Beruflich Dokumente
Kultur Dokumente
Michael Bau
Abstract The parameters which control the behaviour lanthanide tetrad effect, which cannot be adequately
of isovalent trace elements in magmatic and aqueous sys- modelled with current mineralymelt partition coeffi-
tems have been investigated by studying the distribution cients which are smooth functions of ionic radius, reveals
of yttrium, rare-earth elements (REEs), zirconium, and that non-CHARAC trace element behaviour prevails in
hafnium. If a geochemical system is characterized by highly evolved magmatic systems. The behaviour of high
CHArge-and-RAdius-Controlled (CHARAC) trace ele- field strength elements in this environment is distinctly
ment behaviour, elements of similar charge and radius, different from that in basic to intermediate magmas (i.e.
such as the Y-Ho and Zr-Hf twin pairs, should display pure silicate melts), but closely resembles trace element
extremely coherent behaviour, and retain their respective behaviour in aqueous media. “Anomalous” behaviour of
chondritic ratio. Moreover, normalized patterns of Y and REEs, and of Zr and Hf, which are hosted by
REE(III) should be smooth functions of ionic radius and different minerals, and the fact that these minerals show
atomic number. Basic to intermediate igneous rocks “anomalous” trace element distributions only if they
show YyHo and ZryHf ratios which are close to the chon- crystallized from highly evolved magmas, indicate that
dritic ratios, indicating CHARAC behaviour of these ele- non-CHARAC behaviour is a reflection of specific
ments in pure silicate melts. In contrast, aqueous solu- physicochemical properties of the magma. This supports
tions and their precipitates show non-chondritic YyHo models which suggest that high-silica magmatic systems
and ZryHf ratios. An important process that causes trace which are rich in H2O, Li, B, F, P, andyor Cl, are transi-
element fractionation in aqueous media is chemical com- tional between pure silicate melts and hydrothermal flu-
plexation. The complexation behaviour of a trace ele- ids. In such a transitional system non-CHARAC be-
ment, however, does not exclusively depend on its ionic haviour of high field strength elements may be due to
charge and radius, but is additionally controlled by its chemical complexation with a wide variety of ligands
electron configuration and by the type of complexing such as non-bridging oxygen, F, B, P, etc., leading to
ligand, since the latter two determine the character of the absolute and relative mineralymelt or mineralyaqueous-
chemical bonding (covalent vs electrostatic) in the vari- fluid partition coefficients that are extremely sensitive to
ous complexes. Hence, in contrast to pure melt systems, the composition and structure of this magma. Hence, any
aqueous systems are characterized by non-CHARAC petrogenetic modelling of such magmatic rocks, which
trace element behaviour, and electron structure must be utilizes partition coefficients that have not been deter-
considered as an important additional parameter. Unlike mined for the specific igneous suite under investigation,
other magmatic rocks, highly evolved magmas rich in may be questionable. But YyHo and ZryHf ratios provide
components such as H2O, Li, B, F, P, andyor Cl often information on whether or not the evolution of felsic ig-
show non-chondritic YyHo and ZryHf ratios, and “irreg- neous rocks can be quantitatively modelled: samples
ular” REE patterns which are sub-divided into four con- showing non-chondritic YyHo and ZryHf ratios or even
cave-upward segments referred to as “tetrads”. The com- the lanthanide tetrad effect should not be considered for
bination of non-chondritic YyHo and ZryHf ratios and modelling. However, the most important result of this
