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Contrib Mineral Petrol (1996) 123: 323–333 C Springer-Verlag 1996

Michael Bau

Controls on the fractionation of isovalent trace elements

in magmatic and aqueous systems: evidence from Y/Ho, Zr/Hf,
and lanthanide tetrad effect

Received: 4 September 1995 y Accepted: 30 October 1995

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

resembles trace element behaviour in aqueous fluids, and

Introduction is clearly different from trace element behaviour in pure
silicate melts. Owing to the lack of appropriate thermo-
Any quantitative interpretation of geochemical data re- dynamic data andyor models, quantitative treatment of
lies on proper knowledge of the fundamental parameters the processes that control the behaviour of Y, REEs, Zr,
which govern the behaviour of trace elements in geo- and Hf in aqueous media and high-silica magmatic sys-
chemical systems. Hence, this question has always at- tems is often impossible. Consequently, in many cases
tracted the specific interest of geochemists and it was as “quantitative” petrogenetic modelling of highly evolved
early as 1937 that one of the pioneers of modern geo- magmatic systems with the currently available data and
chemistry, V.M. Goldschmidt, suggested that ionic models appears to be of very limited value.
charge and radius are the prime parameters that control
the distribution of trace elements in minerals and rocks.
Despite some limitations (for a recent review see, e.g.
Burns 1993), the general validity of this concept is still
one of the cornerstones of igneous geochemistry. One Concentrations of Y, REEs, Zr, and Hf in the samples discussed in
consequence of Goldschmidt’s Rule is that isovalent this contribution have been obtained by Inductively Coupled Plas-
trace elements of equal or very similar ionic radii should ma Mass Spectrometry (ICPMS). Despite being more accurate,
Isotope Dilution Mass Spectrometry cannot be applied, since Y
remain tightly coupled in geological processes. If, how- and several REEs (Pr, Tb, Ho, and Tm) are monoisotopic elements,
ever, in certain geological systems other properties be- and concentration data for Y and the full set of REEs (excepting
come important, this coherency is likely to break down. Pm) are a prerequisite for the type of study presented here. Since
In this contribution emphasis is placed on the be- data are reported for a large number of different sample types (e.g.
haviours of the rare-earth elements (REEs) and of the seawater, hydroxides, fluorides, carbonates, silicates), the specific
techniques of decomposition and analyses will not be reported in
element pairs yttrium-holmium (Y-Ho) and zirconium- detail and the reader is referred to adequate references, instead.
hafnium (Zr-Hf). In natural environments Y and the However, it is important to note that comparison of data deter-
REEs (with the exceptions of Ce and Eu) occur exclu- mined by different analytical techniques (e.g. YXRFyHoICPMS or
sively in the trivalent oxidation state, whereas Zr and Hf ZrXRFyHfINAA) was often found to yield erroneous results, and
should be treated with caution.
are tetravalent. Moreover, Y (1.11) and the REEs (La: For whole-rock analyses, the samples were crushed and pow-
1.08, Gd: 1.11, Lu: 1.11), and Zr (1.22) and Hf (1.23) dered in an agate mortar, decomposed with HFyHClO4 in pressure
show very similar electronegativities (Little and Jones vessels, evaporated to incipient dryness, and taken up in HCl (e.g.
1960), respectively. The effective ionic radii of the REEs Dulski 1994). Fluorite samples were digested with AlCl3-solution
(Bau and Dulski 1995), whereas carbonate minerals were dis-
decrease systematically from La to Lu, i.e. with increas- solved in HCl. Seawater analyses involved ,0.45 mm filtration of
ing atomic number (Shannon 1976). CHArge-and-RA- 11 L samples, acidification with HNO3, addition of a Lu spike,
dius-Controlled (CHARAC) behaviour of the REEs, preconcentration of Y and REEs with ion exchange resin, and
therefore, should always generate smooth normalized elution with HNO3 (Möller et al. 1992; Bau et al. 1995). Trace
REE patterns, whereas irregular patterns (excepting re- element data have been obtained from these sample solutions with
a Perkin Elmer Sciex Elan 500 ICPMS following procedures de-
dox-related anomalies of Ce and Eu) may indicate non- scribed elsewhere (Möller et al. 1992; Dulski 1994).
CHARAC behaviour. In octahedral coordination Y(III), Precision and accuracy of the ICPMS data, which are frequent-
