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The Biological System of the Elements

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Chemical Evolution

Abstract

Starting (in the 1990s) with abundance correlations among pairs of chemical elements in different kinds of plants which grow at a common site (a drying bog in Lower Saxony), the Biological System of Elements (BSE) was advanced by Bernd Markert striving to understand reasons why these—and no other—elements are used in biology to accomplish certain chemical transformations and how fractionation of elements from surrounding water or soil does take place in quantitative terms. For metals, essentiality apparently is related to coordination chemistry while it turns out that entire plant organs behave like homogeneous (single or equifunctional) ligands with respect to fractionation of elements after uptake from the environment. The BSE is arranged as a triangular picture in which the axes refer to the capability to form highly aggregated (e.g., polymeric) chemical species, the relative role in biological matter, and the response to (changing) salinity. It now is a double-layer body of knowledge, combining statistical statements on analytical bioinorganic chemistry and embracing quantitative chemical pieces of information to account for roles of most chemical elements with Z <84.

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Notes

  1. 1.

    Markert (1994a, b).

  2. 2.

    Extended and more detailed information on the functionality of each chemical element are given in Appendix.

  3. 3.

    While for the actinoids similarity with lanthanoids was driven so far as to name analogs according to similar rules (Z = 63: europium, Z = 95: americium; Z = 65: terbium (alluding to a village in Sweden where it was found first), Z = 97: berkelium) the lighter actinoids (protactinium to americium) differ from their REE analogs in stabilizing oxidation states + V to + VII which the latter will never reach in condensed matter while the heavy ones (Z > 100, Md [mendelevium], No, and Lr) turned out to be commonly much more stable in divalent states than corresponding REEs Tm, Yb, let alone Lu.

  4. 4.

    To our present knowledge it will be almost impossible to prepare atoms with Z > 123 of sufficient half-lives (>0.2 μs) even to identify them (otherwise, nuclei formed in a target would decay during mass separation and hence before reaching the detector device), let alone doing any chemistry.

  5. 5.

    On the opposite, protons and neutrons in nuclei attract both each and the other kind of nucleon due to the strong nuclear force, partially compensating mutual repulsion of protons even though they are tightly packed. Thus the “magic” numbers producing closed, most stable nuclear orbitals (8, 20, 28, 50, 82, 126, plus 14, 34, 62, 108 for non-spherical arrangements) differ from the Z values of noble gases (10, 18, 36, 54, 86, and 118) and fairly inert metal ions (28, 46, 78) which are caused by electron properties alone.

  6. 6.

    Both one-dimensional ones, ylides, and three-dimensional assemblies of charged atoms.

  7. 7.

    There are significantly exergonic reactions which literally will not take place, not even allowing for geological periods of time, like hydrogenations of N2 or of nitriles unless there are efficient specific catalysts, either homogeneous (dissolved) V-, Mo, W- or Re complexes or iron (or Os) chalcogenide particles. Another hard-to-activate reaction (at least if T < 250 °C) which, unlike nitrogenase activity, almost every living being can induce is reduction of sulfate; activation (oxidation) of aliphatic CH bonds without additional functional groups (Hal, OH, -OPO3 2−, -COOR, -COSR) is less far-spread in biota.

  8. 8.

    Oscillations in permanganate-based systems (like others) require addition of orthophosphate plus two reductants to be present besides each other, like nitrite and formate, or NH3OH+ and an organic compound like malonate.

  9. 9.

    There are some exceptions: even humans can make glycine from CO2 and NH4 cations by C(IV) reduction via the folate reduction pathway, and glycine itself is linked to other organics via oxidative desamination affording glyoxylate (in malate synthase glyoxylate is linked to acetyl CoA producing C4 compound malate). Though this process falls far short from C autotrophy, it is an interesting question in how far these “exceptions” can and will influence general dynamics of essential elements.

  10. 10.

    In terms of interplanetary comparison, this means what is a mineral depends on local environmental conditions: in the atmospheres of Earth, Venus, Mars, and Titan, N2 of course is gaseous and not a mineral, but on Triton and possibly Pluto solid nitrogen which is known to be partly crystallized from spectra can well be considered one; conversely solid sulphur (S8) deposited here on Earth around volcano fumaroles or black smokers doubtlessly is a mineral (even forming large crystals) but on Venus elemental sulphur is a gas (mainly forming species S4 to S7) and thus not a mineral!

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  1. Environmental Institute of Scientific Networks (EISN), Haren, Germany

    Bernd Markert & Simone Wünschmann

  2. International Graduate School Zittau, Zittau, Germany

    Stefan Fränzle

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Markert, B., Fränzle, S., Wünschmann, S. (2015). The Biological System of the Elements. In: Chemical Evolution. Springer, Cham. https://doi.org/10.1007/978-3-319-14355-2_2

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