study is that YyHo and ZryHf ratios may be used to verify
whether Y, REEs, Zr, and Hf in rocks or minerals have
been deposited from or modified by silicate melts or
M. Bau aqueous fluids.
GeoForschungsZentrum Potsdam, PB 4.3 Lagerstättenbildung,
Telegrafenberg A-50, D-14473 Potsdam, Germany
Editorial responsibility: J. Hoefs
324
Y [ppm] 0.99 0.84 1.1 1.08 Representative example of each sample type analysed
Zr 25.0 25.5 ND 77.8
Hf 9.9 12.3 ND 49.4 SW FeMnC HV-F M-C S-C HV-C AD-G
La 1.59 1.55 1.82 1.85
Ce 7.44 7.06 9.23 9.05 Y 151 147 207 13.8 3.26 207 1.08
Pr 1.11 1.03 ND 1.15 Zr ND 540 3 ND ND ND 77.8
Nd 2.28 2.02 2.42 2.12 Hf ND 7.39 0.9 ND ND ND 49.4
Sm 0.94 0.75 ND 0.658 La 36.9 219 7.94 44.2 1.20 7.94 1.85
Eu ,0.05 0.011 0.011 0.010 Ce 3.30 923 18.3 99.5 1.16 18.3 9.05
Gd (0.7) 0.26 ND 0.252 Pr 2.63 36.9 3.02 11.3 0.23 3.02 1.15
Tb 0.19 0.12 ND 0.125 Nd 11.64 156 16.5 42.6 1.03 16.5 2.12
Dy 1.19 0.83 1.29 1.25 Sm 2.16 29.4 8.34 6.79 0.22 8.34 0.658
Ho 0.21 0.14 ND 0.247 Eu 0.59 7.27 4.83 1.91 0.063 4.83 0.01
Er 0.87 0.63 1.63 1.33 Gd 3.59 36.4 14.7 5.08 0.29 14.7 0.252
Tm 0.29 0.22 ND 0.487 Tb 0.594 6.92 2.75 0.602 0.051 2.75 0.125
Yb 2.82 2.91 7.09 7.14 Dy 4.88 34.6 15.7 3.15 0.27 15.7 1.25
Lu 0.48 0.42 ND 1.05 Ho 1.53 7.26 2.73 0.504 0.068 2.73 0.247
Er 5.40 22.0 7.17 1.24 0.24 7.17 1.33
ZryHf 2.5 2.1 ND 1.6 Tm 0.875 3.10 0.87 0.152 0.034 0.87 0.487
YyHo 4.7 6.0 ND 4.4 Yb 6.445 20.1 0.47 0.928 0.22 5.47 7.14
YyDy 0.8 1.0 0.7 0.8 Lu ND 3.02 0.66 0.134 0.027 0.66 1.05
YyEr 1.1 1.3 0.9 0.9
non-chondritic YyHo and ZryHf ratios and the lan- thanide tetrad effect, on the other hand, generates a
thanide tetrad effect may be typical features of au- spread of the initial SmyNd ratios of high-silica grani-
tometasomatism. toids. For example, the two samples from the Ghost Lake
granite-pegmatite system (already mentioned in the fore-
going section) yield SmyNd ratios of 0.21 and 0.36, re-
Concluding remarks spectively (data from Breaks and Moore 1992). Hence,
such suites (especially Precambrian ones) may be ideal
Non-CHARAC trace element behaviour appears to be candidates for Sm-Nd isotope geochronology.
much more widespread in natural systems than was pre- Moreover, by considering YyHo and ZryHf ratios it
viously documented. Aqueous solutions of high com- should be possible to determine whether Y, Ho (REEs),
plex-forming capacity and their precipitates typically Zr, and Hf have been deposited from or whether their
show non-chondritic YyHo and ZryHf ratios and occa- distribution has been modified by a silicate melt or an
sionally display the lanthanide tetrad effect. Thus, in aqueous solution (which is still a major problem in stud-
aqueous media non-CHARAC behaviour is more the rule ies of mantle metasomatism and the genesis of ore de-
than the exception. In contrast, pure silicate melts form- posits, for example). One may further suspect that if the
ing basic to intermediate igneous rocks appear to be distribution of rather “immobile” elements such as Y,
characterized by CHARAC trace element behaviour. REEs, Zr, and Hf has been affected, the distribution of
Both experimental and theoretical studies devoted to large ion lithophile elements, such as Rb and Sr, which
the determination of mineralymelt partition coefficients are much more prone to mobilization by aqueous fluids,
suggest CHARAC behaviour of Y, REEs, Zr, and Hf. was modified as well. This is supported by the pro-
However, significant deviations from this rule apparently nounced fractionation of K and Rb which is often ob-
occur in highly evolved magmatic systems which are rich served in highly evolved magmatic rocks (e.g. Shaw
in H2O, CO2, and elements such as Li, B, F, P, andyor Cl, 1968).