Ho(III), Zr(IV), and Hf(IV) show effective ionic radii of ly evaluated and checked by analyses of international reference
1.019, 1.015, 0.84, and 0.83 Å, respectively (Shannon standards (e.g. Dulski 1994) and by comparison to results of other
laboratories employing different analytical techniques (e.g. Bau
1976). Hence, the element pairs Y-Ho and Zr-Hf are geo- and Dulski 1995; Cotten et al. 1995), are usually (much) better
chemical twin pairs, and any significant fractionation of than +10%. In order to demonstrate that the analytical results,
YyHo and ZryHf ratios gives evidence for non-CHARAC particularly for the high-silica igneous rocks presented here
trace element behaviour. The term “non-CHARAC” as it (which may be considered highly unusual), do not result from
analytical error or bias, two samples from the Abu Dabbab granite,
is used here does not necessarily imply that the effects of Egypt, were additionally analysed in other laboratories employing
charge and radius are negligible, but indicates that in different analytical techniques (Table 1). Concentrations of Y, La,
addition to these two parameters other controls are oper- Ce, Nd, Eu, Dy, Er and Yb in an aliquot of the same sample
ating, which leave their imprint on the trace element sig- solution of sample AD14 that had been used for ICPMS analyses
nature. were determined by ICP atomic emission spectrometry (ICPAES)
at the Université de Bretagne Occidentale, Brest, France (analyst:
In the following I will focus on the profound differ- J. Cotten). The results are in good agreement (Table 1; Fig. 1).
ences between the behaviours of Y, REEs, Zr, and Hf in Another aliquot was taken from the same sample powder of sample
pure silicate melts and in aqueous solutions. Specific AD37 that had previously been used for ICPMS analyses, and trace
distributions of the above elements will be asigned to element concentrations were determined by spark source mass
spectrometry (SSMS; note that this technique avoids sample de-
silicate melts forming basic and intermediate igneous composition) at the Max-Planck-Institut, Mainz, Germany (ana-
rocks, to aqueous solutions and their various precipitates lyst: K.P. Jochum). Despite possible problems resulting from in-
(chemical sediments and hydrothermal minerals), and to terelemental interferences (K.P. Jochum, 1995, personal commu-
highly evolved magmas forming high-silica rhyolites, nication), the results suggest YyHo and ZryHf ratios and a normal-
ized REE pattern similar to those determined by ICPMS, although
granites, and pegmatites. It will be shown that the be- the REE pattern shows a somewhat higher level for heavy REEs
haviour of the above high field strength elements in high- (Table 1; Fig. 1). These differences are unsatisfactory from an
ly evolved H2O-, Li-, B-, F-, P-, andyor Cl-rich magmas analytical point of view, but they are of minor importance for the
Table 1 Comparison of concentration data determined by differ- Table 2 Representative example of each sample type analysed.
ent laboratories employing different analytical techniques. (SSMS Concentration in ppm, except seawater (SW) in pmolykg; all data
spark source mass spectrometry; Max-Planck-Institut, Mainz, obtained by ICPMS. [ND not determined, SW mean South Pacific
Germany; analyst: K.P. Jochum, ICPAES inductively coupled plas- seawater (1000–2000 m depth), FeMnC hydrogenetic marine fer-
ma mass spectrometry, Univ. Brest, France; analyst: J. Cotten, romanganese crust from Tuvalu, South Pacific, HV-F hydrother-
ICPMS inductively coupled plasma mass spectrometry, GFZ Pots- mal vein fluorite from Beihilfe mine, Erzgebirge, Germany, M-C
dam, Germany, ND not determined) magmatic carbonate: sövite from Søve carbonatite, Fen district,
Norway, S-C marine sedimentary carbonate: Carboniferous Lime-
AD37 AD14 stone, Magharees Formation, Ireland, HV-C hydrothermal vein
calcite from Werlau, Rhenish Massif, Germany, AD-G Abu Dab-
Method SSMS ICPMS ICPAES ICPMS bab granite, Egypt]

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

geochemical interpretation, because the anomalous YyHo and Zry

Hf ratios and the shape of the irregular REE pattern are confirmed.
Moreover, these differences may partly be attributed to inhomo-
geneity of the sample powder.
Data for one representative example of each sample type
analysed and discussed here are given in Table 2 (additional infor-
mation are available from the author upon request).

