Early Earth zircons formed in residual granitic melts produced by tonalite differentiation

The oldest geological materials on Earth are Hadean (>4 Ga) detrital zircon grains. Their chemistry and apparently low Ti-in-zircon temperatures (≤700 °C) are considered to be inconsistent with crystallization in a magma of the tonalite-trondhjemite-granodiorite (TTG) suite, although these are the dominant Archean (4.0–2.5 Ga) silicic rocks. Using a new data set of trace element contents in zircons from Paleoarchean Barberton TTGs (South Africa) and thermodynamic modeling, we show that these zircons have crystallized at near-solidus conditions from a compositionally uniform granitic melt. This melt is residual from the crystallization of a less evolved (tonalitic) parent and thereby shows major and trace element compositions different from bulk TTG rocks. A global compilation reveals that most Hadean detrital and Archean TTG-hosted grains share a peculiar zircon trace element signature that is distinct from the chemical trends defined by Phanerozoic zircons. Our model shows that the low Ti contents of early Earth zircons reflect crystallization at higher temperatures (720–800 °C) than initially inferred due to lower modeled TiO2 activity in the melt relative to previous estimates. We therefore propose that near-solidus zircon crystallization from a chemically evolved melt in a TTG-like magmatic environment was the dominant zircon-forming process on the early Earth.

Trace Element and Isotope Systematics in Vent Fluids and Sulphides From Maka Volcano, North Eastern Lau Spreading Centre: Insights Into Three-Component Fluid Mixing

Back-arc spreading centres and related volcanic structures are known for their intense hydrothermal activity. The axial volcanic edifice of Maka at the North Eastern Lau Spreading Centre is such an example, where fluids of distinct composition are emitted at the Maka hydrothermal field (HF) and at Maka South in 1,525–1,543 m water depth. At Maka HF black smoker-type fluids are actively discharged at temperatures of 329°C and are characterized by low pH values (2.79–3.03) and a depletion in Mg (5.5 mmol/kg) and SO4 (0.5 mmol/L) relative to seawater. High metal (e.g., Fe up to ∼6 mmol/kg) and rare Earth element (REE) contents in the fluids, are indicative for a rock-buffered hydrothermal system at low water/rock ratios (2–3). At Maka South, venting of white smoke with temperatures up to 301°C occurs at chimneys and flanges. Measured pH values range from 4.53 to 5.42 and Mg (31.0 mmol/kg), SO4 (8.2 mmol/L), Cl (309 mmol/kg), Br (0.50 mmol/kg) and Na (230 mmol/kg) are depleted compared to seawater, whereas metals like Li and Mn are typically enriched together with H2S. We propose a three-component mixing model with respect to the fluid composition at Maka South including seawater, a boiling-induced low-Cl vapour and a black smoker-type fluid similar to that of Maka HF, which is also preserved by the trace element signature of hydrothermal pyrite. At Maka South, high As/Co (>10–100) and Sb/Pb (>0.1) in pyrite are suggested to be related to a boiling-induced element fractionation between vapour (As, Sb) and liquid (Co, Pb). By contrast, lower As/Co (<100) and a tendency to higher Co/Ni values in pyrite from Maka HF likely reflect the black smoker-type fluid. The Se/Ge ratio in pyrite provides evidence for fluid-seawater mixing, where lower values (<10) are the result of a seawater contribution at the seafloor or during fluid upflow. Sulphur and Pb isotopes in hydrothermal sulphides indicate a common metal (loid) source at the two vent sites by host rock leaching in the reaction zone, as also reflected by the REE patterns in the vent fluids.

Petrological and geochemical characterisation of the sarsen stones at Stonehenge

Little is known of the properties of the sarsen stones (or silcretes) that comprise the main architecture of Stonehenge. The only studies of rock struck from the monument date from the 19th century, while 20th century investigations have focussed on excavated debris without demonstrating a link to specific megaliths. Here, we present the first comprehensive analysis of sarsen samples taken directly from a Stonehenge megalith (Stone 58, in the centrally placed trilithon horseshoe). We apply state-of-the-art petrographic, mineralogical and geochemical techniques to two cores drilled from the stone during conservation work in 1958. Petrographic analyses demonstrate that Stone 58 is a highly indurated, grain-supported, structureless and texturally mature groundwater silcrete, comprising fine-to-medium grained quartz sand cemented by optically-continuous syntaxial quartz overgrowths. In addition to detrital quartz, trace quantities of silica-rich rock fragments, Fe-oxides/hydroxides and other minerals are present. Cathodoluminescence analyses show that the quartz cement developed as an initial <10 μm thick zone of non-luminescing quartz followed by ~16 separate quartz cement growth zones. Late-stage Fe-oxides/hydroxides and Ti-oxides line and/or infill some pores. Automated mineralogical analyses indicate that the sarsen preserves 7.2 to 9.2 area % porosity as a moderately-connected intergranular network. Geochemical data show that the sarsen is chemically pure, comprising 99.7 wt. % SiO2. The major and trace element chemistry is highly consistent within the stone, with the only magnitude variations being observed in Fe content. Non-quartz accessory minerals within the silcrete host sediments impart a trace element signature distinct from standard sedimentary and other crustal materials. 143Nd/144Nd isotope analyses suggest that these host sediments were likely derived from eroded Mesozoic rocks, and that these Mesozoic rocks incorporated much older Mesoproterozoic material. The chemistry of Stone 58 has been identified recently as representative of 50 of the 52 remaining sarsens at Stonehenge. These results are therefore representative of the main stone type used to build what is arguably the most important Late Neolithic monument in Europe.