and which share similarities with aqueous fluids or Hence, non-radius-dependent fractionation of isova-
which may even be regarded as transitional between a lent trace elements, leading to non-chondritic YyHo and
pure silicate melt and an aqueous fluid (e.g. London ZryHf ratios, and generating the lanthanide tetrad effect,
1986, 1987). In these “transitional” meltsyaqueous-flu- may have the potential to become a very valuable indica-
ids with their specific chemical composition and struc- tor in geochemical studies.
ture, highly charged cations such as Y(III), REEs(III),
Zr(IV), and Hf(IV) may form complexes with a variety of Acknowledgements Thanks are due to S. Jahn who generously
provided samples from the Abu Dabbab Granite, to H.J. Förster
ligands such as non-bridging oxygen (NBO), F, B, etc. and G. Tischendorf who kindly contributed some of their unpub-
(e.g. Ponader and Brown 1989; Keppler 1993). In this lished data on the Eibenstock Granite, and to V. Lüders and U.
case, the behaviour of a trace element can no longer be Hein who provided numerous samples of hydrothermal minerals.
described as a mere function of its ionic charge and ra- Special thanks to P. Dulski for his analytical expertise, and to W.
dius, but is additionally constrained by its electron con- Irber for long discussions on what we initially used to call “non-
Goldschmidt fractionation”. The kind collaboration of K.P.
figuration which affects the nature of chemical bonding Jochum and J. Cotten in cross-checking analytical quality is grate-
in its various compounds, hence the stability of its vari- fully acknowledged. This contribution benefited considerably
ous chemical complexes. Indeed, the strong dependance from comments by P. Möller, R.C. Maury and J. Brenan on earlier
of absolute and relative mineralyaqueous-fluid partition versions of this paper. Thanks go to the CMP journal referees, one
of which was Scott Wood, for constructive critizism.
coefficients on the chemical composition of the aqueous
fluid is well documented in the literature (e.g. Brenan
and Watson 1991; Keppler 1993; Fleet and Pan 1995; and
Appendix
references therein). Owing to the wide range of possible
fluid compositions (which will further change in the
International geostandards (n 5 48) used in Fig. 3 (from
course of differentiation), however, mineralyaqueous-
Govindaraju 1994)
fluid partition coefficients may be considerably more
variable (and less predictable) than mineralymelt parti- Sample number Sample name
tion coefficients. Thus, petrogenetic modelling of the [001] G-1 Granite
evolution of high-silica igneous suites using mineraly [002] W-1 Diabase
melt or mineralyaqueous-fluid partition coefficients [003] AGV-1 Andesite
which have not been determined for the specific chemi- [004] BCR-1 Basalt
cal composition of the magma studied can only be quali- [006] G-2 Granite
[007] GSP-1 Granodiorite
tative and may even lead to erroneous conclusions. How- [009] BHVO-1 Basalt
ever, YyHo and ZryHf ratios may be used as probes for [011] QLO-1 Quartz latite
testing whether or not a suite of igneous rocks is suitable [012] RGM-1 Rhyolite
for quantitative petrogenetic modelling. Conclusions [016] STM-1 Syenite
[017] BIR-1 Basalt
derived from rocks that show YyHo and ZryHf ratios far [018] DNC-1 Dolerite
from those of chondrites or which even display the lan- [019] W-2 Diabase
thanide tetrad effect are at least questionable. The lan- [029] SY-2 Syenite
332
[030] SY-3 Syenite Breaks FW, Moore JM Jr (1992) The Ghost Lake Batholith, Supe-
[031] MRG-1 Gabbro rior Province of northwestern Ontario: a fertile, S-type, pera-
[052] GA Granite luminous granite – rare-element pegmatite system. Can Miner-
[053] GH Granite al 30: 835–875
[054] BR Basalt Brenan JM, Watson EB (1991) Partitioning of trace elements be-
[057] DR-N Diorite tween olivine and aqueous fluids at high P and T: implications
[062] GS-N Granite for the effect of fluid composition on trace-element transport.
[066] BE-N Basalt Earth Planet Sci Lett 107: 672–688
[070] AC-E Granite Burns RG (1993) Mineralogical applications of crystal field theo-
[146] JG-1 Granodiorite ry, 2nd edn. Cambridge University Press, Cambridge
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