Results and Discussion

Silicate melt systems

It is well established that the Nernst mineralymelt parti-

tion coefficient for a lithophile incompatible element is
predominantly controlled by the ionic charge and ionic
radius of the element considered and by the size and
elasticity of the crystal lattice site into which it is incor-
porated (e.g. Goldschmidt 1937; Taylor 1965; Onuma et
al. 1968; Jensen 1973; Philpotts 1978; Möller 1988;
Beattie 1994; Blundy and Wood 1994). Recently, Blundy
Fig. 1 Comparison of REE data for granite samples from Abu and Wood (1994) have developed a thermodynamic mod-
Dabbab, Egypt, obtained at different laboratories employing dif- el that allows the prediction of mineralymelt partition
ferent analytical techniques. Data for samples AD14 and AD37 coefficients. In Fig. 2 their approach has been used to
were determined from aliquots of the same sample solution and
same sample powder, respectively. ICPMS and ICPAES data for predict partition coefficients between albite and coexist-
the former are in good agreement, whereas differences between ing silicate melts for REE(III) and Y(III) relative to
ICPMS and SSMS data for the latter increase from LREEs to Lu(III) (utilizing Eq. 3 and parameters from Table 1 from
HREEs, possibly due to inhomogeneities of the sample powder. Blundy and Wood 1994, and ionic radii in VIII-fold coor-
Note that the irregular shape of the ICPMS-determined REE pat-
terns is confirmed, indicating that the ICPMS data does not suffer dination from Shannon 1976). This simple example
from analytical bias. Chondrite data from Anders and Grevesse shows that the partition coefficients for isovalent Y and
(1989) REEs are a smooth function of the ionic radius. A well-

