Download NORSK GEOLOGISK TIDSSKRIFT 45 DISTRIBUTION PATTERNS

NORSK GEOLOGISK TIDSSKRIFT 45
DISTRIBUTION PATTERNS OF RARE EARTH
ELEMENTS IN TERRESTRIAL ROCKS
BY
BRENDA B. jENSEN and ARILD 0. BRUNFELT
(Mineralogical-Geological Museum, University of Oslo, Sarsgt. l, Oslo 5)
Abstract. This paper gives a brief account of the present state of knowledge
concerning rare earth element fractionation in terrestrial rocks, reviews present
methods of plotting and comparing results, and examines the comparability of
data obtained by neutron-activation analysis and X-ray spectrographic tech­
niques. A large number of analyses have been replotted by a new method, and
several conclusions conceming differentiation in terrestrial rocks are drawn
from the results.
Introduction
Recent advances in techniques of rare earth element (REE)1 analysis
have made possible much more accurate determination of REE in the
relative!y low concentrations in which they occur in terrestrial rocks;
as a result many new data on REE abundances in meteoritic and
terrestrial matter are now available. These have contributed greatly
to our knowledge of the distribution of REE in the earth's crust and
have confirmed many of the early hypotheses of GoLDSCHMIDT (1954).
It can now be taken as established that:
l. At an early stage in the earth's history, the relative abundance
of the individual REE was closely akin to that of chondritic meteorites.
2. During the natura! chemical processes which have produced the
present complexity of crustal rock types from this material, the REE
have tended to act geochemically as a unit and be totally increased
or depleted in any given rock. Certain processes can, however, cause
major variations in the relative abundances of the individual REE.
1
Elements nos. 57-71 (La to Lu, inclusive).
250
BRENDA B. JENSEN AND ARILD O. BRUNFELT
3. Any failure of the REE to act coherently may be attributed to:
a) differences in ionic radius (the radius decreases from La to Lu),
b) differences in basicity (the basicity decreases from La to Lu),
or c) ability of a number of REE to exist in an oxidation state other
than +3 (i.e. Ce-+4, Sm+2, Eu+2, and Yb+2).
4. When fractionation occurs within the REE group the most
common tendency is for a relative enrichment in the lighter REE.
A study of the degree of enrichment and the range of enrichments
observed in certain rock types provides some interesting results.
Four groupings of terrestrial rocks have so far been suggested on
the basis of equivalent degree of fractionation of the REE. In order
of increasing enrichment in the lighter REE they are:
Basaltic group A. This was first recognized by FREY and HASKIN
(1964) under the name 'oceanic basalts', but this is not a good name
to designate the group, since it does not include the basalt of Kilauea
(Hawaii). Four rocks show this REE distribution, three basalts from
the mid-Atlantic ridge and one from the trial Mohole, all analyzed by
Frey and Haskin. The relative abundance of the individual REE is
similar to the average of seventeen chondritic meteorites determined
by SCHMITT et al. (1963, 1964), although the total amount of REE is
higher, which suggests that the REE in these rocks are concentrated,
but undifferentiated with respect to earlier terrestrial distributions.
The number of analyses is regrettably small, but in view of the
correspondence with chondritic rocks it is probably a valid grouping.
Basaltic group B. Three other analyses of basaltic rocks are avail­
able and these again show virtually identical REE distributions. They
are the Kilauea basalt and the Columbia Plateau basalt, analyzed by
ScHMITT et al. (1963, 1964) and the standard diabase (W-1) analyzed by
HASKIN and GEHL (1963). There is a marked enrichment of total REE
and a considerable increase in the relative abundance of the lighter
REE in these rocks as compared with group A.
There is little evidence from other fields of geological research to
justify the division of these seven basaltic analyses into two such
groups, and the possibility must be borne in mind that these groupings
are fortuitous and that further analyses will show that the REE
distributions of basalts cover a range which includes these two groups.
Sedimentary group. On the basis of seven analyses of sediments,
Haskin and Gehl have suggested that sedimentary rocks show a rela-
DISTRIBUTION PATTERNS OF RARE EARTH ELEMENTS
251
tively constant degree of REE fractionation, and have further sug­
gested that an average value for sediments may indicate the average
relative abundance of REE in the earth's crust. A number of recent
papers have adopted this suggestion (ScHOFIELD and HASKIN 1964,
GOLDBERG et al. 1964, TAYLOR 1964).
