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Geochemistry

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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.[1] The realm of geochemistry extends beyond the Earth, encompassing the entire solar system[2] 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.[1]

History

The term geochemistry was first used by the Swiss-German chemist Christian Friedrich Schönbein in 1838. In his paper, Schönbein predicted the birth of a new field of study, stating:

"In a word, a comparative geochemistry ought to be launched, before geochemistry can become geology, and before the mystery of the genesis of our planets and their inorganic matter may be revealed."[3]

The field began to be realised a short time after Schönbein's work, but his term - 'geochemistry' - was initially used neither by geologists nor chemists and there was much debate over which of the two sciences should be the dominant partner.[3] There was little collaboration between geologists and chemists and the field of geochemistry remained small and unrecognised. During the early 20th Century, a number of geochemists produced work that began to popularise the field, including Frank Wigglesworth Clarke who had begun to investigate the abundances of various elements within the Earth and how the quantities were related to atomic weight. The composition of meteorites and their differences to terrestrial rocks was being investigated as early as 1850 and in 1901, Oliver C. Farrington hypothesised although there were differences, that the relative abundances should still be the same.[3] This was the beginnings of the field of cosmochemistry and has contributed much of what we know about the formation of the Earth and our Solar System.[2]

Subfields

Some subsets of geochemistry are:

  1. Isotope geochemistry:Determination of the relative and absolute concentrations of the elements and their isotopes in the earth and on earth's surface.
  2. 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.
  3. Cosmochemistry: Analysis of the distribution of elements and their isotopes in the cosmos.
  4. Biogeochemistry: Field of study focusing on the effect of life on the chemistry of the earth.
  5. Organic geochemistry: A study of the role of processes and compounds that are derived from living or once-living organisms.
  6. Aqueous geochemistry: Understanding the role of various elements in watersheds, including copper, sulfur, mercury, and how elemental fluxes are exchanged through atmospheric-terrestrial-aquatic interactions.
  7. Regional, environmental and exploration geochemistry: 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.

Acid, intermediate and basic igneous rocks

Those rocks that contain the most silica, and on crystallizing yield free quartz, form a group generally designated the "acid" rocks. Those again that contain least silica and most magnesia and iron, so that quartz is absent while olivine is usually abundant, form the "basic" 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 basic rocks. Lastly a small sub-group rich in olivine and without feldspar has been called the "ultrabasic" 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 basic rocks labradorite, anorthite and bytownite prevail, being rich in lime and poor in silica, potash and soda. Augite is the commonest ferro-magnesian of the basic rocks, but biotite and hornblende are on the whole more frequent in the acid.

Commonest Minerals Acid Intermediate Mafic Ultramafic
Quartz
Orthoclase (and Oligoclase), Mica, Hornblende, Augite 		Little or no Quartz:
Orthoclase hornblende, Augite, Biotite 		Little or no Quartz:
Plagioclase Hornblende, Augite, Biotite 		No Quartz
Plagioclase Augite, Olivine 		No Felspar
Augite, Hornblende, Olivine
Plutonic or Abyssal type Granite Syenite Diorite Gabbro Peridotite
Intrusive or Hypabyssal type Quartz-porphyry Orthoclase-porphyry Porphyrite Dolerite Picrite
Lavas or Effusive type Rhyolite, Obsidian Trachyte Andesite Basalt Limburgite

Rocks that contain leucite or nepheline, either partly or wholly replacing felspar, are not included in this table. They are essentially of intermediate or of basic character. We might in consequence regard them as varieties of syenite, diorite, gabbro, etc., in which feldspathoid minerals occur, and indeed there are many transitions between syenites of ordinary type and nepheline — or leucite — syenite, and between gabbro or dolerite and theralite or essexite. But, as many minerals develop in these "alkali" rocks that are uncommon elsewhere, it is convenient in a purely formal classification like that outlined here to treat the whole assemblage as a distinct series.

Nepheline and Leucite-bearing Rocks
Commonest Minerals Alkali Feldspar, Nepheline or Leucite, Augite, Hornblend, Biotite Soda Lime Feldspar, Nepheline or Leucite, Augite, Hornblende (Olivine) Nepheline or Leucite, Augite, Hornblende, Olivine
Plutonic type Nepheline-syenite, Leucite-syenite, Nepheline-porphyry Essexite and Theralite Ijolite and Missourite
Effusive type or Lavas Phonolite, Leucitophyre Tephrite and Basanite Nepheline-basalt, Leucite-basalt

This classification is based essentially on the mineralogical constitution of the igneous rocks. Any chemical distinctions between the different groups, though implied, are relegated to a subordinate position. It is admittedly artificial by it has grown up with the grown of the science and is still adopted as the basis on which more minute subdivisions are erected. The subdivisions are by no means of equal value. The syenites, for example, and the peridotites, are far less important than the granites, diorites and gabbros. Moreover, the effusive andesites do not always correspond to the plutonic diorites but partly also to the gabbros. As the different kinds of rock, regarded as aggregates of minerals, pass gradually into one another, transitional types are very common and are often so important as to receive special names. The quartz-syenites and nordmarkites may be interposed between granite and syenite, the tonalites and adamellites between granite and diorite, the monzoaites between syenite and diorite, norites and hyperites between diorite and gabbro, and so on.[4]

See also

Further reading

References

  1. ^ a b Albarède, Francis (2003). Geochemistry: An Introduction. Cambridge University Press. p. 1. ISBN 0-521-81468-5. {{cite book}}: Cite has empty unknown parameter: |coauthors= (help)
  2. ^ a b White, William M. Geochemistry (Unpublished). p. 1. Retrieved 14 March 2012. {{cite book}}: Cite has empty unknown parameter: |coauthors= (help)
  3. ^ a b c Reinhardt, Carsten (2008). Chemical Sciences in the 20th Century: Bridging Boundaries. John Wiley & Sons. p. 161. ISBN 3-527-30271-9. {{cite book}}: Cite has empty unknown parameter: |coauthors= (help)
  4. ^ Public Domain This article incorporates text from a publication now in the public domain: Chisholm, Hugh, ed. (1911). "Petrology". Encyclopædia Britannica (11th ed.). Cambridge University Press.
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