Fig. 2 Plot of the Lu-normalized Nernst partition coefficients for

Y and REEs between albite and silicate melt, (Dalbiteymelt)Lu, ver-
sus the effective VIIIY(III) and VIIIREE(III) ionic radius (from
Shannon 1976). Partition coefficients were calculated from Eq. 3
and parameters in Table 1 from Blundy and Wood (1994). Note that Fig. 3 Plot of YyHo ratio versus ZryHf ratio for 48 international
(Dalbiteymelt)Lu is a smooth function of ionic radius, and that the igneous geostandards (data from Govindaraju 1994) and C1-chon-
difference between Y and Ho is negligible compared to the varia- drite (data from Anders and Grevesse 1989). The majority (73%)
tion within the REE series of samples plots within +30% of the chondritic ratios as is expect-
ed for CHArge-and-RAdius-Controlled (CHARAC) trace element
behaviour. Six of the thirteen samples showing larger deviations
known consequence of this relation is that chondrite-nor- are high-silica rocks. 83% of the geostandards showing SiO2 ,
malized REE (REECN; C1-chondrite from Anders and 70% allow an arbitrary definition of a “CHARAC field” with 24 ,
YyHo , 34 and 26 , ZryHf , 46 into which common igneous
Grevesse 1989) patterns of igneous rocks (excepting re- rocks crystallized from pure silica melt systems should fall
dox-sensitive Eu) vary smoothly with ionic radius. Isova-
lent trace elements of similar radii such as the Y-Ho and
Zr-Hf twin pairs show the same degree of incompatibili- (which will be discussed later), chondritic YyHo and Zry
ty, suggesting extremely coherent behaviour of these Hf ratios, indicating CHARAC behaviour of these ele-
twins in basic to intermediate silicate melts. This is in ments, appear to be typical of silicate melt systems. The
agreement with predictions from the Blundy and Wood predicted and apparent coherency of Y-Ho and Zr-Hf
model which suggests that in comparison to the degree during mineralymelt partitioning have even made YyHo
of fractionation within the REE(III) series, Y-Ho frac- and ZryHf ratios valuable probes for testing the validity
tionation should be minor to negligible (Fig. 2). of Henry’s law in partitioning experiments (Beattie
That natural igneous rocks are indeed characterized 1994; Skulski et al. 1994).
by coherent behaviour of Y-Ho and Zr-Hf is exemplified In Fig. 3, the YyHo ratios of 48 international igneous
by mid-ocean-ridge and ocean-island basalts which are geostandards (data from Govindaraju 1994; standards
typified by YyHo (27.7+2.7; n 5 75) and ZryHf are specified in Appendix 1) are plotted versus their Zry
(36.6+2.9, n 5 69) ratios (Jochum et al. 1986) that are Hf ratios. The majority (73%) of samples plots within
similar to the C1-chondritic ratios of 28 and 38, respec- +30% of the chondritic ratios as is expected for
tively. It is further supported by data for komatiites and CHARAC trace element behaviour. Six of the thirteen
for spinel peridotite xenoliths (Jochum et al. 1989). This samples showing larger deviations are high-silica rocks.
implies that the YyHo and ZryHf ratios of basic rocks For simplification of the following figures and discus-
largely reflect the respective ratio of their mantle source. sion, one may arbitarily define a “CHARAC field”
Even more evolved melts do not readily fractionate Y (Fig. 3) with 24 , YyHo , 34 and 26 , ZryHf , 46,
from Ho which is shown, for example, by the chondritic which is based on 83% of the geostandards showing SiO2
YyHo ratios of magmatic zircons (Hinton and Upton , 70%. This range allows for minor fractionation of Yy
1991; Paterson et al. 1992). However, non-chondritic Zry Ho and ZryHf ratios, presumably resulting from the
Hf ratios have occasionally been observed in basalts small but nevertheless potentially important differences
(Garg 1981; Dupuy et al. 1992) and occur more frequent- in ionic radii and hence ionic volumes. Analytical arte-
ly in high-silica rhyolites, granites, and pegmatites (But- facts may contribute to the variability in Fig. 3, since not
ler and Thompson 1965; Möller and Dulski 1983; Černý all data used are considered “recommended values” by
et al. 1985; Wang et al. 1992; and references therein). Govindaraju (1994). Nevertheless, defining the
Although this phenomenon is well known, the principles CHARAC field from international reference standards
that govern Zr-Hf fractionation in highly evolved mag- has the advantage of utilizing an analytically well de-
matic systems are not yet fully understood (Černý 1993). fined data base of a wide variety of mineralogical and
However, excluding highly evolved felsic magmas chemical compositions. Hence, common igneous rocks

