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Chapter 1


Very soon after the birth of igneous geochemistry, geologists like Alfred Harker
(Harker 1909) recognized the existence of igneous rock “series”, i.e. rock suites
sharing common geochemical features and having progressively changing compo-
sitions. Such variation was, and still frequently is, ascribed to evolution by frac-
tional crystallization at depth, in a putative magma chamber. Research over the
following century, however, has demonstrated that the chemistry of magmatic
suites may in fact be shaped by many contrasting petrogenetic processes. Geo-
chemistry, especially in combination with petrology, represents a powerful tool for
deciphering and parameterizing of such processes.

1.1 Causes of Whole-Rock Chemical Variation in Igneous


Human beings—and geologists in particular—have always been fascinated by

magmas. Due to the well-known increase of temperature with depth, it was be-
lieved for a long time that there is a planetary-scale reservoir of molten rocks
beneath the crust (e.g., Kircher 1664; Moro 1740; Cordier 1827). This archaic
concept has long been abandoned as seismic data demonstrated that, apart from
the outer core, the interior of the Earth is solid (Oldham 1906; Gutenberg 1914;
Jeffreys 1926, among others). Suddenly a more complex picture has arisen—that
of vigorous deep interactions between solid and liquid materials, including at least
two successive petrogenetic processes: melting and crystallization. Of course,
these mechanisms are inaccessible to direct observation, which is why their inves-
tigation has been mainly indirect, based on petrological and geochemical methods.
In the beginning of the 20th century, two distinct and complementary ap-
proaches to the problem emerged. The first one, based on experiments, was devel-
oped by Bowen (1912, 1928) who demonstrated the existence of mineral reaction
series in magmatic systems. Indeed, during the crystallization of magma, minerals
do not grow simultaneously but, as the magma cools, the individual mineral
phases appear in a succession determined by their crystallization temperature. This
concept showed crystallization as a dynamic process with a certain temporal

© Springer-Verlag Berlin Heidelberg 2016 1

V. Janoušek et al., Geochemical Modelling of Igneous Processes – Principles
And Recipes in R Language, Springer Geochemistry,
DOI 10.1007/978-3-662-46792-3_1
2 1 Introduction

development. Thus, the evolution is not linear, but it can take different directions
in response to the changes in physico–chemical parameters and, in turn, of mineral
chemistry of crystallizing assemblages.
It was about the same time that a second approach, exemplified by Harker
(1909) was developed based on interpretation of whole-rock compositions. This
author came up with the concept of a variation diagram, plotting oxides of major
elements against an “index of differentiation”. Harker’s suggestion to use SiO2 as
a differentiation index was ground-breaking at the time and marked the dawn of
modern geochemistry. He showed that when the bulk composition of rocks be-
longing to the same petrographic province, or even a single volcanic (or plutonic)
complex, are plotted in such variation diagrams, they define more or less continu-
ous evolutionary trends (Fig. 1.1). Harker proposed to interpret these trends in
terms of magmatic differentiation, directly correlated to the nature of the crystal-
lizing mineral phases.

Fig. 1.1 An example of early depiction of differentiation trends in binary plots of silica vs.
major-element oxides, for the volcanic rocks from Lassen Peak (California) (Harker 1909).
These later became known as the Harker plots.

Even though both these approaches have been an important step forward, they
have for long remained essentially descriptive, or qualitative at best. The first at-
tempts on quantifying and modeling the behaviour of trace elements in magmas
date back to the late 1960’s (Gast 1968; Shaw 1970). Similarly, even if the chemi-
cal fractionation laws had been long known for gases (Rayleigh 1896), it was only
at this same period that they were invoked to model the fractionation of crystalliz-
ing magmatic liquids (Neumann et al. 1954; Greenland 1970; Albarède and
Bottinga 1972). Also the analysis of mineral chemistry was revolutionized by the
appearance of the first commercially available electron microprobes (Castaing
1951). Lastly, the prestigious lunar program in the 1960’s required precise and ac-
curate chemical, and then isotopic, analyses of small samples, leading to innova-
tions (Johnson et al. 2013).