These rocks are, with one exception, all from the North American
continent. The spread of the analyses is appreciable, and the results
for three Precambrian rocks, analyzed at the same time, have been
excluded because they increased the spread still more. It is, therefore,
a somewhat suspect grouping.
Acidic group. TAYLOR (1964) used the standard granite analyzed
by HASKIN and GEHL (1963) and the Kirovograd granite analyzed by
GAVRILOVA and TURANSKAYA (1958, by spectrochemical technique) to
arrive at an average REE distribution for acidic rocks.
Any conclusions concerning REE abundances in acidic rocks based
on just two analyses are bound to be highly tentative.
These four groups were based primarily on a consideration of the
results of neutron-activation analysis (NAA), but many additional,
accurate new data are also available owing to recent improvements
in X-ray spectrographic techniques (SA). Workers using the two dif­
ferent methods have tended to follow independent lines, and we felt
that some useful purpose could be achieved by collecting and reviewing
as much as possible of the data available to date.
When attempting to study these groupings in greater detail, we
come up against the problem that various analysts have used different
methods when plotting their results, and, in some cases, a grouping
noted by one author cannot be seen, or is not nearly so convincing if
the data are plotted according to the method of another. We therefore
embarked on a short study of plotting methods before replotting the
wealth of data on terrestrial rocks to a unified system.
Method of Plottin� of Data
In a simple graph giving a plot of total abundance of each REE versus
atomic number Z or ionic radius, there are two problems: a) the much
higher concentration of even Z elements compared to the adjacent odd
elements results in a zig-zag pattern in which the minor differences
due to differentiation tend to be masked, and b) rocks with the same
252
BRENDA B. JENSEN AND ARILD O. BRUNFELT
degree of REE differentiation may be widely separated on the plot
because of differing total REE content.
The problem of the zig-zag pattern plot can be overcome by draw­
ing separate curves through the odd and even Z as proposed by
SEMENOV and BARINSKII (1958). Another procedure is to ratio two
analyses element by element and then plot the ratios against Z or
ionic radius, as discussed by CORYELL et al. (1963). ScHMITT et al. (1963)
suggested that, in view of the chemical processes involved, plots
against ionic radius rather than Z should be more significant.
The second problem is sometimes overcome by plotting each ele­
ment as a percentage of the total REE content of the rock. If one or
more of the REE has not been determined, it is, however, simpler to
take the concentration of one element as the unit and divide the con­
centration of all other elements by this value. ScHMITT et al. (1963,
1964) quote all analyses to the base La= 1.00, while HASKIN et al.
(1963, 1964) and BALASHOV et al. (1963) normalized to Yb
1.00 and
Nd= 1.00, respectively.
We decided to examine the effect of making similar plots of data
given in the literature to other bases, but decided, in order to be quite
certain of the comparability of data, to use only results obtained by
=
NAA in our first calculations. First we chose the group A basalts which
are clearly very similar, if not identical, in REE distribution pattern,
and plotted abundances normalized to each element in turn (i.e.
La= 1.00, Ce= 1.00, Pr= 1.00, etc.) according to the method pro­
posed by SEMENOV and BARINSKII (1958). The result showed that La
or Pr, when used as the base, tended to spread out the grouping. A
similar series of plots of the secondary basalts group gave poor grouping
if Ce and the heavy elements Er to Lu were used as normalizing
elements. Elements in the range Nd-Tb all gave fair grouping
for both series of analyses with Eu and Tb slightly hetter than
the rest.
The superiority of Eu and Tb as bases is probably, in part, a
reflection of analytical precision.2 A large range of rock types was
plotted twice using first Eu and then Tb as bases. These plots gave
similar results for al� but one or two analyses. Failure of these analyses
to fit is most probably due to an anomalous value for one of the base
2 In NAA, Eu and Tb are readily distinguished from their neighbouring
elements owing to large differences in half-life of the isotopes used.
DISTRIBUTION PATTERNS OF RARE EARTH ELEMENTS
253
elements. There is the possibility that the Eu value could vary because
of the existance of Eu2+, but our plots suggest that in the process of
igneous differentiation this is not a common occurrence.