Fig. 5 Plot of YyHo ratio versus ZryHf ratio schematically show-

Fig. 4 Plot of YyHo ratio versus ZryHf ratio for 14 Precambrian ing fields of seawater (Y-Ho data from Bau et al. 1995; Zr-Hf data
and 24 Phanerozoic shales (data from Ebeling 1994; Bau and Dul- from L. Godfrey 1995, personal communication), hydrogenetic
ski 1996, and unpublished data). Note that the majority of samples marine Fe-Mn crusts (data from Bau et al. 1996, and unpublished
plots within the CHARAC field defined in Fig. 3 data) and hydrothermal vein fluorites (data from Bau and Dulski
1995) in comparison to C1-chondrite and the CHARAC field de-
fined in Fig. 3. In contrast to pure silicate melt systems, aqueous
solutions and theprecipitates show non-chondritic YyHo and Zry
crystallized from pure silicate melt systems can be ex- Hf ratios, indicating that aqueous systems are characterized by
pected to fall within this CHARAC field. non-CHARAC trace element behaviour
Interestingly, shales display YyHo and ZryHf ratios
that scatter closely around the chondritic ratios. This is
illustrated in Fig. 4 by Precambrian and Phanerozoic epi- Y-Ho fractionation is common as is evidenced by hy-
clastic sediments the majority of which plot within the drothermal vein fluorites (Bau and Dulski 1995) which
CHARAC field. Hence, non-CHARAC behaviour of Y, show non-chondritic, elevated YyHo ratios of up to
Ho, Zr, and Hf during erosion, transport, and deposition .200. Preliminary data on Zr and Hf abundances sug-
is exceptional, and epiclastic sediments largely reflect gest that this type of fluorite also shows non-chondritic
the (commonly chondritic) YyHo and ZryHf ratios of ZryHf ratios between 2 and 5. Fractionation of Y-Ho in
their source rocks. hydrothermal fluorites can be related to the relative sta-
bilities of Y and REE fluoride complexes which are
higher for Y than for Ho (Walker and Choppin 1967),
Aqueous systems resulting in increasing YyHo ratios during migration of
fluorine-rich hydrothermal fluids (Bau and Dulski
Compared to pure silicate melts, a completely different 1995). Non-chondritic YyHo ratios of seawater and Y-
picture unfolds in aqueous systems (Fig. 5). Seawater, Ho fractionation during formation of marine hydrogenet-
which is probably the geochemically best studied, natu- ic ferromanganese crusts are due to differences in the
ral low-temperature aqueous solution, is characterized marine particle reactivity of these elements, predomi-
by YyHo ratios (Zhang et al. 1994; Bau et al. 1995) be- nantly resulting from different stabilities of both organic
tween 44 and 74 and by ZryHf ratios between 85 and 130 and inorganic surface complexes of Y and Ho (Bau et al.
(note that these ZryHf ratios are considerably higher than 1995; 1996).
those suggested by Boswell and Elderfield (1988) who Comparing carbonate minerals of different origins,
apparently determined Hf abundances that were too high; Fig. 6 shows that magmatic carbonates from carbonatites
L. Godfrey 1995, personal communication). The YyHo are characterized by chondritic YyHo ratios, indicating
and ZryHf ratios of seawater are significantly higher than CHARAC behaviour of Y and Ho (REEs) during evolu-
those of chondrites or shales. Hydrogenetic marine fer- tion of carbonatitic melts. In contrast, sedimentary car-
romanganese crusts which are low-temperature precipi- bonates (marine limestones) display elevated YyHo ra-
tates in equilibrium with seawater, display lower YyHo tios similar to but slightly lower than those of seawater.
ratios (17–25) compared to both seawater and alumi- Hydrothermal carbonates from calcite veins within
nosilicates, and show ZryHf ratios (50–90) that are inter- marine limestone (not shown in Fig. 6) show YyHo ratios
mediate between the ratios of seawater and clastic alumi- which correspond to those of their host rock, whereas
nosilcates (Bau et al. 1996; and unpublished data). Even hydrothermal calcites from veins within crystalline
in medium-temperature (100–4008C) aqueous systems country rock show non-chondritic YyHo ratios ranging

