Sami Mikhail

Experimental investigation of F, Cl, and OH partitioning between apatite and Fe-rich basaltic melt at 1.0-1.2 GPa and 950-1000 °c

Abstract Apatite-melt partitioning experiments were conducted in a piston-cylinder press at 1.0-1.2 GPa and 950-1000 °C using an Fe-rich basaltic starting composition and an oxygen fugacity within the range of ΔIW-1 to ΔIW+2. Each experiment had a unique F:Cl:OH ratio to assess the partitioning as a function of the volatile content of apatite and melt. The quenched melt and apatite were analyzed by electron probe microanalysis and secondary ion mass spectrometry techniques. The mineral-melt partition coefficients (D values) determined in this study are as follows: DFAp-Melt = 4.4-19, DClAp-Melt = 1.1-5, DOHAp-Melt = 0.07-0.24. This large range in values indicates that a linear relationship does not exist between the concentrations of F, Cl, or OH in apatite and F, Cl, or OH in melt, respectively. This non- Nernstian behavior is a direct consequence of F, Cl, and OH being essential structural constituents in apatite and minor to trace components in the melt. Therefore mineral-melt D values for F, Cl, and OH in apatite should not be used to directly determine the volatile abundances of coexisting silicate melts. However, the apatite-melt D values for F, Cl, and OH are necessarily interdependent given that F, Cl, and OH all mix on the same crystallographic site in apatite. Consequently, we examined the ratio of D values (exchange coefficients) for each volatile pair (OH-F, Cl-F, and OH-Cl) and observed that they display much less variability: KdCl-FAp-Melt = 0.21± 0.03, KdOH-FAp-Melt = 0.014 ± 0.002, and KdOH-ClAp-Melt = 0.06 ± 0.02 . However, variations with apatite composition, specifically when mole fractions of F in the apatite X-site were low (XF < 0.18), were observed and warrant additional study. To implement the exchange coefficient to determine the H2O content of a silicate melt at the time of apatite crystallization (apatitebased melt hygrometry), the H2O abundance of the apatite, an apatite-melt exchange Kd that includes OH (either OH-F or OH-Cl), and the abundance of F or Cl in the apatite and F or Cl in the melt at the time of apatite crystallization are needed (F if using the OH-F Kd and Cl if using the OH-Cl Kd). To determine the H2O content of the parental melt, the F or Cl abundance of the parental melt is needed in place of the F or Cl abundance of the melt at the time of apatite crystallization. Importantly, however, exchange coefficients may vary as a function of temperature, pressure, melt composition, apatite composition, and/or oxygen fugacity, so the combined effects of these parameters must be investigated further before exchange coefficients are applied broadly to determine volatile abundances of coexisting melt from apatite volatile abundances.

Empirical evidence for the fractionation of carbon isotopes between diamond and iron carbide from the Earth's mantle

We have studied two samples of mantle diamond containing iron carbide inclusions from Jagersfontein kimberlite, South Africa. Syngenetic crystal growth is inferred using morphological characteristics. These samples provide an opportunity to investigate the isotopic partitioning of 13C in a terrestrial natural high-pressure and high-temperature (HPHT) system. The difference for the δ13C values between the diamond and coexisting iron carbide averaged 7.2 ± 1.3‰. These data are consistent with available data from the literature showing iron carbide to be 13C-depleted relative to elemental carbon (i.e., diamond). We infer that the minerals formed by crystallization of diamond and iron carbide at HPHT in the mantle beneath the Kaapvaal Craton. It is unclear whether crystallization occurred in subcratonic or sublithospheric mantle; in addition, the source of the iron is also enigmatic. Nonetheless, textural coherence between diamond and iron carbide resulted in isotopic partitioning of 13C between these two phases. These data suggest that significant isotopic fractionation of 13C/12C (Δ13C up to >7‰) can occur at HPHT in the terrestrial diamond stability field. We note that under reducing conditions at or below the iron-iron wustite redox buffer in a cratonic or deep mantle environment in Earth, the cogenesis of carbide and diamond may produce reservoirs of 13C-depleted carbon that have conventionally been interpreted as crustal in origin. Finally, the large Δ13C for diamond-iron carbide shown here demonstrates Δ13C for silicate-metallic melts is a parameter that needs to be constrained to better determine the abundance of carbon within the Earths metallic core.

