CHEMICAL

GEOLOGY
. ~~ - ~ ~ IS()TOI~E (;EOS¢5"IE \ ( "1."
ELSEVIER Chemical Geology 118 ( 1994 ) 143-153

A procedure for calculating the equilibrium distribution of trace

elements among the minerals of cumulate rocks, and the
concentration of trace elements in the coexisting liquids I
J e a n H. B 6 d a r d
Geological Survey of Canada, Centre Gkoscientifique de Qug'bec, 2700 Einstein, CP 7500, Ste.-Fov Quk. G1 V 4C7, Canada
Received 1 December 1993; revision accepted 25 May 1994

Abstract

Whole-rock trace-element analyses can be used in conjunction with partition coefficients and mineral modes to
calculate a liquidus-temperature equilibrium distribution of trace elements among the constituent minerals of
cumulate rocks. Once the concentration of a trace element in a given mineral phase is known, then the trace-
element concentration in the liquid that was in equilibrium with this mineral can be calculated if certain assump-
tions are made about the temperature and major-element chemistry of the liquid. The effects of a trapped melt
fraction (TMF) are accounted for by: ( 1) including in the calculation a phase (the trapped melt) with a mineral/
melt partition coefficient of 1; and (2) adjusting the rock's mode to reflect removal of the TMF. The method
yields results comparable to those given by mineral separation or in situ analysis for trace elements.

1. Introduction and concepts proportions and compositions of the minerals

A common problem encountered in igneous
petrology is that many intrusive rocks are not
quenched liquids, but are crystal segregations or
cumulates [see Wager and Brown (1968) and
Irvine (1982) for reviews and definition of con-
cepts and terminology ]. Liquid compositions are
needed for paleo-tectonic classification (e.g.,
Pearce and Cann, 1973, and see review in Wang
and Glover, 1992), for determining whether or
not a suite of rocks belong to the same liquid line
of descent, and for quantitative modelling of ig-
neous processes. The chemistry of cumulate plu-
tonic rocks is principally controlled by the modal
[EW]
Geological Survey of Canada contribution No. 15393.
that accumulated, and the proportion and com-
position of the melt entrapped during crystalli-
zation. Possible complicating factors include:
episodic expulsion of variably fractionated en-
trapped melt, reactions between entrapped melt
and the cumulate crystals, and post-cumulus me-
tasomatic reactions with migrating melt derived
from other parts of the cumulate pile.
The concentrations of elements in the liquids
that coexisted with plutonic rocks can be esti-
mated in three ways. One method is to separate
the minerals using magnetic separators and heavy
liquids, with final hand-picking of grains under
a microscope. The mineral separates are then an-
alysed for the trace elements, and mineral/melt
partition coefficient data are used to calculate the
liquid composition. There are many problems

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144 J.H. Bkdard / Chemical Geology 118 (1994) 143-153

Table 1
D-values used in calculations for Figs. 1-4 and A-l-A-3

CPX Refer- OPX Refer- Olivine Refer- PLAG Refer- Spinel Refer- ILM Refer- MT Refer- AMP Refer-
ence ence ence ence ence ence ence ence

