press. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com 2311 J O U R N A L O F P E T R O L O G Y Journal of Petrology, 2017, Vol. 58, No. 12, 2311–2338 doi: 10.1093/petrology/egy009 Advance Access Publication Date: 14 February 2018

A Reconnaissance Study of Ti-minerals in Cratonic Granulite Xenoliths and their Potential as Recorders of Lower Crust Formation and Evolution

A comprehensive petrographic and in situ major and trace element study of rutile, ilmenite and Ti-magnetite was undertaken in six lower crustal xenoliths of metabasaltic (?underplate) and metasedimentary (subduction) origin from the Diavik kimberlites (central Slave Craton, Canada). The aims of the study were to improve our understanding of trace element incorporation into these Ti-minerals, and to use these systematics to obtain insights into lower continental crust formation and evolution. Abundant (oxy)exsolution of titanomagnetite lamellae, blocky rutile, as well as minor pleonaste and zircon in ilmenite from metabasaltic granulites are proposed to reflect cooling from magmatic or metamorphic temperatures and subsequent secular mantle cooling. This explains the large spread in Zr-in-rutile temperatures (>200 C) and may partly be responsible for the substantial heterogeneity of other trace element concentrations in rutile and ilmenite. Even after accounting for trace element heterogeneity and modal uncertainties, mass-balance calculations indicate that both Ti and Nb in lower crustal granulites are largely controlled by rutile and ilmenite. Rutile U–Pb data define discordia arrays that yield upper intercept ages broadly coincident with the 1 27 Ga giant Mackenzie dike swarm event, suggesting reheating of the lower crust above the rutile U–Pb closure temperature, whereas lower intercept ages roughly correspond to the age of Cretaceous to Eocene kimberlite magmatism. Subsequent cooling led to partial resetting and data spread along the concordia. Closer inspection reveals that inter-grain concentrations of elements that are compatible in rutile (Nb, Ta, W, U), but highly incompatible in the abundant silicate minerals (in equilibrium with melt), are heterogeneous and contrast with the more homogeneous concentrations of the transition metals (NiO, V). This may indicate that local reaction partners for diffusive homogenization of these element concentrations were absent. Nb/Ta is also highly variable at the sample scale. This may be explained by prograde growth from high-Nb/Ta mineral precursors (e.g. biotite) in the metasedimentary granulites and crystallization of the protoliths to the metabasaltic granulites from a mafic magma that had experienced fractionation of ilmenite with low Nb/Ta in a crustal magma chamber. Thus, (Fe)–Ti minerals represent high field strength element ‘islands’ in the granulite silicate matrix. The lack of homogenization and persistence of high-energy grain boundaries, such as exsolution lamellae, further indicate that the lower continental crust remained essentially dry and did not recrystallize, possibly since Neoarchaean metamorphism.

Evaluation of Mantle Processes in an Extensional Regime: Insight from In Situ O and Sr Isotope Systematics of Mantle Xenoliths from Ethiopia

New O and Sr isotope compositions of minerals from well-characterized and variably metasomatized mantle xenoliths in Cenozoic basalts from the northwestern plateau (Gundeweyn area) and southern rift zone (Dillo and Megado areas) of Ethiopia were acquired to further evaluate the nature and effects of metasomatic processes affecting the lithospheric mantle beneath the East African Rift System (EARS), where a transition from plume impingement to rifting is recorded. The studied samples are dominantly fresh spinel lherzolites with subordinate spinel harzburgites and clinopyroxenites. The in situ δ18O composition of olivine is largely homogeneous, with average values of 5.31‰ for Gundeweyn, 5.22‰ for Dillo, and 5.25‰ for Megado xenoliths. The values are within the range of normal mantle olivine (δ18O = 5.1‰–5.4‰), and there is no systematic variation of δ18O values with petrographic characteristics, elemental compositions, Sr isotopic ratios, or tectonic setting (i.e., plateau [Gundeweyn] vs. rift [Dillo and Megado]). This suggests the absence of major tectonic controls on the δ18O ratios of lithospheric mantle beneath the EARS and indicates buffering of mantle oxygen with respect to metasomatic fluids or melts. The average in situ 87Sr/86Sr ratios of clinopyroxenes vary from 0.70300 to 0.70371 for Gundeweyn, 0.70254 to 0.70327 for Dillo, and 0.70288 to 0.70330 for Megado mantle xenoliths. In contrast to O isotopes, radiogenic Sr isotope compositions combined with light rare earth element enrichment in clinopyroxenes in both tectonomagmatic settings betray interaction with metasomatic melts or fluids that may be related to the Afar plume, and neither precludes nor requires influence of a Pan-African subduction component to the continental lithospheric mantle beneath the area. However, slightly higher 87Sr/86Sr and a higher abundance of enriched peridotite types in the plateau xenolith suite suggest a stronger contribution from plume or aged metasomatized lithospheric mantle sources than in the rift peridotites.