It also became clear from these plots that the trend of progressive
relative enrichment in the lighter REE is of major significance only
in the range La to Eu. A plot of the variation in the ratios La/Pr,
Nd/Sm, Eu/Tb, and Ho/Tm for 10 igneous rocks analyzed by NAA
shows (Fig. lA) that differentiation is greatest for the lighter REE
and minimal in the range Eu to Tb. A plot of 17 igneous rocks analyzed
by SA (Fig. lB) is not strictly comparable, since the ratios Gd/Dy
and Er/Yb had to be used for the heavier REE; nevertheless, the
minimum in the middle of the series is again clearly seen.3
In view of this we feel that it is logical to base an assess­
ment of REE fractionation in terrestrial rocks on a consideration
of lighter elements (La-Tb) only, and to normalize not to one
element, but to an average figure for the 'undifferentiated' range
Eu, Gd, Tb.
Since these lighter elements so clearly act as one series, it is inap­
propriate to work with two curves plotting odd and even Z separately.
The alternative is to use the method of CoRYELL et al. (1963) (see
p. 252), and relate all other results to one base analysis. The most
desirable distribution to use as a base would be the initial distribution
in the earth. ScHMITT et al. (1963, 1964) have assumed that this was
dose to, if not identical with, chondrites, and use the average of 17
chond.rites analyses as a base. HASKIN et al. (1963, 1964) frequently
use their average of 7 sediments on the assumption that this represents
the average distribution for the earth's crust. The spread of analyses
within these two groups is, however, appreciable (particularly in the
case of sediments), and we have looked for an alternative. It appears
that the group A basalts might be the most logical choice, but so far
there are only analyses from two localities. We chose instead to use
group B basalts. Here again there are only three analyses, but they
are from very different localities and are virtually identical in relative
abundance of REE (over the range La to Tb). An average value was
obtained by normalizing each group B basalt analysis to the base
Tb
1.00 and averaging the results. All other analyses were ratioed
=
3
This break in the region of Gd has been established by a number of in­
dependent laboratory studies.
254
BRENDA B. JENSEN AND ARILD O. BRUNFELT
B
A
Fig. l. Variation of selected REE ratios: (A) 10 rocks analyzed by NAA (mainly
basaltic), (B) 17 rocks analyzed by SA (mainly granites and syenites). Ratios
plotted in these Figures are related to the minimum ratio in each column (i.e. for
sample l d1
(LafPr)1- (La/Pr)min; (NdfSm)t- (NdfSm)min etc.
=
element for element with this average and normalized to the base
Eu+Gd+Tb
.
=
1.00 to minirmze the analytical error.
3
Raving established a method of calculation for the data obtained
by NAA, we next tried to apply it to the large number of analyses
obtained recently by SA. In particular we have worked with data
obtained by BALASHOV and co-workers (see refs.). In the majority of
cases no figures are available for Eu and Tb. It is therefore necessary
to normalize to base Gd
1.00, but this should not cause great inac­
curacy since this element can be determined with relatively high
precision by SA.
=
DISTRIBUTION PATTERNS OF RARE EARTH ELEMENTS
255
BALASHOV (1963) has made a comprehensive study of the recent
spectrographic work on rocks, which has been done largely by Russian
workers. He uses a number of methods current among Russian
authors for reporting and comparing data.
l. Most commonly used is the ratio 'f.Cej'f.Y ('f.Ce is the sum of the
light elements La to Eu and 'f.Y is the sum of the heavy elements Gd
to Lu plus Y). This ratio will give some measure of the degree of
differentiation of the lighter REE, but will be affected by: a) the
additional variations which sometimes occur in the end member with
highest and lowest Z (see p. 252), b) lack of sensitivity in the
SA of
heavy REE.
2. It is also becoming common among Russian authors to ratio to
the base
Nd
=
1.00 since
BALASHOV (1963) shows that, over the com­
plete range of igneous rocks, the absolute abundance of this element
varies less than any other. The degree of differentiation is then fre­
quently measured by a comparison of ratios Ce/Nd and Er/Nd. This
method is open to objection, since it relies heavily on the element Ce
which is known to be liable to variations unconnected with the general
trend (due to oxidation-reduction of Ce between the trivalent and
tetravalent states).