La 0.0536 [11 0.016 [221 0.00044 [7] 0.042 [23] 0.0006 [8] 0.0072 [15] 0.029 [1.510.17 [5]
Ce 0.0858 [1] 0.04 [22] 0.0003 [7] 0.036 [23] 0.0006 [8] 0.00783 A 0.0217 A 0.26 [5]
Nd 0.1873 [1] 0.037 [22] 0.0002 [7] 0.029 [23] 0.0006 [8] 0.00847 A 0.0145 A 0.44 [5]
Sm 0.291 [1] 0.054 [22] 0.00018 [7] 0.022 [23] 0.0006 [8] 0.0091 [ 1 5 ] 0.0072 [15] 0.76 [5]
Eu 0.3288 A 0.063 [22] 0.0002 [7] 0.22 [23] 0.0006 [8] 0.0084 A 0.00635 A 0.88 [5]
Gd 0.367 A 0.097 [22] 0.00025 [7] 0.014 [23] 0.0006 [8] 0.0077 [ 1 5 ] 0.0055 [15] 0.86 [5]
Tb 0.404 A 0.094 [22] 0.000475 A 0.013 [23] 0.00105 A 0.00913 A 0.0063 A 0.83 [5]
Dy 0.442 [1] 0.1621 [22] 0.0007 [7] 0.013 [23] 0.0015 [8] 0.0106 A 0.0071 A 0.78 [5]
Ho 0.4145 A 0.1633 [22] 0.00122 A 0.013 [23] 0.0023 A 0.012 [15] 0.0079 [15] 0.73 A
Er 0.387 [I] 0.1816 [22] 0.00174 [7] 0.012 [23] 0.003 [8] 0.01625 A 0.0117 A 0.68 [5]
Tm 0.4085 A 0.259 [22] 0.00348 A 0.012 [23] 0.00375 A 0.0205 A 0.0155 A 0.64 A
Yb 0.43 [I] 0.2605 [22] 0.00522 [7] 0.012 [23] 0.0045 [8] 0.02475 A 0.01923 A 0.59 [5]
Lu 0.433 [I] 0.318 [22] 0.00852 [7] 0.012 [23] 0.0045 A 0.029 [15] 0.023 [15] 0.51 [5]
Ba 0.00068 [I] 0.0006 A 0.0005 A Eq.I [18] 0.0005 [3] 0.01 [13] 0.001 [16] 0.71 [5]
Sr 0.1283 [1] 0.062 [22] 0.016 [2] Eq. ll [18] 0.0005 [3] 0.7 [14] 0.4 [13] 0.64 [5]
Sc 3.9 [1] 1.4 [4] 0.25 [2] 0.02 [11] 0.048 [4] 1 A 1.3 [I3] 1.6 [5]
V 3.1 [1] 0.3 [2] 0.09 [2] 0.01 [13] 38 [4] 12 [4] 24 [13] 7 [21]
Cr 3.8 [1] 1.9 [8] 0.6 A 0.02 [13] 200 [8] 4 [I4] 20 16 0.34 [5]
Co 1.2 [2] 2 [4] 4 [4] 0.05 [11] 2 [4] 4 [14] 8 17 1.4 [5]
Ti 0.384 [1] 0.162 [9] 0.007 [9] 0.045 [4] 0.07 [9] 16 (~) I A 1 [20] ~
Ni 3 [2] 3.5 [8] Eq. IlI [8] 0.04 [4] 10 [8] 4 [14] 12 [4]1.6 [5]
Zr 0.1234 [1] 0.16 [22] 0.003 [9] 0.09 [11] 0.04 [9] 0.4 A 0.2 [13] 0.37 [11]
Hf 0.256 [I] 0.248 [22] 0.024 [4] 0.04 [11] 0.08 [6] 0.42 [13] 0.2 [13] 0.38 [5]
Nb 0.0077 [1] 0.004 A 0.01 [3] 0.001 [13] 0.01 [3] 2.3 [13] 0.7 [13] 0.1 [20]
Ta 0.07 [5] 0.07 [22] 0.02 [11] 0.03 [I1] 0.0001 [6] 2.7 [13] 0.8 [13] 0.1 [20]
Th 0.00026 [3] 0.0001 [3] 0.02 [I1] 0.05 [11] 0.001 [3] 0.1 A 0.19 [11] 0.038 [5]
U 0.00036 [3] 0.0001 [3] 0.03 [11] 0.05 [11] 0.001 [3] 0.1 A 0.26 [11] 0.08 [11]
Y 0.467 [1] 0.17 A 0.002 [2] 0.01 [4] 0.01 [3] 0.0045 [ 1 5 ] 0.0039 [15] 0.73 A,[20]
Rb 0.011 [3] 0.005 A 0.0005 A 0.08 [4] 0.0005 [3] 0.001 A 0.32 [11] 0.2 [5]
Cs 0.002 [4] 0.001 A 0.0001 A 0.1 [19] 0 A 0.0001 A 0.001 [16] 0.1 A
CPX -- clinopyroxene; OPX = orthopyroxene; PLAG = plagioclase; 1LM = ilmenite; MT = magnetite; AMP = amphibole. Most values are appro-
priate for liquidus-temperature basaltic liquids. Where nothing else was available, data from other magma types were used. Sources: [ 1 ] = Hart
and Dunn ( 1993 ); [2] =Frey et al. ( 1978 ); [3] =Hawkeswortb et al. ( 1993); [4] =Irving ( 1978); [5] =Irving and Frey ( 1984); [6] = Kostopoulos
and James ( 1992); [ 7] =Prinzhofer and All~gre ( 1985 ); [8] =Kelemen et al. ( 1990); [9] =Johnson and Dick ( 1992); [ 10] =Fujimaki et al.
(1984); [ l l ] = L e M a r c h a n d et al. (1987); [12]=Nakada and Kamata (1991); [ 1 3 ] = F u r m a n et al. (1991); [14]=Villemant et al. (1981):
[15] =Nielsen et al. (1992); [16] =Smith and Leeman (1987); [17]=Gill (1978); [18]=Blundy and Shimizu (1991); [19] =Romick et al.
( 1992 ); [20] = A d a m et al. ( 1992); [21 ] =calculated from data in B6dard et al. ( 1987 ); [22] =calculated from data in Lightfoot et al. ( 1c~93).
A = assumed, calculated, or interpolated to give smooth profiles. By fitting a straight line through a plot of available micro-probe data on TiO2 from
coexisting CPX and OPX in several hundred cumulate rocks of the Bay of Islands Complex, the following values were calculated: °px/liqDcr = cpx/
~'qDcr/2 and °px/liqDTi = cPx/liqDTi/2.4.NO Cr was detected in microprobe analyses of olivine. The value of °l/liqDcr was fixed so that it would yield
abundances just below the detection limit on the microprobe, and is therefore a maximum value. °~mqDB~and °~/~qDRb were fixed at values inferior
to those in OPX. °px/liqDNb w a s arbitrarily fixed at halfofCVx/liqDNb.The Plag/liqDRE E w e r e derived as follows. The ratio ofcpx/IiqDREE/plag/IiqDREEw a s
calculated from the analyses of mineral separates of Komor and Elthon ( 1990 ), assuming that CPX and PLAG crystallized together at equilibrium.
Ptag/~iqDrtEEwas calculated from these ratios and the cPx/tiqDrtEEdata of Hart and Dunn (1993). The resulting values were then corrected upward
slightly to force °lag/liqDLa into the range of data found in the literature. The calculated P~aS/~IqDHrtEE-valuesare lower than most data found in the
literature. The problems of inheritance of phenocrysts (Blundy and Shimizu, 1991 ), and the slow equilibration of REE in plagioclase, lead me to
favour the calculated values given here. The problem is particularly acute in the choice of P~as/~qDEu,since this value is a composite of two D-values
( Plag/liqDEu3+ and Plag/liqDEu2+ ), and depends on the temperature, the composition and the oxidation state of the melt (e.g., Philpotts, 1970; Drake
and Weill, 1975). Not surprisingly, the range of P~aS/~qDEu/PJaSmqDsmin published tabulations varies widely (1.6-290). °Px:~IqDREE._Zr._r~f.-T~.-Y.
r~b~d -C~were calculated the same way as V~S/I~qDREE,using the data in Lightfoot et al. ( 1993 ). The °tmqDN~was linked to the content of Fo in olivine
(eq.) as follows. °~/a'qDN~is a function of liquid composition, principally the MgO content (Budahn, 1986). His equation 5, based on the data of
Hart and Davies (1978), was used to link MgO in the liquid and °l/liqDNi. The FeO and MgO of the liquid line of descent for Bay of Islands rocks
was estimated from plots of analyses of the sheeted dykes and lavas (Siroky et al., 1985; Jenner et al., 1991 ) together with reasonable extensions to
