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Theoretical isotopic fractionation of magnesium between chlorophylls.

ABSTRACT: Magnesium is the metal at the center of all types of chlorophyll and is thus crucial to photosynthesis. When an element is involved in a biosynthetic pathway its isotopes are fractionated based on the difference of vibrational frequency between the different molecules. With the technical advance of multi-collectors plasma-mass-spectrometry and improvement in analytical precision, it has recently been found that two types of chlorophylls (a and b) are isotopically distinct. These results have very significant implications with regards to the use of Mg isotopes to understand the biosynthesis of chlorophyll. Here we present theoretical constraints on the origin of these isotopic fractionations through ab initio calculations. We present the fractionation factor for chlorphyll a, b, d, and f. We show that the natural isotopic variations among chlorophyll a and b are well explained by isotopic fractionation under equilibrium, which implies exchanges of Mg during the chlorophyll cycle. We predict that chlorophyll d and f should be isotopically fractionated compared to chlorophyll a and that this could be used in the future to understand the biosynthesis of these molecules.

SUBMITTER: Moynier F

PROVIDER: S-EPMC5539320 | biostudies-literature | 2017 Aug

REPOSITORIES: biostudies-literature

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Theoretical isotopic fractionation of magnesium between chlorophylls.

Moynier Frédéric F Fujii Toshiyuki T

Scientific reports 20170801 1

Magnesium is the metal at the center of all types of chlorophyll and is thus crucial to photosynthesis. When an element is involved in a biosynthetic pathway its isotopes are fractionated based on the difference of vibrational frequency between the different molecules. With the technical advance of multi-collectors plasma-mass-spectrometry and improvement in analytical precision, it has recently been found that two types of chlorophylls (a and b) are isotopically distinct. These results have ver ...[more]

PMID: 28765587

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Project description:The chemical and isotopic signatures of moderately volatile elements are useful for understanding processes of volatile depletion in planetary formation and differentiation. However, the fractionation factors between gas and melt phases during evaporation that are required to model these planetary volatile depletion processes are still sparse. In this study, twenty heating experiments were conducted in 1 atm gas-mixing furnaces to constrain the behavior of K, Cu, and Zn evaporation and isotopic fractionation from basaltic melts at high temperatures. The temperatures range from 1300 °C to 1400 °C, and durations are from 2 to 8 days. Oxygen fugacities (fO2) range from one log unit below to ten log units above that of the iron-wüstite buffer (IW-1 to IW+10, corresponding to logfO2 of -10.7 to -0.68 at 1400 °C). The conditions were selected to achieve an evaporation-dominated regime (where timescales of diffusion << evaporation for trace elements) in order to avoid diffusion-limited evaporation. Our results show during evaporation Zn behaved as the most volatile, followed by Cu and then K, regardless of temperature and oxygen fugacity. Partitioning of Zn into spinel layers within experimental capsules, however, has been observed, which has substantial effects on the Zn isotope fractionation factor. Therefore, Zn results are presented but further discussion is excluded. Element loss depends on both temperature and oxygen fugacity, where higher temperatures and lower oxygen fugacities promote evaporation. However, with varying temperature and oxygen fugacity, the kinetic isotopic fractionation factors, α (where, RR0=fα-1 ), for K and Cu remain constant, thus these factors can be applied to a wider range of conditions than those in this study. The experimentally determined fractionation factors for K, and Cu during evaporation from basaltic melts are 0.9944, and 0.9961, respectively. The fractionation factors for these elements with varying volatilities are all significantly larger than the "apparent observed fractionation factors," which approach one and are inferred from lunar basalts relative to the Bulk Silicate Earth. This observation suggests near-equilibrium conditions during volatile-element loss from the Moon as the "apparent observed fractionation factors" of lunar basalts are similar for all three elements.

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Theoretical isotopic fractionation of magnesium between chlorophylls.

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Theoretical isotopic fractionation of magnesium between chlorophylls.

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