3. Finally, a number of analyses are reported as 'correlation
ratios' La/Ce, Ce/Pr, Pr/Nd, etc. This method also removes the effect
of absolute concentration of the REE and thus enables direct com­
parison of various rocks. It is good in that one element, if poorly
determined, will affect only the adjoining elements and not the whole
analysis. It is not, however, a system which can be readily adapted
for graphical representation since the zig-zag effect is not eliminated.
When attempting to relate the
SA data to that obtained by NAA
(by ratioing to the average of the secondary group basalts, analyzed
by
NAA,4 and normalizing to Gd
=
1.00) we found that, with two
exceptions, all igneous rocks showed a distribution which was either
group
B or more highly differentiated. The two exceptions were
peridotite from the Urals and pyroxenite from the Kola Peninsula.
The figure for Ce tended to be low in all cases, which suggested that
the absolute value for Ce as determined by
' It was necessary to
use
SA is lower than that
the NAA average since, to our knowledge, there
are no SA data on rocks which can be safely assumed to have a group B distri­
bution.
256
BRENDA B. JENSEN AND ARILD O. BRUNFELT
obtained by NAA. A 'correction factor' (Table l) was therefore applied
to the Ce figure of the average for group B basalts when ratioing SA
data. It was assumed that for all other REE the absolute values ob­
tained by the two methods are comparable. It is unfortunate that,
to our knowledge, no one rock has been analyzed by both NAA and
SA. Until this has been done, some doubt must remain concerning this
assumption; and, for this reason, the data obtained by the two tech­
niques have been plotted separately (Figs. 4-10).
The data of SAHAMA (1939, 1945) are obviously less precise than
those of more recent workers and do not give smooth curves when
ratioed to the average of group B basalts. His results for the rocks of
southern Finnish Lapland (1945), however, if ratioed to his own
analyses of gabbros and dolerites (Fig. 10), give relatively smooth
curves and provide some useful additional information. Caution must
be exercised in comparing these results with other graphs in this
paper, since we have no proof that his gabbro and dolerite average
has a true group B distribution.
Deductions based on Replotting of Data
Table 2lists all data which have been replotted to the new system and
from which Figs. 2-10 have been constructed. It becomes apparent
that some revision must be made of the groupings, based on equivalent
degree of REE fractionation, which have been suggested previously
(see p. 250).
The two groupings of basaltic rocks (Fig. 2) are probably valid.
(There is no SA data to confirm or refute them.) Since eclogitic rocks
fall into the same two groups, it is perhaps preferable to exclude the
word 'basaltic' and refer to groups A and B. Sediments and acidic
rocks do not group, but each covers a wide range.
IGNEOUS ROCKS
Group A. In addition to the basalts of the mid-Atlantic ridge and the
trial Mohole, the plots show that group A includes an eclogite from
Australia (Fig. 4). This is a most valuable addition to the group since
it confirms the existence of this REE distribution in deep seated
DISTRIBUTION PATTERNS OF RARE EARTH ELEMENTS
Fig. 2.
Generalized diagram of
257
REE
distributions in terrestrial rocks, based
on Figs. 4-10. AA' Average for group
A rocks. BA' Average for group B
rocks. The area of vertical shading
indicates the range of
REE
tions found in crustal
distribu­
igneous and
metasomatic rocks. The area of in­
clined shading indicates the range of
REE
distributions found in sedimentary rocks.
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La
Ce
Pr
Nd
Pm Sm Eu
Gd
continental rocks. (LovERING and MoRGAN (1963) regard this eclogite
as possible upper mantle material on the basis of U/Th ratios.)
Since group A rocks have a low total content of REE, show a REE
distribution dose to that of chondrites and are all of deep seated
origin, we would agree with FREY and HASKIN (1964) that this group
probably represents a primary or near primary stage of terrestrial
REE distribution, but would emphasize, as they do, that this state­
ment does not carry the implication that these rocks are unaltered
mantle material.
Group B. In addition to the three basaltic rocks of Kilauea ( Hawaii) ,
Columbia plateau, and Fairfax County (W-1), the plots show that
258
BRENDA B. JENSEN AND ARILD O. BRUNFELT
group B includes an eclogite froni the South African Kimberlite pipes
(Fig. 4).