higher MgO contents. Liquid and olivine FeO and MgO contents were linked by assuming an exchange reaction coefficient of 0.3 (Roeder and
Emslie, 1970). Eq. I, for Fo>0.65, °tDN~=-0.8480769X(100×FOo~)+87.37307692 (Foot is in molar fractions). Eq. I1:
PlaSDaa=exp[(lO.2-(38.2×lOO×An)]/(T×O.O08314) (Blundy and Shimizu, 1991; An is in molar fractions, T is in K). Eq. I11: Pl~gDs~
exp[ (26.8-- (26.7× 100×An) ] / ( T× 0.008314) (Blundy and Shimizu, 1991: An is in molar fractions, Tis in K ).
Stoichiometric.
b Interpreted.
 .1.11. Bbdard / Chemical Geology 118 (1994) 143-153
with this approach. First, considerable work is
involved in extracting sufficient amounts of ma-
terial, especially when the rocks are fine-grained.
Secondly, the mineral separate may not be rep-
resentative (Lutz, 1991), since it will tend to
over-sample the coarser grains and grain cores.
Thirdly, since partition coefficients commonly
vary with temperature (e.g., Ni in olivine; Hart
and Davies, 1978), post-cumulus re-equilibra-
tion may lead to significant redistribution of
some elements. In addition, the minerals may
contain inclusions, and the effects of a trapped
melt fraction (TMF) are generally ignored. Fi-
nally, this method is useless when minerals are
strongly altered or metamorphosed.
Alternatively, the trace-element contents of
minerals may be analysed in situ by using an
electron, ion or proton probe. This circumvents
some of the difficulties outlined above, but the
problems of severe alteration or metamorphism,
and post-cumulus re-equilibration remain. The
problem of the TMF can perhaps be avoided by
analysing relict cores, but post-cumulus anneal-
ing may destroy such relics. In addition, the elec-
tron probe is not suitable for analysis of trace
elements at very low concentration levels, while
the ion and proton probes are expensive to op-
erate and their calibration is difficult.
A simple method of calculating the composi-
tion of the melts in equilibrium with a cumulate
rock is presented in the next section. An accurate
whole-rock analysis, modal abundances and a
consistent set of mineral/melt partition coeffi-
cient data are all that is required. A mineral/melt
partition coefficient, D, is simply the concentra-
tion of an element in a mineral, divided by the
concentration of that element in the coexisting
liquid at equilibrium [the conventions advo-
cated by Beattie et al. (1993) were used in this
paper ]. A large body of such data now exists for
many different minerals and melts, and is stead-
ily improving in quantity and quality. A compi-
lation of such data thought to be appropriate for
basaltic compositions at liquidus temperatures is
presented as Table 1.
Modal data is commonly obtained either
through point counting (followed by a correc-
tion to transform volumetric fractions into
145
weight fractions), or by a least-squares method
(Bryan et al., 1969 ) using the whole-rock major-
element composition and microprobe data on
minerals. For metamorphosed rocks, the inter-
pretation ofpseudomorphic textures, norms and
a trial-and-error approach with the least-squares
mixing program should yield sufficiently accu-
rate estimates of the mode. A comparison of the
point-counting and least-squares methods for
adcumulate rocks from Rhum, Scotland, U.K.
(Tait, 1985 ) showed good agreement. However,
each approach has its pitfalls. For example, point-
counting may provide erroneous modes if there
is preferential alteration of one phase, if the rock
is very heterogeneous or coarse-grained (making
the thin section unrepresentative), or if misi-
dentification of phases occurs. Where possible,
modes derived from point-counting should be
verified using a least-squares approach, to test for
self-consistency. Conversely, metasomatic alter-
ation during metamorphism, or systematic ana-
lytical bias may invalidate the results of the least-
squares approach. Least-squares results should
always be checked against the petrography, as has
been done for the results presented in later sec-
tions. In any case, the calculated liquid compo-
sition is relatively insensitive to small variations
in the proportions of the constituent minerals
(see Appendix).
2. Assumptions and concepts
If the whole-rock concentration of trace ele-
ments and the modal proportions of mineral
phases are known, then it is possible to calculate
the equilibrium distribution of trace elements
among the different minerals from mass balance.
Once we know the concentrations of trace ele-
ments in one of the minerals, we can use min-
eral/melt partition coefficient data to calculate
the concentration of trace elements in the coex-
isting liquid. The discussion will center around
cumulate rocks, but the method is applicable to
any solid-liquid system for which partition coef-
ficient data exist. Below, I discuss some of the
assumptions that underpin the approach, pres-
ent the equations that allow the calculations to
146 J.H. B~dard / Chemical Geology 118 (1994) 143-153
Table 2
Phase proportions used in back-stripping the T M F to correct the solid assemblages
CPX OPX PLAG
0.429 0,429
0.667
0.667 0,667
0.333 0,333 0.333
0.429 0.286 0,429
2 -1
0.667
-0.5
-1
-0.5
0.214 0.214 0.071
C P X =- clinopyroxene; O P X = orthopyroxene; PLAG = plagioclase; MT = magnetite; ILM = ilmenite; A M P = amphibole.
be made, and provide comparisons with in situ
analytical and mineral separate data.
The fundamental assumption made is that all
of the minerals in a given rock crystallized from
the same melt at the same temperature; and that
equilibrium prevails. Undetected trace phases
(apatite, zircon, ilmenite) with high D-values, or
post-cumulate metasomatism invalidate the cal-
culations. The consequences of modal variations
of high-D trace phases were investigated by Ay-
ers (1993), who developed a similar set of dis-
tribution equations.
A question of particular importance is the de-