defined by the other REE complexes (e.g. Byrne and

Kim 1990; Lee and Byrne 1993; Bau et al. 1996). Oppos-
ing directions of Y-Ho fractionation in hydrothermal
vein fluorites and hydrothermal vein carbonates reveal
that the behaviour of the pseudolanthanide Y with
respect to the lanthanides is controlled by the type of
complexing ligand which dominates the speciation of Y
and REEs, i.e. by fluid composition (Bau and Dulski
1995). This dependency may be explained by slight dif-
ferences in the character of the chemical bonding (cova-
lent vs electrostatic) in aqueous complexes, which is
controlled by the electron configuration of the cation
and by the type of complexing ligand (e.g. Jørgensen
1970; Borkowski and Siekierski 1992; Kawabe 1992).
Hence, non-CHARAC behaviour of Y, REEs, Zr, and
Hf in aqueous fluids results from chemical complexa-
tion, and electron structure must be considered as an
additional parameter which besides valency and size
controls the behaviour of trace elements in aqueous sys-
Fig. 6 Plot of Y concentration versus YyHo ratio for carbonate
minerals of magmatic, marine sedimentary, and hydrothermal Highly evolved magmatic systems
origin, respectively. Whereas magmatic carbonates from carbon-
atites show chondritic ratios, indicating CHARAC behaviour of Y
and Ho (REEs) during genesis and evolution of carbonatitic melts, As mentioned earlier, Zr-Hf fractionation has been re-
marine limestones show elevated, non-chondritic YyHo ratios sim- ported for highly evolved magmatic systems. To evaluate
ilar to those of seawater. Hydrothermal carbonates from calcite whether or not Zr-Hf fractionation in these rocks is ac-
veins show variable but non-chondritic YyHo ratios which are
smaller than those of the rock from which Y and REEs have been companied by Y-Ho fractionation, Fig. 7 presents data
mobilized for several granite-pegmatite systems. Obviously, all
sample suites plot outside the CHARAC field, and the
most extreme case of fractionation is represented by al-
from 15 to 55. The YyHo ratio of hydrothermal vein cal- bite granites from Abu Dabbab, Egypt (for geological
cite partly depends on the type of rock from which Y and details see Mohamed 1993; Jahn 1994). Samples from
REEs have been mobilized, but is usually smaller than the Eibenstock Granite, Germany, even constitute a trend
the YyHo ratio of this source rock (M. Bau and P. Dulski, that evolves away from the CHARAC field. Figure 7 sug-
work in preparation). For example, a hydrothermal fluid gests that a close relationship exists between the “anoma-
that mobilizes Y and REEs from a marine limestone se- lous” behaviours of the elements Y, Ho, Zr, and Hf in
quence initially displays an elevated YyHo ratio which is high-silica magmatic systems. However, whereas
similar to that of the limestone. However, the YyHo ratio “anomalous” ZryHf ratios appear to be always below the
of the fluid will progressively decrease with increasing chondritic ratio, the YyHo ratio may evolve in both direc-
migration distance. The chondritic YyHo ratios of some tions, i.e. granite-pegmatite suites may show either
hydrothermal vein calcites, therefore, cannot be taken as higher or lower ratios than C1-chondrite (e.g. Fig. 7).
evidence for CHARAC behaviour of Y and REEs. The apparent association between anomalous be-
More detailed discussion of the various implications haviours of Y, Ho, Zr, and Hf does even include the com-
of these results is beyond the scope of this communica- plete REE series. All samples from the Pleasant Ridge
tion. The important point to be made here is that in con- Granite, Canada (data from Taylor 1992), which show
trast to silicate melt systems, the geochemical twin pairs non-chondritic YyHo (18–20) and ZryHf (9–13) ratios,
Y-Ho and Zr-Hf are highly fractionated in aqueous me- display REECN patterns which no longer increase or de-
dia (Figs. 5 and 6). Aqueous solutions and their precipi- crease smoothly with ionic radius but which show inter-
tates do not fall into the CHARAC field defined in Fig. 3, nal irregularities (in the form of four concave-upward
indicating that aqueous systems are characterized by segments) often referred to as “tetrads” or “lanthanide
non-CHARAC behaviour of (these) trace elements. This tetrad effect” (Fig. 8a). The same is observed for high-
is further substantiated by the presence of non-redox-re- silica granitoids from several plutons in the Erzgebirge,
lated, positive La and Gd anomalies in normalized REE Germany (e.g. Förster and Tischendorf 1994; Irber et al.
patterns of seawater and marine precipitates (e.g. de 1994). The granites from Abu Dabbab which yield high-
Baar et al. 1991; Kawabe et al. 1991; Lee and Byrne ly fractionated YyHo (4.2–17) and ZryHf (1.5–2.4) ratios
1993; Möller et al. 1994; Bau and Dulski 1996; Bau et al. and plot farthest away from the CHARAC field in Fig. 7,
1996), which result from deviations of the stability of show the most pronounced lanthanide tetrad effect of all
aqueous La and Gd complexes from the smooth trend samples considered (Fig. 8b). The “normal” REECN pat-

related to their number of 4f electrons (Kawabe 1992).