The group B basaltic rocks have a higher total REE content than
the group A rocks and show a marked relative enrichment of the
lighter REE over group A. In view of this, we postulate that this
group represents a first stage, or early stage, in fractionation of the
REE; although there is adrnittedly no other geological evidence to
indicate that these rocks are any less 'primary' than the basalts of
group A.
FREY and HASKIN (1964) have shown that the group A basalts are
a terrestrial parallel of the calcium rich achondrites among meteorites,
which are basaltic in the chernistry of their major elements and have
REE abundances much greater than chondrites, although the relative
abundance of the individual REE is virtually identical. ScHMITT et al.
(1963) have pointed out a sirnilar parallel between group B basalts
and Nakhlitic meteorites (which have basaltic mineralogy and texture).
lf the concept of a single parent body for meteorites is accepted, then
it can be postulated that terrestrial and meteoritic differentiation run
parallel to this point (Figs. 4 and 5).
Any suggestion as to the mechanism which rnight be responsible
for these observed differences in REE distribution must be highly
tentative. lf, however, the first stage of REE fractionation is com­
monly a 'jump' from group A to group B distribution, then fractional
crystallization is not a likely mechanism, since this could be expected
to produce all gradations between the two groups. Partial melting of
mantle rock is, perhaps, more likely to result in fixed steps of REE
fractionation. In support of this suggestion VINOGRADOV (1961) showed
that basaltic liquid could be produced from a chondritic meteorite by
'zone melting' leaving a residuum of olivine rock. He also showed that
the Eu/Dy ratio of a chondrite lay between those of a basalt and a
dunite. Unfortunately complete REE analyses of the rocks which he
studied are not available.
The seven analyses of basaltic rocks show either group A or group
B distribution, but other igneous rocks (with two exceptions) are
enriched in the lighter REE compared to group B. The exceptions are:
l) late stage hydrotherrnal and metasomatic rocks, and 2) ultramafic
rocks, both of which have distributions lying between group A and
group B (Fig. 6, a and b).
DISTRIBUTION PATTERNS OF RARE EARTH ELEMENTS
259
The data on gabbroic and dioritic rocks are scanty, but plots of
the available analyses show slight enrichment of the lighter REE over
group B (Fig. 6, b).
Granitic and syenitic rocks show, when plotted by this method,
a very wide range of possible REE distributions (Fig. 6, c and d) varying
from group B to extreme enrichment in the lighter REE. Plotting only
granites from 'batholithic' environments does not narrow this range.
Studies of individual massifs (Fig. 6, e, f and g) show that a trend
of steady enrichment in the lighter REE can frequently be traced in
a melt until it becomes granitic or syenitic in composition. Such a
trend can be explained in terms of crystal fractionation of the rock­
forming minerals. In the early stages of crystallization of a magma,
most of the REE are retained in the melt, but a small percentage
occupy Fe, Mg or Ca positions in the early-formed ferro-magnesian
minerals. Preferential take-up of the heavier REE in these positions
can be predicted on the grounds of ionic radius and co-ordination
number (KHOMYAKOV 1963). This type of fractionation in a basaltic
magma of group B distribution would also account for the production
of ultramafic rocks depleted in the lighter REE relative to group B.
The eclogite from South African Kimberlite (Fig. 4), which shows
a group B distribution, is an anomalous rock. It has a low total abun­
dance of REE, which, together with its mineralogy and geological
environment, suggests that the REE distribution should be group A
type. A peridotite of the Kimberlite pipes is also anomalous, showing
a very appreciable relative enrichment of the lighter REE, although
total REE content is still low. It would appear that an unusual line
of REE fractionation has taken place in these rocks. The reported
presence of perovskite in South African Kimberlite may provide a
due. Structural factors play an important role in determining the
substitution of REE for Ca (KHOMYAKOV 1963). In the majority of
rock forming minerals the co-ordination number of Ca is low, and the
heavier REE are more readily incorporated in the lattice. Analyses of
a number of perovskites show, however, that in this mineral, which
has a high Ca co-ordination number, preference is shown for the
lighter members of the series (BORODIN and BARINSKII 1960). Early
formation of this mineral could, therefore, upset the normal trend of
REE fractionation.