The geobiological nitrogen cycle : from microbes to the mantle

Abstract Nitrogen forms an integral part of the main building blocks of life, including DNA, RNA, and proteins. N2 is the dominant gas in Earths atmosphere, and nitrogen is stored in all of Earths geological reservoirs, including the crust, the mantle, and the core. As such, nitrogen geochemistry is fundamental to the evolution of planet Earth and the life it supports. Despite the importance of nitrogen in the Earth system, large gaps remain in our knowledge of how the surface and deep nitrogen cycles have evolved over geologic time. Here, we discuss the current understanding (or lack thereof) for how the unique interaction of biological innovation, geodynamics, and mantle petrology has acted to regulate Earths nitrogen cycle over geologic timescales. In particular, we explore how temporal variations in the external (biosphere and atmosphere) and internal (crust and mantle) nitrogen cycles could have regulated atmospheric pN2. We consider three potential scenarios for the evolution of the geobiological nitrogen cycle over Earths history: two in which atmospheric pN2 has changed unidirectionally (increased or decreased) over geologic time and one in which pN2 could have taken a dramatic deflection following the Great Oxidation Event. It is impossible to discriminate between these scenarios with the currently available models and datasets. However, we are optimistic that this problem can be solved, following a sustained, open‐minded, and multidisciplinary effort between surface and deep Earth communities.

A petrological assessment of diamond as a recorder of the mantle nitrogen cycle

Abstract Nitrogen is fundamental to the evolution of Earth and the life it supports, but for reasons poorly understood, it is cosmochemically the most depleted of the volatile elements. The largest reservoir in the bulk silicate Earth is the mantle, and knowledge of its nitrogen geochemistry is biased, because ≥90% of the mantle nitrogen database comes from diamonds. However, it is not clear to what extent diamonds record the nitrogen characteristics of the fluid/melts from which they precipitate. There is ongoing debate regarding the fundamental concept of nitrogen compatibility in diamond, and empirical global data sets reveal trends indicative of nitrogen being both compatible (fibrous diamonds) and incompatible (non-fibrous monocrystalline diamonds). A more significant and widely overlooked aspect of this assessment is that nitrogen is initially incorporated into the diamond lattice as single nitrogen atoms. However, this form of nitrogen is highly unstable in the mantle, where nitrogen occurs as molecular forms like N2 or NH4+

Evidence for multiple diamondite-forming events in the mantle

{\rm{NH}}_4^ +

Nitrogen speciation in upper mantle fluids and the origin of Earth's nitrogen-rich atmosphere

, both of which are incompatible in the diamond lattice. A review of the available data shows that in classic terms, nitrogen is the most common substitutional impurity found in natural diamonds because it is of very similar atomic size and charge to carbon. However, the speciation of nitrogen, and how these different species disassociate during diamond formation to create transient monatomic nitrogen, are the factors governing nitrogen abundance in diamonds. This suggests the counter-intuitive notion that a nitrogen-free (Type II) diamond could grow from a N-rich media that is simply not undergoing reactions that liberate monatomic N. In contrast, a nitrogen-bearing (Type I) diamond could grow from a fluid with a lower N abundance, in which reactions are occurring to generate (unstable) N atoms during diamond formation. This implies that diamond’s relevance to nitrogen abundance in the mantle is far more complicated than currently understood. Therefore, further petrological investigations are required to enable accurate interpretations of what nitrogen data from mantle diamonds can tell us about the deep nitrogen budget and cycle.

Constraining the internal variability of the stable isotopes of carbon and nitrogen within mantle diamonds

Abstract A collection of 35 diamondite samples (polycrystalline diamond aggregates, sometimes referred to as framesites), assumed to be from southern Africa, have been studied to investigate their infrared (IR) spectroscopic characteristics. Due to the abundance of sub-micrometer, interlocking diamonds (polycrystalline) with mineral and fluid inclusions within the diamond material affecting their transparency, only fragments from 10 of the samples provided high-quality data. The IR spectra showed a wide range of generally high-nitrogen concentrations (386-2677 ppm), with a full range of nitrogen aggregation states, from pure IaA to pure IaB. Platelet characteristics were interpreted as being regular (i.e., not having been affected by deformation and/or heating events), meaning the nitrogen aggregation data could be interpreted with confidence. Surprisingly, the platelet data showed a positive correlation between their intensity (integrated area) and peak position. The primary hydrogen band (at 3107 cm-1) and secondary band (at 1405 cm) are both often present in the samples’ spectra, but show no correlation with any other characteristic. There is also no correlation between the samples’ paragenesis (as defined by their garnet chemistry) and any of the IR characteristics. While we have no independent determination of the samples mantle residence age, nor the temperature they resided at, we infer that diamondite formation has occurred episodically over a large time frame in single and distinct growth events (as opposed to over a short time frame but over a large depth/temperature range). This idea is more in keeping with the theory that C-O-H diamond- (and diamondite-) forming fluids are the result of localized small volume processes. Interestingly, one sample contained fluid inclusions that exhibited a water:carbonate molar ratio (~0.8), similar to the saline and silicic end-members of the monocrystalline diamond-forming fluid chemical spectrum.