Moreover, the Racah parameters decrease with increas-
ing covalent character of the bonding between cation and
complexing ligand. Hence, the type of ligand involved in
REE complexation may enhance or suppress the intere-
lectron repulsion and thereby affects the behaviour of the
REEs (both as a group and individually) in geochemical
The precise determination of complete REE patterns
(except Pm) is a prerequisite for any discussion of lan-
thanide tetrad effects, but even if these data are available
(e.g. from ICPMS analyses) the situation is complicated
because of the lack of Pm data and due to the possibility
of anomalous behaviour of redox-sensitive Ce and Eu.
Hence, although A. Masuda and co-workers have repeat-
edly claimed to have found evidence for the existence of
the lanthanide tetrad effect (e.g. Masuda et al. 1987;
Masuda and Akagi 1989; Akagi et al. 1993; and refer-
ences therein), its occurrence in geological solid materi-
als is still not widely accepted and often ascribed to ana-
lytical problems or to the normalization procedure (e.g.
Fig. 7 Plot of YyHo ratio versus ZryHf ratio for high-silica gran-
McLennan 1994). However, patterns shown in Fig. 8 are
ites from Abu Dabbab, Eastern Desert, Egypt (for geological de- based on data obtained at different laboratories, and dis-
tails see Mohamed 1993; Jahn 1994); from Eibenstock, Erzge- play deviations from smooth trends which are much too
birge, Germany (for details see Förster and Tischendorf 1994); large to result from erroneous REE determination or nor-
from Pleasant Ridge, Canada (data from Taylor 1992); and from malization. This is further supported by the country rock
Calamity Peak, U.S.A. (data from Duke et al. 1992). All samples
show non-chondritic YyHo and ZryHf ratios, and the Eibenstock of the Abu Dabbab granite which does not show the lan-
suite even constitutes a trend that evolves away from the CHARAC thanide tetrad effect, despite being decomposed and
field. Trace element behaviour in highly evolved felsic magmas is analysed along with the granite samples. Unfortunately,
obviously not exclusively controlled by ionic charge and radius, the lanthanide tetrad effect is often less well developed,
but, similar to trace element behaviour in aqueous solutions, is
additionally affected by other parameters. The similarity between and presuppositions regarding its general existence or
aqueous systems and highly evolved magmatic systems, which both non-existence in geological samples may occasionally
are characterized by non-CHARAC behaviour of Y, Ho, Zr, and have misguided the geochemical interpretation of data
Hf, corroborates models (e.g. London 1986, 1987) suggesting that sets.
high-silica magmatic systems are transitional between pure sili- Rejecting the hypothesis that the irregular REECN
cate melts and aqueous solutions
patterns of some high-silica igneous rocks are due to the
lanthanide tetrad effect (as was promoted by Masuda and
tern of their gneissic country rock indicates that this fea- Akagi, 1989, for example), McLennan (1994) suggested
ture is restricted to the plutonic body, and is not related to that fractional crystallization of individual mineral
a younger regional-scale hydrothermal overprint. It is phases such as the apatites studied by Jolliff et al. (1989)
important to note that these irregular REECN patterns may produce these “anomalous” REECN patterns. How-
(the lanthanide tetrad effect) cannot be modelled ade- ever, this reasoning does not invalidate Masuda’s hy-
quately with currently available mineralymelt partition pothesis, since it does not address the question, why
coefficents which from a maximum value all decrease these apatites display such an unusual trace element sig-
smoothly and steadily with ionic radius (as was dis- nature (the reason may well be the lanthanide tetrad ef-
cussed earlier). fect). The apparent link between irregular REECN pat-
The lanthanide tetrad effect is well known from terns and non-chondritic YyHo and ZryHf ratios argues
aqueous geochemistry where it was first observed by Fi- against McLennan’s suggestion, because fractionation of
delis and Siekierski (1966) and Peppard et al. (1969). apatite alone cannot explain non-CHARAC behaviour of
The term “tetrad effect” refers to the sub-division of the Zr and Hf. In highly evolved igneous rocks different ac-
fifteen members of the REE series into four groups (I: La cessory minerals are likely to control the whole-rock dis-
to Nd; II: Pm to Gd; III: Gd to Ho; IV: Er to Lu) with tribution of Y and REEs which may be hosted by apatite,
“breaks” at Gd and between Nd and Pm, and between Ho for example, and of Zr and Hf which are hosted by zircon.
and Er, corresponding to the 1y2-, 1y4-, and 3y4-filled 4f The combination of non-chondritic YyHo and ZryHf ra-
sub-shell, respectively. The tetrad effect results from re- tios and the lanthanide tetrad effect in whole-rock grani-
pulsion between electrons in the 4f orbital. This intere- toid samples, therefore, indicates that all these minerals
lectron repulsion can be expressed by the Racah parame- display an irregular trace element distribution. More-
ters (e.g. Jørgensen 1970). These depend on the effective over, the occurrence of non-chondritic YyHo and ZryHf
nuclear charge which in the case of the REEs is closely ratios and the lanthanide tetrad effect in magmatic ap-
Fig. 8a–c REECN patterns of granites from: a Pleasant Ridge,
Canada (data from Taylor 1992), b Abu Dabbab, Egypt (including
one sample of the country rock); c biotite granite E17-8B from
unit GLB-1and leucogranite E31-1 from unit GLB-5 of the Ghost
Lake batholith, Canada (data from Breaks and Moore 1992). All
samples show irregular REECN patterns displaying the lanthanide
tetrad effect, i.e. four concave-upwards segments, except the coun-
try rock (gneiss) of the Abu Dabbab Granite in b, and the biotite
granite from unit GLB-1 in c. The question marks indicate that Eu
concentrations were below the determination limit. For further
explanation see text

