Abstract. Long viewed as a mostly noble, atmospheric species, recent work demonstrates that nitrogen in fact cycles throughout the Earth system, including the atmosphere, biosphere, oceans, and solid Earth. Despite this new-found behaviour, more thorough investigation of N in geologic materials is limited due to its low concentration (one to tens of parts per million) and difficulty in analysis. In addition, N can exist in multiple species (NO3−, NH4+, N2, organic N), and determining which species is actually quantified can be difficult. In rocks and minerals, NH4+ is the most stable form of N over geologic timescales. As such, techniques designed to measure NH4+ can be particularly useful.We measured a number of geochemical rock standards using three different techniques: elemental analyzer (EA) mass spectrometry, colorimetry, and fluorometry. The fluorometry approach is a novel adaptation of a technique commonly used in biologic science, applied herein to geologic NH4+. Briefly, NH4+ can be quantified by HF dissolution, neutralization, addition of a fluorescing reagent, and analysis on a standard fluorometer. We reproduce published values for several rock standards (BCR-2, BHVO-2, and G-2), especially if an additional distillation step is performed. While it is difficult to assess the quality of each method, due to lack of international geologic N standards, fluorometry appears better suited to analyzing mineral-bound NH4+ than EA mass spectrometry and is a simpler, quicker alternative to colorimetry.To demonstrate a potential application of fluorometry, we calculated a continental crust N budget based on new measurements. We used glacial tills as a proxy for upper crust and analyzed several poorly constrained rock types (volcanics, mid-crustal xenoliths) to determine that the continental crust contains ∼ 2 × 1018 kg N. This estimate is consistent with recent budget estimates and shows that fluorometry is appropriate for large-scale questions where high sample throughput is helpful.Lastly, we report the first δ15N values of six rock standards: BCR-2 (1. 05 ± 0. 4 ‰), BHVO-2 (−0. 3 ± 0. 2 ‰), G-2 (1. 23 ± 1. 32 ‰), LKSD-4 (3. 59 ± 0. 1 ‰), Till-4 (6. 33 ± 0. 1 ‰), and SY-4 (2. 13 ± 0. 5 ‰). The need for international geologic N standards is crucial for further investigation of the Earth system N cycle, and we suggest that existing rock standards may be suited to this need.
Abstract. Long viewed as a mostly noble, atmospheric species, recent work demonstrates that nitrogen in fact cycles throughout the Earth system, including the atmosphere, biosphere, oceans, and solid Earth. Despite this new-found behaviour, more thorough investigation of N in geologic materials is limited due to its low concentration (1 to 10 s ppm) and difficulty in analysis. In addition, N can exist in multiple species (NO3−, NH4+, N2, organic-N), and determining which species is actually quantified can be difficult. In rocks and minerals, NH4+ is the most stable form of N over geologic time scales. As such, techniques designed to measure NH4+ can be particularly useful. We measured a number of geochemical rock standards using three different techniques: mass spectrometry, colourimetry, and fluorometry. The fluorometry approach is a novel adaptation of a technique commonly used in biologic science, applied herein to geologic NH4+. Briefly, NH4+ can be quantified by HF-dissolution, neutralization, addition of a fluorescing reagent, and analysis on a standard fluorometer. We reproduce published values for several rock standards (BCR-2, BHVO-2, and G-2), especially if an additional distillation step is performed. While it is difficult to assess quality of each method, due to lack of international geologic N standards, fluorometry appears better suited to analyzing mineral-bound NH4+ than mass spectrometry, and is a simpler, quicker alternative to colourimetry. To demonstrate a potential application of fluorometry, we calculated a continental crust N budget based on new measurements. We used glacial tills as a proxy for upper crust and analyzed several poorly constrained rock types (volcanics, mid-crustal xenoliths) to determine that the continental crust contains ∼ 2 × 1018 kg N. This estimate is consistent with recent budget estimates, and shows that fluorometry is appropriate for large-scale questions where high sample throughput is helpful. Lastly, we report the first δ15N values of six rock standards: BCR-2 (1.05 ± 0.4 ‰), BHVO-2 (−0.3 ± 0.2 ‰), G-2 (1.23 ± 1.32 ‰), LKSD-4 (3.59 ± 0.1 ‰), Till-4 (6.33 ± 0.1 ‰), and SY-4 (2.13 ± 0.5 ‰). The need for international geologic N standards is crucial for further investigation of the Earth system N cycle, and we suggest that existing rock standards may be suited to this need.
Despite extensive research on massive chromitites, the mechanism(s) that form such anomalous chromite segregations remains uncertain. Recent work that considered a theoretical parental melt to the Critical Zone of the Bushveld Complex applied the MELTS thermodynamic model to propose that reduction of pressure upon magma ascent shifts the silicate-in temperature to lower values, such that chromite is the sole liquidus phase, resulting in formation of chromitites. Herein the effect of pressure on Cr solubility at constant fO2 relative to the FMQ buffer is evaluated through laboratory phase equilibrium experiments done at 0.1 MPa, 0.5 GPa, and 1 GPa. Two bulk compositions were employed: (1) the theoretical melt used in the MELTS modelling study and (2) B1, which is a widely accepted parental composition to the Bushveld Critical Zone. Experiments were conducted at 0.1 MPa by equilibrating compositions on Fe-Ir alloy wire loops from 1170-1300°C in a vertical-tube, gas-mixing furnace for 12-48 hours. Experiments at 0.5 GPa and 1 GPa were conducted with a piston-cylinder apparatus at 1230°C and 1280°C for 4-12 hours using Fe-Ir alloy and graphite-lined Pt capsules. Experiments show that the B1 composition reproduces phase equilibria and mineral compositions observed in the Bushveld whereas mineral compositions produced by the theoretical melt composition used in the MELTS modelling study are too Al-rich, excluding it as viable parental liquid. Results show no significant change in Cr content of the melt at chromite saturation with pressure at constant relative fO2. However, reduction of pressure can promote chromite crystallization, as the modal abundance and DCr(px/liq) of orthopyroxene decrease with pressure in experiments, increasing the availability of Cr for chromite crystallization. While a low-pressure interval of chromite-alone crystallization is plausible, results indicate that significant volumes of unusually Cr-enriched B1 magma would be required to produce the chromitites observed in the Bushveld by the pressure reduction mechanism.
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