gree to which the cumulates contain a TMF (e.g.,
Barnes, 1986 ). If the TMF is neglected, then the
calculation overestimates the abundances of in-
compatible trace elements in the minerals and
coexisting equilibrium liquids. In nature, the
TMF crystallizes in the spaces between accumu-
lated crystals, either as adcumulate overgrowths
(difficult to recognize optically), or as discrete
interstitial or reaction phases. A cumulate mush
may contain substantial volumes of interstitial
liquid immediately after accumulation. As the
mush cools, compacts and crystallizes, this inter-
stitial liquid is progressively expelled. During
expulsion, there may be continuous or episodic
re-equilibration between the escaping interstitial
melt and the cumulate minerals. The geochemi-
cal consequences of this process are difficult to
model analytically unless some assumptions are
Olivine Spinel MT ILM AMP
0.143
0,333
-0.333
- 0.143
0.312 0.021
0,5 1
2
0.236 0.264 1
0.236 0.264
O.98 0.O2
made. Adcumulus overgrowths and heteradcu-
mulus oikocrysts are considered as "cumulus" in
the geochemical sense, and so are not included
in the TMF. This because it is generally thought
that they form while there is efficient exchange
(advective or diffusive ) between the main body
of melt (infinite reservoir) and the interstitial-
intracumulate melt at near-liquidus tempera-
tures (Wager and Brown, 1968). To allow the
same D-values to be used throughout and to sim-
plify the equations, I assume that the TMF was
sealed off from the main body of magma at near-
liquidus temperatures.
In this paper the effects of a TMF are simu-
lated by including in the calculations a phase (the
liquid) with D = 1, and calculating a series of liq-
uid profiles for different TMF. The choice of
what TMF to use is arbitrary, but as we shall see
below, comparison with natural magmas and the
internal logic of the method supply some con-
straints. It is necessary to correct the mode to be
used in the calculation by removing the solid
products of the TMF from it. This is concep-
tually analogous to partial melting, and the same
methodology can be applied. If trace phases are
not involved, using a modal melting model to
strip off the TMF precipitates produces results
almost indistinguishable from a non-modal
melting model. Non-modal melting is probably
more realistic, since trace phases (1-3%) will
generally disappear rapidly from the residue. This
 J.H. Bkdard / Chemical Geology 118 (1994) 143-153
makes the eventual calculation of liquid compo-
sitions more robust. Where possible, experimen-
tally determined cotectic proportions of min-
erals should be used in the non-modal melting
calculation. Some data and some reasonable ap-
proximations of trapped melt extraction modes
are given in Table 2. A reaction relationship is
assumed to exist between OPX and OL and
AMPH and CPX.
A correction to the mode and modal assem-
blage may be required to compensate for subso-
lidus exsolution. For basaltic systems, the most
significant exsolution occurs among the pyrox-
enes. Common sense allows a simple correction
to be made for each rock being modelled. For ex-
ample, a rock that contains a small proportion of
low-Ca orthopyroxene (e.g., <5%) as small
blebs, and a large amount of coarse-grained high-
Ca clinopyroxene ( > 70%), was probably a cli-
nopyroxene cumulate affected by subsolidus
exsolution of orthopyroxene. In practice, the or-
thopyroxene is added to the clinopyroxene mode,
and orthopyroxene disappears from the assem-
blage. Where both pyroxenes are abundant and
in subequal proportions, it is probably safer to
assume that both are cumulate phases.
3. Equations
By mass balance, the concentration of an ele-
ment i in a multi-phase assemblage can be ex-
pressed as the sum of the products of the modal
proportions ~ (as mass fractions of 1 ) times the
concentrations C, of element i, in a mineral or
phase j, of which there are n in the assemblage
(Eq. 1 ). A gabbro-norite is used as an example
(Eq. 2 ), but the series can be expanded or short-
ened to accomodate any number of phases. The
phase labelled tm is trapped melt, which has a D
of 1.
n
X~d~ C J,., - -- C ,r°ck
~ ,
j=l
CT°ck = (O cpxc~px) + (0 opxCOpX)
+ (0plagc plag) + ( 0 t m c l iq)
147
If we know the bulk-rock concentrations, C rock ,
and the modal abundances, ~ , we can solve the
equation and obtain the concentration of an ele-
ment in a given mineral since:
CCpX = C°px (cpx/liqDi/°px/liqDi) (3)
= cplag(cpx/liqDi/plag/liqD/)
By substituting equations of this type (Eq. 3 )
into Eq. 2 we can eliminate all but one of the un-
knowns (C minera'). For example, expressing the
concentrations of element i in OPX and PLAG
in terms of CPX, we obtain the concentration of
i in CPX:
CCpx = c r o c k / ( 0 c p x ~ ~j°px°px/liqDicpx/liqDi
(~plagPlag/liqDi + -~tm
- x (4)
cpx/liqoi cpx/liqDiJ
We solve for the other minerals in similar fash-
ion, for example:
COpx=crock/(oopx q Ocpxcpx/liqDiopx/liqDi
"q"~ plagplag/liqo i -~ _O_'m (5)
opx/liqDi opx/liqDi J
These equations can easily be solved using any
of the commercial spreadsheets available. The
advantage of this formulation is that the same
equations can be used unchanged throughout the
TMF stripping process, simply by setting omrf= 0
when a given mineral disappears from the resid-
ual assemblage.
4. Comparison with in situ analyses, mineral
separates and natural magmas
Whenever possible, data from mineral sepa-
rates and in situ analysis should be used in con-
junction with the equilibrium distribution
(1)
method to help calibrate the D-values to the P -
T - X conditions appropriate to those being mo-
(2) delled. Some of the D values presented in Table
1, were derived empirically (see caption of Ta-
ble 1 for details) from the large data set now
148 J.H. Bbdard I Chemical Geology 118 (1994) 143-153

