Patricia Clay

Characteristics of djerfisherite from fluid-rich, metasomatized alkaline intrusive environments and anhydrous enstatite chondrites and achondrites

Abstract Djerfisherite is a K-Cl-bearing sulfide that is present in both ultra-reduced extraterrestrial enstatite meteorites (enstatite chondrites or achondrites) and reduced terrestrial alkaline intrusions, kimberlites, ore deposits, and skarns. Major element chemistry of two terrestrial occurrences of djerfisherite (from the Ilímaussaq and Khibina alkaline igneous suites) and three extraterrestrial examples of djerfisherite have been determined and combined with petrographic characterization and element mapping to unravel three discrete modes of djerfisherite formation. High Fe/Cu is characteristic of extraterrestrial djerfisherite and low Fe/Cu is typical of terrestrial djerfisherite. Ilímaussaq djerfisherite, which has high-Fe contents (~55 wt%) is the exception. Low Ni contents are typical of terrestrial djerfisherite due to preferential incorporation of Fe and/or Cu over Ni, but Ni contents of up to 2.2 wt% are measured in extraterrestrial djerfisherite. Extensive interchange between K and Na is evident in extraterrestrial samples, though Na is limited (<0.15 wt%) in terrestrial djerfisherite. We propose three setting-dependent mechanisms of djerfisherite formation: primitive djerfisherite as a product of nebula condensation in the unequilibrated E chondrites; formation by extensive K-metasomatism in Khibina djerfisherite; and as a product of primary “unmixing” due to silicate-sulfide immiscibility for Ilímaussaq djerfisherite. There are several important reasons why a deeper understanding of the petrogenesis of this rare and unusual mineral is valuable: (1) its anomalously high K-contents make it a potential target for Ar-Ar geochronology to constrain the timing of metasomatic alteration; (2) typically high Cl-contents (~1.1 wt%) mean it can be used as a valuable tracer of fluid evolution during metasomatic alteration; and (3) it may be a potential source of K and magmatic Cl in the sub-continental lithospheric mantle (SCLM), which has implications for metal solubility and the generation of ore deposits.

Halogens in chondritic meteorites and terrestrial accretion

Volatile element delivery and retention played a fundamental part in Earth’s formation and subsequent chemical differentiation. The heavy halogens—chlorine (Cl), bromine (Br) and iodine (I)—are key tracers of accretionary processes owing to their high volatility and incompatibility, but have low abundances in most geological and planetary materials. However, noble gas proxy isotopes produced during neutron irradiation provide a high-sensitivity tool for the determination of heavy halogen abundances. Using such isotopes, here we show that Cl, Br and I abundances in carbonaceous, enstatite, Rumuruti and primitive ordinary chondrites are about 6 times, 9 times and 15–37 times lower, respectively, than previously reported and usually accepted estimates. This is independent of the oxidation state or petrological type of the chondrites. The ratios Br/Cl and I/Cl in all studied chondrites show a limited range, indistinguishable from bulk silicate Earth estimates. Our results demonstrate that the halogen depletion of bulk silicate Earth relative to primitive meteorites is consistent with the depletion of lithophile elements of similar volatility. These results for carbonaceous chondrites reveal that late accretion, constrained to a maximum of 0.5 ± 0.2 per cent of Earth’s silicate mass, cannot solely account for present-day terrestrial halogen inventories. It is estimated that 80–90 per cent of heavy halogens are concentrated in Earth’s surface reservoirs and have not undergone the extreme early loss observed in atmosphere-forming elements. Therefore, in addition to late-stage terrestrial accretion of halogens and mantle degassing, which has removed less than half of Earth’s dissolved mantle gases, the efficient extraction of halogen-rich fluids from the solid Earth during the earliest stages of terrestrial differentiation is also required to explain the presence of these heavy halogens at the surface. The hydropilic nature of halogens, whereby they track with water, supports this requirement, and is consistent with volatile-rich or water-rich late-stage terrestrial accretion.