Geochemistry

Image courtesy of Nature.com
Image courtesy of Nature.com

What is Geochemistry?

Geochemistry is the science that uses the tools and principles of chemistry to explain the mechanisms behind major geological systems such as the Earth’s crust and its oceans. The realm of geochemistry extends beyond the Earth, encompassing the entire Solar System and has made important contributions to the understanding of a number of processes including mantle convection, the formation of planets and the origins of granite and basalt.

Some subsets of geochemistry are:

  • Isotope geochemistry involves the determination of the relative and absolute concentrations of the elements and their isotopes in the earth and on earth’s surface.
  • Examination of the distribution and movements of elements in different parts of the earth (crust, mantle, hydrosphere etc.) and in minerals with the goal to determine the underlying system of distribution and movement.
  • Cosmochemistry includes the analysis of the distribution of elements and their isotopes in the cosmos.
  • Biogeochemistry is the field of study focusing on the effect of life on the chemistry of the earth.
  • Organic geochemistry involves the study of the role of processes and compounds that are derived from living or once-living organisms.
  • Aqueous geochemistry studies the role of various elements in watersheds, including copper, sulfur, mercury, and how elemental fluxes are exchanged through atmospheric-terrestrial-aquatic interactions.
  • Regional, environmental and exploration geochemistry includes applications to environmental, hydrological and mineral exploration studies.
  • Victor Goldschmidt is considered by most to be the father of modern geochemistry and the ideas of the subject were formed by him in a series of publications from 1922 under the title ‘Geochemische Verteilungsgesetze der Elemente’ (geochemical laws of distribution of the elements).

Chemical characteristics

The more common rock constituents are nearly all oxides; chlorides, sulfides and fluorides are the only important exceptions to this and their total amount in any rock is usually much less than 1%. F. W. Clarke has calculated that a little more than 47% of the Earth’s crust consists of oxygen. It occurs principally in combination as oxides, of which the chief are silica, alumina, iron oxides, and various carbonates (calcium carbonate, magnesium carbonate, sodium carbonate, and potassium carbonate). The silica functions principally as an acid, forming silicates, and all the commonest minerals of igneous rocks are of this nature. From a computation based on 1672 analyses of numerous kinds of rocks Clarke arrived at the following as the average percentage composition: SiO2=59.71, Al2O3=15.41, Fe2O3=2.63, FeO=3.52, MgO=4.36, CaO=4.90, Na2O=3.55, K2O=2.80, H2O=1.52, TiO2=0.60, P2O5=0.22, total 99.22%). All the other constituents occur only in very small quantities, usually much less than 1%.

These oxides combine in a haphazard way. For example, potash (potassium carbonate) and soda (sodium carbonate) combine to produce feldspars. In some cases they may take other forms, such as nepheline, leucite, and muscovite, but in the great majority of instances they are found as feldspar. Phosphoric acid with lime (calcium carbonate) forms apatite. Titanium dioxide with ferrous oxide gives rise to ilmenite. Part of the lime forms lime feldspar. Magnesium carbonate and iron oxides with silica crystallize as olivine or enstatite, or with alumina and lime form the complex ferro-magnesian silicates of which the pyroxenes, amphiboles, and biotites are the chief. Any excess of silica above what is required to neutralize the bases will separate out as quartz; excess of alumina crystallizes as corundum. These must be regarded only as general tendencies. It is possible, by rock analysis, to say approximately what minerals the rock contains, but there are numerous exceptions to any rule.

Mineral constitution

Hence we may say that except in acid or siliceous rocks containing 66% of silica and over, quartz will not be abundant. In basic rocks (containing 20% of silica or less) it is rare and accidental. If magnesia and iron be above the average while silica is low, olivine may be expected; where silica is present in greater quantity over ferro-magnesian minerals, such as augite, hornblende, enstatite or biotite, occur rather than olivine. Unless potash is high and silica relatively low, leucite will not be present, for leucite does not occur with free quartz. Nepheline, likewise, is usually found in rocks with much soda and comparatively little silica. With high alkalis, soda-bearing pyroxenes and amphiboles may be present. The lower the percentage of silica and the alkalis, the greater is the prevalence of calcium feldspar as contracted with soda or potash feldspar. Clarke has calculated the relative abundance of the principal rock-forming minerals with the following results: apatite=0.6, titanium minerals=1.5, quartz=12.0, feldspars=59.5, biotite=3.8, hornblende and pyroxene=16.8, total=94.2%. This, however, can only be a rough approximation.

The other determining factor, namely the physical conditions attending consolidation, plays on the whole a smaller part, yet is by no means negligible, as a few instances will prove. Certain minerals are practically confined to deep-seated intrusive rocks, e.g., microcline, muscovite, diallage. Leucite is very rare in plutonic masses; many minerals have special peculiarities in microscopic character according to whether they crystallized in depth or near the surface, e.g., hypersthene, orthoclase, quartz. There are some curious instances of rocks having the same chemical composition, but consisting of entirely different minerals, e.g., the hornblendite of Gran, in Norway, which contains only hornblende, has the same composition as some of the camptonites of the same locality that contain feldspar and hornblende of a different variety. In this connection we may repeat what has been said above about the corrosion of porphyritic minerals in igneous rocks. In rhyolites and trachytes, early crystals of hornblende and biotite may be found in great numbers partially converted into augite and magnetite. Hornblende and biotite were stable under the pressures and other conditions below the surface, but unstable at higher levels. In the ground-mass of these rocks, augite is almost universally present. But the plutonic representatives of the same magma, granite and syenite contain biotite and hornblende far more commonly than augite.

Felsic, intermediate and mafic igneous rocks

Those rocks that contain the most silica, and on crystallizing yield free quartz, form a group generally designated the “felsic” rocks. Those again that contain least silica and most magnesia and iron, so that quartz is absent while olivine is usually abundant, form the “mafic” group. The “intermediate” rocks include those characterized by the general absence of both quartz and olivine. An important subdivision of these contains a very high percentage of alkalis, especially soda, and consequently has minerals such as nepheline and leucite not common in other rocks. It is often separated from the others as the “alkali” or “soda” rocks, and there is a corresponding series of mafic rocks. Lastly a small sub-group rich in olivine and without feldspar has been called the “ultramafic” rocks. They have very low percentages of silica but much iron and magnesia. Except these last, practically all rocks contain felspars or feldspathoid minerals. In the acid rocks the common feldspars are orthoclase, perthite, microcline, and oligoclase—all having much silica and alkalis. In the mafic rocks labradorite, anorthite and bytownite prevail, being rich in lime and poor in silica, potash and soda. Augite is the most common ferro-magnesian in mafic rocks, but biotite and hornblende are on the whole more frequent in felsic rocks.