available from rocks of the Bay of Islands com-
plex, Newfoundland, Canada, and may not be
appropriate for other suites (e.g., alkaline
basalts).
The Ti contents of clinopyroxenes calculated
with the equilibrium distribution method is
compared to electron microprobe analyses in Fig.
1 (the D-values used and the methods by which
they were derived are given in Table 1 ). The cal-
culations used whole-rock X-ray fluorescence
(XRF) analyses and modes obtained by a least-
squares fit of probe analyses of the minerals to
major-element whole-rock XRF analyses (with
concurrent petrographic verification), assuming
0% and 5% TMF. The rocks and minerals used
are from published and unpublished analyses
from the peridotites, pyroxenites and gabbros
from the North Arm Mountain massif of the Bay
of Islands ophiolite (B6dard, 1991 and refer-
ences therein). The fit is fairly good. Using the
5% TMF values gives better fits for the more
primitive rocks, while 0% TMF gives better fits
for the more evolved (Fe-rich) rocks. This may
reflect a change in the absolute value of Px/~iqDT~
as the liquid compositions evolve.
Rare-earth element (REE) profiles in the con-
stituent minerals of granular, "cumulate" gab-
bro-norites from the North Arm Mountain mas-
sif were calculated using the equilibrium
distribution method. The calculations used un-
published whole-rock and mineral analyses. Us-
ing the D data of Table 1, the calculated concen-
trations in clinopyroxene and plagioclase from
two gabbro-norites are compared (Fig. 2 ) to val-
ues measured (Komor and Elthon, 1990) in
mineral separates of gabbroic rocks from the
same ophiolitic massif. The calculated profiles
show reasonably good matches with the mea-
sured profiles. This supports the hypothesis that
the two gabbro-norites used in these calculations
are cogenetic with the suite studied by Komor
and Elthon (1990).
Shown in Fig. 3 are a series of liquid profiles
calculated to be in equilibrium with lower-crus-
tal ultramafic cumulate wehrlite 8911 and dun-
ite 8863 from the North Arm Mountain massif.
Profiles for different TMF are shown, the cu-
mulate mode having been corrected using the
TMF extraction modes shown in the insets. The
profiles are normalized to mid-ocean ridge ba-
salt (MORB) (data mostly from Sun and Mc-
Donough, 1989) and compared with naturally
occurring boninitic magmas (data from Coish,
1989; Falloon et al., 1989; Murton, 1989; Har-
nois et al., 1990; Swinden et al., 1990; Falloon
and Crawford, 1991; Stern et al., 1991 ). Several