A remarkable discovery of electrum on the island of Sylt, northern Germany, and its Scandinavian origin

An electrum–quartz pebble with a weight of 10.4 g was discovered in a cliff of Saalian glaciogenic sediments on the west coast of the German North Sea island of Sylt in 2012. It has a roundish water-worn appearance and consists of intergrown electrum and milky quartz. It is the largest known electrum find in Germany, and regarding its weight it also ranks amongst the largest gold finds discovered in Germany. We document and characterize this unusual discovery. Furthermore, an attempt is made to investigate its provenance. Therefore, reference samples of southern Scandinavian gold and electrum deposits and occurrences have been studied and compared to the Sylt find. The Au–Ag content determined by electron microprobe (EMP), trace element signature measured by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), and Pb isotope compositions by multi-collector ICP MS (MC-ICP-MS) suggest a southern Norwegian origin. The most probable source might be the Kongsberg ore district or an adjacent, yet undiscovered, mineralization in the Oslo region. In general, Saalian glaciogenic sediments in Schleswig-Holstein (northern Germany) are dominated by rocks of Swedish provenance. Due to the intake of older Elsterian sediments by younger Saalian glaciers, southern Norwegian rocks are also not uncommon in Saalian sediments. A Saalian ice advance or a combination of Elsterian and Saalian ice advances might have provided a transport mechanism for an electrum sample from a south Norwegian mineralization to the island of Sylt.

Tectono-magmatic Interplay and Related Metasomatism in Gabbros of the Chenaillet Ophiolite (Western Alps)

The Jurassic Chenaillet ophiolite in the Western Alps consists of a gabbro–mantle association exhumed to the seafloor through detachment faulting and partly covered by basaltic lavas. One of the Chenaillet gabbroic bodies includes mylonites that are transected by a network of felsic veins, thereby testifying to the interplay of ductile shearing and magma emplacement. The deformed gabbros preserve clinopyroxene porphyroclasts of primary magmatic origin, which are typically mantled by amphibole (titanian edenite) and minor secondary clinopyroxene. Titanian edenite and secondary clinopyroxene also occur as fine-grained syn-kinematic phases locally associated with fine-grained plagioclase. The felsic veins are made up of anorthite-poor plagioclase and minor titanian edenite. Geothermometric investigations document that the ductile gabbro deformation and the crystallization of the felsic veins occurred at 765 ± 50 °C and 800 ± 55 °C, respectively. With respect to undeformed counterparts, the deformed gabbros are variably enriched in SiO2 and variably depleted in Mg/(Mg + Fetot2+) and Ca/(Ca + Na). In addition, the deformed gabbros show relatively high concentrations of incompatible trace elements such as rare earth elements (REE), Y, Zr and Nb. The felsic veins are characterized by low Mg/(Mg + Fetot2+) and Ca/(Ca + Na), high SiO2 and high concentrations of incompatible trace elements. Relict clinopyroxene porphyroclasts from the deformed gabbros display a rather primitive, mid-ocean ridge-type geochemical signature, which contrasts with the trace element fingerprint of titanian edenite from both the deformed gabbros and the felsic veins. For instance, titanian edenite typically has relatively high REE abundances, with chondrite-normalized REE patterns characterized by a pronounced negative Eu anomaly. A similar trace element signature is shown by secondary clinopyroxene from the deformed gabbros. Amphibole from both the deformed gabbros and the felsic veins displays high F/Cl values. We show that the SiO2-rich hydrous melts feeding the felsic veins were involved in the high-temperature gabbro deformation and that melt–gabbro reactions led to major and trace element metasomatism of the deforming gabbros.

Petrogenesis of plagiogranites in the Muslim Bagh Ophiolite, Pakistan: implications for the generation of Archaean continental crust

High-SiO2 rocks referred to as oceanic plagiogranites are common within the crustal sequences of ophiolites; however, their mode of petrogenesis is controversial with both late-stage fractional crystallization and partial melting models being proposed. Here, we present new whole-rock data from plagiogranitic dyke-like bodies and lenses from the lower and middle sections of the sheeted dyke complex of the Cretaceous Muslim Bagh Ophiolite, northwestern Pakistan. The plagiogranites have similar geochemical signatures that are inconsistent with them being the fractionation products of the mafic units of the Muslim Bagh Ophiolite. However, the plagiogranites all display very low TiO2 contents (<0.4 wt%), implying that they formed by partial melting of mafic rocks. Melt modelling of a crustal gabbro from the Muslim Bagh Ophiolite shows that the trace-element signature of the plagiogranites can be replicated by 5–10% melting of a crustal hornblende gabbro with amphibole as a residual phase, resulting in a concave-up middle rare Earth element pattern. Compositional similarities between the Muslim Bagh Ophiolite plagiogranites and Archaean TTG (trondhjemite–tonalite–granodiorite) has implications for the generation of juvenile Archaean continental crust. As the Muslim Bagh Ophiolite was derived in a supra-subduction zone, it is suggested that some Archaean TTG may have been derived from melting of mafic upper crust in early subduction-like settings. However, due to the small volume of Muslim Bagh Ophiolite plagiogranites, it is inferred that they can be instructive on the petrogenesis of some, but not all, Archaean TTG.