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Trace Element Geochemistry
Lecture 1
A. Beginnings of Geochemistry:
Geology in 1700 and 1800’s (James Hutton, 1726-1797, is known as the “Father
(see Geochemical Society Spec. Pub. No. 4 by B. Mason (1992) for a biography
described as major elements because they form more than 99 wt% of most
pyroxenes and amphiboles. These major elements (ME) are indicated in the
periodic table (Figure 1). They are in order of increasing atomic number O, Na,
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Periodic Table of the Elements
and Ground-State Electronic Configurations
Group
Period IA
1
1 H 2
He
1S
1 IIA IIIB IVB VB VIB VIIB 1S
2
3 4 5 6 7 8 9 10
2 Li Be B C N O F Ne
1 2
[He]2s [He]2s 2 1 2 2 2 3 2 4 2 5 2 6
2s 2p 2s 2p 2s 2p 2s 2p 2s 2p 2s 2p
11 12 13 14 15 16 17 18
3 Na Mg Al Si P S Cl Ar
[Ne]3s
1
[Ne]3s
2
IIIA IVA VA VIA VIIA VIII IB IIB 2
3s 3p
1 2
3s 3p
2 2
3s 3p
3 2
3s 3p
4 2
3s 3p
5 2
3s 3p
6
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
1 2 1 2 2 2 3 2 5 1 5 2 6 2 7 2 8 2 10 1 10 2 2 1 2 2 2 3 2 4 2 5 2 6
[Ar]4s [Ar]4s 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s 4s 4p 4s 4p 4s 4p 4s 4p 4s 4p 4s 4p
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
1 2 1 2 2 2 4 1 5 1 6 1 7 1 8 1 10 10 1 10 2 2 1 2 2 2 3 2 4 2 5 2 6
[Kr]5s [Kr]5s 4d 5s 4d 5s 4d 5s 4d 5s 4d 5s 4d 5s 4d 5s 4d 4d 5s 4d 5s 5s 5p 5s 5p 5s 5p 5s 5p 5s 5p 5s 5p
55 56 57 * 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
6 Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Ti Pb Bi Po At Rn
1 2 1 2 2 2 3 2 4 2 5 2 6 2 7 2 9 1 10 1 10 2 2 1 2 2 2 3 2 4 2 5 2 6
[Xe]6s [Xe]6s 5d 6s 5d 6s 5d 6s 5d 6s 5d 6s 5d 6s 5d 6s 5d 6s 5d 6s 5d 6s 6s 6p 6s 6p 6s 6p 6s 6p 6s 6p 6s 6p
87 88 89 104 105 106 107
7 Fr Ra Ac Unq Unp Unh Uns
1 2 1 2
[Rn]7s [Rn]7s 6d 7s
* 58 59 60 61 62 63 64 65 66 67 68 69 70 71
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
1 1 2 3 2 4 2 5 2 6 2 7 2 7 1 2 9 2 10 2 11 2 12 2 13 2 14 2 14 1 2
4f 5d 6s 4f 6s 4f 6s 4f 6s 4f 6s 4f 6s 4f 5d 6s 4f 6s 4f 6s 4f 6s 4f 6s 4f 6s 4f 6s 4f 5d 6s
90 91 92 93 94 95 96 97 98 99 100 101 102 103
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
2 2 2 1 2 3 1 2 4 1 2 6 2 7 2 7 1 2 8 1 2 10 2 11 2 12 2 13 2 14 2 14 1 2
6d 7s 5f 6d 7s 5f 6d 7s 5f 6d 7s 5f 7s 5f 7s 5f 6d 7s 5f 6d 7s 5f 7s 5f 7s 5f 7s 5f 7s 5f 7s 5f 6d 7s
Figure 1: Periodic Table – The periodic table of the elements is organized according to
electron configuration; that is the systematic arrangement of electrons in orbitals
surrounding the nucleus. This table indicates for each element the outermost electrons;
these are the electrons that determine the chemical bonds between elements. In order to
understand and predict the behavior of a trace element in an igneous system, it is essential
to know where the element of interest lies in the periodic table.
Elements that typically occur as major elements (ME) in igneous rocks and minerals are
indicated by yellow squares. Note that ME are in the first four periods of the periodic
table; all other elements typically occur in lower abundance, <0.1 wt.%, and are
described as Trace Elements.
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C. Modern Development of Trace Element Geochemistry:
The origins of this field clearly arise from the efforts of Goldschmidt but full
development of the field was hindered by the paucity of precise and accurate
abundance data for trace elements in rocks. This hindrance has gradually been
ray fluorescence and more recently other analytical techniques such as isotope
dilution mass spectrometry, neutron activation analysis and most recently the
through use of techniques which can determine the compositions of small “spots”
(10’s of microns) using focused beams, such as the ion microprobe (secondary ion
element geochemist become familiar with the pros and cons of analytical
not discuss analytical techniques but there are numerous useful books. Two are:
With the acquisition of trace element abundance data sets, a need for
theoretical understanding of trace element behavior was needed. Perhaps the first
landmark papers in this field are those of Gast (1968, Geochim. Cosmochim.
Acta, 32, 1957-1986) and Schilling and Winchester (1967, pp. 267-283, In:
in this course.
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D. Sites for Trace Elements (TE) in Minerals (see Figure 2)
2. Defect sites: Minerals do not have perfect arrangement of cations and anions,
and there are defect sites such as Schottky defects whereby a vacancy within
surface of the crystal. Another type of vacancy defect is the Frenkel defect
solid inclusions trapped within a growing mineral. One way to form such
boundary surface where the activity of the excluded element may be sufficient
to form an accessory phase, such as zircon where the dominant cations are Zr
and Si or apatite where the dominant cations are Ca and P (Figure 2d). When
leaching.
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In summary, all of these mechanisms for TE incorporation into minerals are
important, but the mechanism of direct substitution of TE into a structural site is the only
process that is well understood; hence we will emphasize this mechanism. However, we
will read and discuss papers focused on Melt Inclusions and the Role of Surfaces in
of dissolving TE in minerals.
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Figure 2: Two dimensional arrays of a structure composed of X and M ions showing
possible mechanisms for incorporation of ions of trace element Y.
M X Y
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(c) Formation of vacancies that can be occupied by TE.
Upper – Schottky defects form when atoms of X and M leave interior sites in the
crystal. The vacancies formed, indicated by squares, can be occupied by TE.
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(d) Inclusion of TE rich zones within a host crystal, e.g., zircon (ZrSiO4) in biotite.
(e) Absorption of TE on surface of a crystal where bonding differs from that in the
crystal interior.