12000 m /////.
• 0% TMF ,-" [] ~] • O%~F
1OOOO- [-'7 5 0 TMF ./
) /'z3
Dcpx/liq = 0.384
~z~ 1 oop~iq_-0.~ //" •

•/ " o
.~ 6000- ///

~J • / " / / " miraa

4ooo-
G~c~

ix 2000-

0
o 260o 4ooo ~ 8ooo 1o6o0 l=ooo 14000 0 500 1000 1500 2000 ~ 3000 3500
(a) Ti (ppm) in CPX from Kd and modal data (b) Ti (ppm) in CPX from Kd and modal data

Fig. 1. Ti ( p p m ) in CPX calculated by the equilibrium distribution method (0% and 5% T M F ) , vs. probe analyses for Ti in
CPX for the same rocks. The diagonal line is a 1: 1 correspondence. Ti in the minerals was analysed on a wavelength-dispersive
Cam6ca ® Cam6bax, with an accelerating voltage of 10 kV and a beam intensity of 29 nA. Rutile was used as a standard. Long
counting times (25 s) were used because of the low abundances. Whole-rock TiO2 was analysed by conventional X RF techniques
on fused glass pellets at the Canadian Geological Survey laboratories in Ottawa.
 J.H. B#dard / Chemical Geology 118 (1994) 143-I53 149

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La Ce Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu La Ce Nd Sm Eu Gd To Dy Ho Er Tm Yb Lu
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10
LOG LOG

, *!! =~ KE90

..i.......~.~... . . . . . . . . . . . . . . . . . . . . . . . . .

2 -'k. ~"
GN 8862

%i"M

~,-,,'-~. ..................... j
"'." . . . . . . . . . : . . . . . . KEg0 ,. °/oJM "~
............... _-_"_-_-_-_-_-_._.___. ; #,

0.1 J 0.1 [~ . . . . . . .~. . . . . . . . . . ~ ~ "'

(C) ~ Ce Nd Sm Eu C.,-d Tb Dy Ho Er Tm Yb L (d) ~ Ce Nd Sm Eu Gd To Dy Ho Er Tm "Co Lu

Fig. 2. Comparison of calculated and measured rare-earth element profiles. The curves+symbols represent calculated REE pro-
files in clinopyroxenes (A and B) and feldspars (C and D), from two gabbro-norites of the North Arm Mountain massif of the
Bay of Islands ophiolite. These profiles were calculated for different TMF. Whole-rock REE analyses of 8819 and 8862 were
done by ICP-MS (20 ppb detection limit) at the Canadian Geological Survey laboratories in Ottawa by N. Bertrand. The modes
were calculated from the whole-rock major-element analyses (XRF) and probe analyses of the minerals, using a least-squares
method (Bryan et al., 1969) with a program written by O. Stecher. The thin dotted lines labelled KE90 are profiles of mineral
separates from the "uniform" gabbros of Komor and Elthon (1990). These mineral separates were analysed by instrumental
neutron activation analysis (INAA).

interesting insights can be gained from such pro- ments, and so cannot have formed from a
files. For example, the calculated liquids have MORB-like magma. If 0% TMF is assumed, both
very low abundances of most incompatible ele- calculated profiles have excessively high large ion
150 J.H. BOdard I Chemical Geology 118 (I 994) 143--153
1000
i 0-1.98"1o CPX,'PIJOL = 0.43/0.43/0.14 (b) ..t~ 0-6.3"1,, CPX/OPX/OlJSP = .66L66/-.33/0
LOG 2°I~3'~ ca 1.98-7°1. CPX,'OL = 0.666/0.333 ca. 6.3*1o-8.4% CPX/OL./SP = .671.33/0
>8.4% OL/SP .98/.02
Ldt NoTM TMF EXTRACTION MODES
O 7
t~. \ L. -Ca I DUNITE 8863 III
2"/0D . . : ~ k ~ ,.. i I
3 D. ~..' "El
O' I!I::::D-" ~'t 8 5 t~ "~i~'.'~'.. '~"t~ CALCULATED LIQUIDS

<

8911 ROCK
', °0.,,2
0.01 i , , , , , , , , , , , , , , , , , , ,--
Rb Th Ce Nd Eu Gd Dy Ho Tm Lu Rb Th Ce Nd Eu Gd Dy Ho Tm Lu
(a) Cs Ba La Sr Sm "l'i Tb Y Er Yb (b) Cs Ba La Sr Sm Ti Tb Y Er Yb

Fig. 3. MORB-normalized spidergram normalized to MORB, for liquids calculated to be in equilibrium with wehrlite 8911 (a)
and dunite 8863 (b) (Bay of Islands complex) at different TMF. Trapped melt extraction modes shown in inset.