atites and zircons is exceptional (e.g. Fleischer and

Altschuler 1986; and Butler and Thompson 1965; Černý
et al. 1985; Hinton and Upton 1991, respectively) and
usually confined to minerals crystallized from high-sili-
ca magmas. Thus, this type of trace element fractiona-
tion cannot be ascribed to specific properties of the crys-
tallizing minerals, but rather is a reflection of specific
physicochemical properties of the magma. Differences
in the solution behaviour of these elements between in-
termediate-silica and high-silica melts, however, are un-
likely to produce the “anomalous” fractionation trends
shown by the latter, as was experimentally shown for Zr
and Hf (Ellison and Hess 1986).
In the magmatic realm, non-CHARAC trace element
behaviour is apparently restricted to highly evolved sili-
cate magmas rich in components such as H2O, CO2, Li,
B, F, P, andyor Cl, which is illustrated in Fig. 8c by sam-
ples from the Ghost Lake granite-pegmatite system (data
from Breaks and Moore 1992). The series starts with
biotite granite (sample E17-8B) which shows chondritic
YyHo (26) and ZryHf (37) ratios and REECN patterns
without tetrad effect. In the more evolved units, however,
YyHo and ZryHf ratios decrease significantly and
REECN patterns start to display the tetrad effect (exem-
plified in Fig. 8c by a fine grained leucogranite, sample
E31-1, with YyHo and ZryHf ratios of 21 and 18, respec-
tively). Interestingly, in this case this evolution is accom-
panied by a pronounced increase of the B content from
14 to 2300 ppm, whereas abundance variations of other
components are minor to negligible (F: 440 and 410 ppm;
Cl: 75 and 60 ppm; CO2: 0.19 and 0.14%; Li: 9 and
16 ppm; P2O5: 0.11 and 0.11%; data from Breaks and
Moore 1992). From these (few) data one may speculate
that the concentration of B exerts an important control
on the behaviours of Y, REEs, Zr, and Hf in highly
evolved magmatic systems, although the opposing trends
for the YyHo ratio in Fig. 7 indicate that other compo-
nents should also be considered. Apparently, trace ele-
ment behaviour in highly evolved magmatic systems is
different from that in basic to intermediate melts, but
closely resembles trace element behaviour in aqueous
systems. This may be explained by increasing impor-
tance of chemical complexation with an increasing vari-
ety of ligands during the evolution of magmatic systems.
Since in magmatic systems non-CHARAC behaviour of
incompatible trace elements is confined to highly
evolved magmas, it may frequently occur in the upper
parts of magma chambers containing felsic magmas, and

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
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
[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
[147] JG-1a Granodiorite Butler JR, Thompson AJ (1965) Zirconium: hafnium ratios in
[148] JG-2 Granite some igneous rocks. Geochim Cosmochim Acta 29: 167–175
[149] JG-3 Granodiorite Byrne RH, Kim KH (1990) Rare earth element scavenging in sea-
[150] JB-1 Basalt water. Geochim Cosmochim Acta 54: 2645–2656
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[157] JA-2 Andesite and mechanisms. Can Mineral 23: 381–421
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