lithophile element (LILE) contents for equilib- loo

rium with either MORB or boninitic magmas. LOG TRAPPED MELT EXTRACTION MOD E
C PX/OPX/PL = 0.3/0.3/0.3
However, for moderate TMF ( ~ 5%), the cal-
culated profiles closely resemble modern bonin- ©
0%tin ~ ( GABBRO-NORITE 8819 i

ites, suggesting that both of these rocks are cu- 3 "{~ "
mulates from boninitic magmas. This -~
= ~-" "-..~,,'\b~ CALCULATED LIQUIDS
comparison allows the "efficiency" of melt ex-
traction from the cumulates to be estimated. ~ ~ : ~ l ~ ' ' . .: . ~ --:( :::![~
9 " : /" !~=
' t ;~;:' ~. ::; : ;;;.
~ ;;; ::: ...
TMF around 5% gave good fits for six different ~1
peridotite cumulates, and so this value of the u
TMF was then used for all the rocks in this suite.
A different example is shown in Fig. 4; here,
an evolved gabbro-norite (8819) is examined, o~
The calculated liquids have smooth MORB-nor- Rb Th Ce Nd Eu Gd Dy Ho Tm Lu
Cs Ba La Sr Sm Ti Tb Y Er Yb
malized profiles with calculated abundances that
are slightly higher than N-MORB. This is consis-
tent with this rock's Fe-rich, relatively fraction- Fig. 4. MORB-normalized spidergram for liquid profiles cal-
ated mineralogy. The high MORB-normalized culated to be in equilibrium with gabbro-norite 8819. Notes
LILE abundances may suggest an arc affinity. as per Fig. 3.

ferent approaches should be used in conjunc-

5. Discussion and conclusions tion. The advantages of the equilibrium distri-
bution method lie in its low cost and ease of
Comparisons between the different ap- application, and in its ability to compensate for
proaches discussed above suggest that, in the ab- a trapped melt fraction, which the in situ analyt-
sence of other data, the equilibrium distribution ical approaches cannot do. In some senses the
method is probably an acceptable means of de- equilibrium distribution method may be supe-
termining the trace-element concentrations of rior to the other approaches, since liquidus-tem-
phases in cumulate rocks and of the liquids in perature distributions can be determined (re-
equilibrium with them. Where possible the dif- moving the effects of post-cumulus re-
 J.H. Bkdard / Chemical Geology 118 (1994) 143-153 151

equilibration), and there is no danger of under- Acknowledgements

sampling grain boundaries or of contaminating
separates by fine-grained inclusions. The results Marc Lafl~che, Tony Peterson, Julian Pearce
do depend strongly on the choice of D-values, but and two anonymous referees supplied useful
then, so do all of the other approaches. In the case comments.
of severely altered or metamorphosed rocks,
where in situ analysis or separation of primary
minerals is impossible, then the equilibrium dis- Appendix - - Error propagation
tribution method is the only way to calculate the
trace-element concentrations in the coexisting The principal potential sources of error are (in decreasing
equilibrium liquid, and so verify consanguinity order of importance): analytical error, uncertainty in the D-
among cumulate rocks. values, imprecision of modal data and use of the wrong TMF
stripping modes.
IOO0
WEHRLITE 8911 Analytical error is significant for extremely depleted rocks
LOG such as the ultramafic cumulates illustrated in Fig. 3. A suite
REPRODUCIBILITY ENVELOPE
of 50 samples were analysed twice (in 1993 and 1994). The
LATED LIQUIDS, 5% TMF results were plotted against one another and an envelope of
variation was drawn. The diameter of this envelope was used
as an empirical estimate of the reproducibility of the data.
Since the data were analysed at different times, the values
~~ ,,. /"7 BONINiTES derived in this way should also provide an estimate of the
analytical uncertainty. The error margins defined in this way
are larger than the 95% confidence limits commonly used as
estimates of uncertainty. The error bars on the whole-rock
analyses plotted in Fig. A-I represent simple addition and
subtraction to the average whole-rock analyses. The maxi-
mum and minimum values were then used in the calculations
0.01 to yield the error bars on the calculated liquid compositions.
Rb Th Ce Nd Eu Gd Dy Ho Tm [_u Although the errors are quite large for the ultramafic cumu-
(a) Cs Ba La Sr Sm "17 Tb Y Er Yb
late (Fig. A-I a), the spectrum of plausible melts is still within
the boninitic feld. Analytical uncertainty is the principal
source of error in this case. For the relatively less-depleted

1000
1000"
GABBRO-NORITE 8862 WEHRLITE 8911
LOG CALCULATED LIQUIDS, 5% TMF D FROM TABLE 1
LOG
REPRODUCIBILITY ENVELOPE
DCPX= 10x & 2x TABLE 1 ......E3....
l CALCULATED LIQUIDS, 5% TMF . DCPX = 0.1X & 0.5X TABLE 1 - | .....
©

¢~"-o-.. E]...,E]....E3.,~....D....O....G-..~E]-,"G--.75y..,~3

0.O1 0.0 . . . . . . . . . . . . , , , , , , , ,

Rb Th Ce Nd Eu Gd Dy Ho Tm Lu Rb Th Ce Nd Eu C-id Dy Ho Tm Lu
(b) Cs Ba La Sr Srn qq Tb Y Er Yb Cs Ba La Sr Sm 77 Tb Y Er Yb

Fig. A- 1. Estimates of the consequences of analytical error Fig. A-2. MORB-normalized spidergram. The solid line is the
shown on MORB-normalized spidergrams. Error bars are 5% TMF profile of Fig. 3 for wehrlite 8911. The dotted lines
shown on whole-rock and calculated liquid profiles. See text represent profiles calculated assuming that the ¢px/uqDi var-
for discussion. ied from those of Table 1.
152
1000
WEHRLITE 8911
1.0(3
CALCULATED LIQUIDS
~ ~5%TMF
i
O 0.8 CPX 0.20L
c~
:~
e ................................. ~:':"::"" ~i .............................................................................................
5 for plagioclase recycling in calc-alkaline magmas. Earth
-- ~ t
0.0 ~ , , , , , , , ,
Rb Th Ce Nd
Cs Ba La Sr
Fig. A-3. MORB-normalized spidergram. The solid line is the
5% TMF profile of Fig. 3 for wehrlite 8911. The mineral
modes were changed by ~ 20%, yet the profiles do not vary
greatly.
gabbro-norite (Fig. A-1b) the errors are much smaller.
The consequences of errors in mr~/~iqDi are evaluated in Fig.
A-2, using wehrlite 8911 as an example. Since this is a CPX-
rich rock where CPX is the principal repository for incom-
patible trace elements, the cPx/~iqDiwas varied systematically.
Variations in the calculated liquid induced by variations in
D-values are greater than the analytical uncertainty if the cp~/
liqO i is over- or underestimated by factors greater than 2.
Fig. A-3 explores the consequences of uncertainty in the
modal data. In Fig. A-3, the thick line is the 5% TMF profile
of Fig. 3 (wehrlite 8911 ). The two dotted lines represent the
composition of liquids calculated for substantially different
modal assemblages. The variations are generally smaller than
those caused by uncertainty in the D-values and by analytical
uncertainty. Uncertainty caused by the different possible TMF
stripping processes is almost negligible unless trace phases are
left in the residue,
References
Adam, J., Green, T.H. and Sie, S.H., 1993. Proton micro-
probe determined partitioning of Rb, Sr, Ba, Y, Zr, Nb
and Ta between experimentally produced amphiboles and
silicate melts with variable F content. Chem. Geol., 109:
29-49.
Ayers, J.C., 1993. Partitioning and mass-balance relations in
lherzolites. Chem. Geol., 107: 19-27.
Barnes, S.J., 1986. The effect of trapped liquid crystallization
on cumulus mineral compositions in layered intrusions.
Contrib. Mineral. Petrol., 93:524-531.
Beattie, P., Drake, M., Jones, J., Leeman, W., Longhi, J.,
McKay, G., Nielsen, R., Palme, H., Shaw, D., Takahashi,
J.H. B~dard / Chemical Geology 118 (1994) 143-153
E. and Watson, B., 1993. Terminology for trace-element
0.63 CPX 0.37 OL
partitioning. Geochim. Cosmochim. Acta, 57:1605-1606.
( C A L C U L A T EMODE)
D
B6dard, J.H., 1991. Cumulate recycling and crustal evolution
in the Bay of Islands ophiolite. J. Geol., 99: 225-249.
......E3.... B6dard, J.H., Ludden, J.N. and Francis, D.M., 1987. The
0.4 CPX 0.60L .....| .... M6gantic intrusive complex, Qu6bec: a study of the deri-
vation of silica-oversaturated anorogenic magmas of al-
kaline affinity. J. Petrol., 28: 355-388.
Blundy, J.D. and Shimizu, N., 1991. Trace element evidence
...- - I----.-i--...t
- . ............
. I--',--I
. .-''l''-.,
i ...--'|
Planet. Sci. Lett., 102: 178-197.
Bryan, W.B., Finger, L.W. and Chayes, F., 1969. A least
squares approximation for estimating the composition of
a mixture. Carnegie Inst. Washington Yearbk., 67: 243-
, , , , . . . . , r , ,
244.
Eu Gd Dy Ho Tm Lu Budahn, J.R., 1986. Evidence for equilibrium conditions
Sm Ti Tb Y Er Yb
during the partitioning of nickel between olivine and ko-
matiite liquids. Am. Mineral., 71: 1337-1342.
Coish, R.A., 1989. Boninitic lavas in Appalachian ophiolites:
a review. In: A.J. Crawford (Editor), Boninites. Unwyn
Hyman, London, pp. 264-287.
Drake, M.J. and Weill, D.F., 1975. Partition ofSr, Ba, Ca, Y,
Eu2+, Eu3+, and other REE between plagioclase feldspar
and magmatic liquid: an experimental study. Geochim.
Cosmochim. Acta, 39:689-712.
Falloon, T.J. and Crawford, A.J., 1991. The petrogenesis of
high-calcium boninite lavas dredged from the northern
Tonga ridge. Earth Planet. Sci. Lett., 102: 375-394.
Falloon, T.J., Green, D.H. and McCulloch, M.T., 1989. Pe-
trogenesis of high-Mg and associated lavas from the north
Tonga trench. In: A.J. Crawford (Editor), Boninites. Un-
wyn Hyman, London, pp. 357-395.
Frey, F.A., Green, D.H. and Roy, S.D., 1978. Integrated
model of basalt petrogenesis: a study of olivine melilitites
to quartz tholeiites from southeastern Australia utilizing
geochemical and experimental petrological data. J. Pe-
trol., 19: 463-513.
Fujimaki, H., Tatsumoto, M. and Aoki, K., 1984. Partition
coefficients of Hf, Zr and REE between phenocrysts and
groundmass. Proc. 14th Lunar Planet. Sci. Conf., Part 2,
J. Geophys. Res., 89 (Suppl.): B662-B672.
Furman, T.H., Frey, F.H., Jakobsson, S.P. and Park, K.-H.,
1991. Petrogenesis of mildly alkaline lavas from Vest-
mannaeyjar, Iceland: the Eldfell (1973) and Surtsey
(1963-1967) eruptions. Contrib. Mineral. Petrol., 109:
19-37.
Gill, J.B., 1978. Role of trace element partition coefficients
in models ofandesite genesis. Geochim. Cosmochim. Acta,
42: 709-724.
Harnois, L., Trottier, J. and Morency, M., 1990. Rare earth
element geochemistry of Thetford-Mines ophiolite com-
plex, northern Appalachians, Canada. Contrib. Mineral.
Petrol., 105: 433-445.
Hart, S.R. and Davies, K.E., 1978. Nickel partitioning be-
tween olivine and silicate melt. Earth Planet. Sci. Lett.,
40: 203-219.
Hart, S.R. and Dunn, T., 1993. Experimental cpx/melt par-
 J.H. Bkdard / Chemical Geology 118 (1994) 143-153
titioning of 24 trace elements. Contrib. Mineral. Petrol.,
113: 1-8.
Hawkesworth, C.J., Gallagher, K., Hergt, J.M. and Mcder-
mott, F., 1993. Trace element fractionation processes in
the generation of island arc basalts. Philos. Trans. R. Soc.
London, Set. A, 342: 179-191.
Irvine, T.N., 1982. Terminology for layered intrusions. J. Pe-
trol., 23: 127-162.
Irving, A.J., 1978. A review of experimental studies of crys-
tal/liquid trace element partitioning. Geochim. Cosmo-
chim. Acta, 42: 743-770.
Irving, A.J. and Frey, F.A., 1984. Trace element abundances
in megacrysts and their host basalts: constraints on parti-
tion coefficients and megacryst genesis. Geochim. Cos-
mochim. Acta., 48: 1201-1221.
Jenner, G.A., Dunning, G.R., Malpas, J., Brown, M. and
Brace, T., 1991. Bay of Islands and Little Port complexes,
revisited: age, geochemical and isotopic evidence confirm
suprasubduction-zone origin. Can. J, Earth Sci., 28: 1635-
1652.
Johnson, K.T.M. and Dick, H.J.B., 1992. Open system melt-
ing and temporal and spatial variation of peridotite and
basalt at the Atlantis-II fracture zone. J. Geophys. Res.,
97:9219-9241.
Kelemen, P.B., Johnson, K.T.M., Kinzler, R.J. and Irving,
A.J., 1990. High-field-strength element depletions in arc
basalts due to mantle-magma interaction. Nature (Lon-
don), 345: 521-524.
Komor, S.C. and Elthon, D., 1990. Formation of anorthos-
ite-gabbro rhythmic phase layering: an example at North
Arm Mountain, Bay of Islands ophiolite. J. Petrol., 31: 1-
50.
Kostopoulos, D.K. and James, S.D., 1992. Parameterization
of the melting regime of the shallow upper mantle and the
effects of variable lithospheric stretching on mantle modal
stratification and trace-element concentrations in mag-
mas. J. Petrol., 33: 665-691.
LeMarchand, F., Villemant, B. and Calas, G., 1987. Trace
element distribution coefficients in alkaline series. Geo-
chim. Cosmochim. Acta, 51: 1071-1081.
Lightfoot, P.C., DeSouza, H. and Doherty, W., 1993. Differ-
entiation and source of the Nipissing Diabase intrusions,
Ontario, Canada. Can. J. Earth Sci., 30:1123-1140.
Lutz, T.M., 1991. Trace element and isotopic zoning in min-
erals: models of compositional fractionation by mineral
separation procedures. Lithos, 27:1-1 l.
Murton, B.J., 1989. Tectonic controls on boninite genesis. In:
A.D. Saunders and M.J. Norry (Editors), Magmatism in
the Ocean Basins. Geol. Soc. London, Spec. Publ., 42: 347--
377.
Nakada, S. and Kamata, H., 1991. Temporal change in
chemistry of magma source under central Kyushu, south-
west Japan: progressive contamination of mantle wedge.
Bull. Volcanol., 53: 182-194.
Nielsen, R.L., Gallahan, W.E. and Newberger, F., 1992. Ex-
perimentally determined mineral-melt partition coeffi-
153
cients for Sc, Y and REE for olivine, orthopyroxene, pi-
geonite, magnetite and ilmenite. Contrib. Mineral. Petrol.,
110: 488-499.
Pearce, J.A. and Cann, J.R., 1973. Tectonic setting of basic
volcanic rocks determined using trace element analyses.
Earth Planet. Sci. Lett., 19: 290-300.
Philpotts, J.A., 1970. Redox estimation from a calculation of
EU 2+ and EU 3+ concentrations in natural phases. Earth
Planet. Sci. Lett., 9: 257-268.
Prinzhofer, A. and Allbgre, C.J., 1985. Residual peridotites
and the mechanisms of partial melting. Earth Planet. Sci.
Lett., 74:251-265.
Roeder, P i . and Ernslie, R.F., 1970. Olivine-liquidequilib-
rium. Contrib. Mineral. Petrol., 29: 275-289.
Romick, J.D., Kay, S.M. and Kay, R.W., 1992. The influence
of amphibole fractionation on the evolution of calc-alka-
line andesite and dacite tephra from the central Aleu-
tians, Alaska. Contrib. Mineral. Petrol., 112:101-118.
Siroky, F.X., Elthon, D.L., Casey, J.F. and Butler, J.C., 1985.
Major element variations in basalts and diabases from the
North Arm Mountain Massif, Bay of Islands Ophiolite:
implications for magma chamber processes at mid-ocean
ridges. In: G.F. Sharman and J. Francheteau (Editors),
Oceanic Lithosphere. Tectonophysics, 116: 41-61.
Smith, D.R. and Leeman, W.P., 1987. Petrogenesis of Mount
St. Helens dacitic magmas. J. Geophys. Res., 92: 10313-
10334.
Stern, R.J., Morris, J., Bloomer, S.H. and Hawkins, J.W.,
1991. The source of the subduction component in conver-
gent margin magmas: trace element and radiogenic iso-
tope evidence from Eocene boninites, Mariana forearc.
Geochim. Cosmochim. Acta, 55: 1467-1481.
Sun, S.-S. and McDonough, W.F., 1989. Chemical and iso-
topic systematics of oceanic basalts: implications for
mantle compositions and processes. In: A.D. Saunders and
M.J. Norry (Editors), Magmatism in the Ocean Basins.
Geol. Soc. London, Spec. Publ., 42: 313-345.
Swinden, H.S., Jenner, G.A., Fryer, B.J., Hertogen, J. and
Roddick, J.C., I990. Petrogenesis and paleotectonic his-
tory of the Wild Bight Group, an Ordovician rifted island
arc in central Newfoundland. Contrib. Mineral. Petrol.,
105: 219-241.
Tait, S.R., 1985. Fluid dynamic and geochemical evolution
of cyclic unit I0, Rhum, Eastern Layered Series. Geol.
Mag., 122: 469-484.
Villemant, B., Jaffrezid, H., Joron, J.-k. and Treuil, M., 1981.
Distribution coefficients of major and trace elements:
fractional crystallization in the alkali basalt series of
Chaine des Puys (Massif Central, France). Geochim.
Cosmochim. Acta, 45: 1997-2016.
Wager, L.R. and Brown, G.M., 1968. Layered Igneous Rocks.
Oliver & Boyd, Edinburgh, 588 pp.
Wang, P. and Glover IlI, L.I., 1992. A tectonics test of the
most commonly used geochemical discriminant diagrams
and patterns: Earth-Sci. Rev., 33:111-131.