The wide range of REE distributions observed in granites and
260
BRENDA B. JENSEN AND ARILD O. BRUNFELT
syenites is undoubtedly a reflection of the variety of ways in which
rocks of this composition can be formed. Derivation from basic mag­
mas, by extensive fractionation of the type previously described, will
tend to produce extreme differentiates, but anatexis or assimilation
may be expected to produce melts of granitic or syenitic composition
with a range of REE distributions at least as great as that of sedi­
ments. In addition, the 'normal' trend of fractionation in a melt is
apparently sometimes reversed when the melt becomes granitic or
syenitic in composition (Fig. 6, f). This can be attributed to two factors:
a) When crystal fractionation continues to the point where potas­
sium felspar is being formed, similarities of ionic radius will favour
the take-up of the lighter REE in the potassium positions.
b) In a melt greatly enriched in alkalis, volatiles and REE, there
is a tendency for the REE to form complexes, in which case those
formed by the heavier REE are less easily removed from the melt
( MINEYEV 1963). It is this mechanism which is thought to be respon­
sible for the very strong relative depletion of the lighter REE in
hydrothermal and metasomatic rocks.
To summarize, it would appear that major fractionation of REE
is caused by crystallization of a melt, when preferential substitution
of REE occurs during crystal fractionation, and complexing of REE
takes place when alkalis and volatiles are high. Fig. 3 shows a suggested
sequence of REE fractionation from basaltic magma to late stage
hydrothermal liquids. It is not, of course, intended to imply that such
a sequence normally takes place in its entirety without interruption or
modification by other mechanisms.
These differences in degree and type of REE differentiation can
be a most useful tool. Several studies of massifs by Russian workers,
where the intrusion history is relatively well known from field or other
evidence, have shown the potentialities of this type of analysis in
tracing consanguinities and differentiation histories when other evi­
dence is inconclusive:
a) The essexite-nepheline syenite rocks of the Sandyk massif
(Fig. 6, e) were studied by ZLOBIN and BALASHOV (1961). The massif
was built up by five separate injections, each showing slightly greater
REE differentiation than the one before. Two phases of injection have
been recognized on the basis of field evidence, the pause occurring
between the third and fourth injections. This too is indicated by our
DISTRIBUTION PATTERNS OF RARE EARTH ELEMENTS
a)
Basaltic magma showing group
B REE
distri-
bution.
261
Bl-------lA
b) Ultramafic rocks formed by crystal sinkingmelt relatively enriched in the lighter
c)
REE.
A
5 ....:-:_:
--.J
______
Further fractional crystallization of the melt
with
continued
heavier
REE
preferential
take-up of the
s
in the solid-intermediate rocks
Bf---�=-�--=:!lo..-l A'
d) This trend continues until the melt becomes
Br---A
---=...."""l
formed.
granitic or syenitic in composition.
e)
When
crystallization
proceeds
to
M
the point
where K felspars are being formed, the trend
will be reversed with preferential take-up of
the lighter
f)
REE
Br------"""''--lA
in the solid.
At later stages the reverse trend will be contin-
M
ued owing to the formation of complexes in the
melt, which will show steady relative depletion
of the lighter
g)
REE.
The final phase is frequently depleted in the
lighter
REE
relative to the group
B
average.
It solidifies as dike rocks, hydrothermal rocks,
Bl---���----� A.
pegmatites, etc.
sL
Fig. 3. Schematic sequence of changes in
;
REE
-
Gd
distribution between melt and
solid fractions during differentiation of a magma (plotted as in Fig. 2). S =solid,
M
=
melt.
262
BRENDA B. JENSEN AND ARILD O. BRUNFELT
plot of the REE analyses. Chemical analyses of the major constituents
give no such clear indications of consanguinity and relative age.
b) The gabbro-granite of the Susamyr batholith (Fig. 6, f) was
studied by LEONOVA and BALASHOV (1961). Emplacement of these
rocks took place in three major intrusive phases followed by a period
of dike injection. The REE distribution in the gabbro and dolerite of
the first phase is only slightly differentiated with respect to the group
B distribution, while the granites and granodiorites of the second phase
are highly enriched in the lighter REE. The third phase of leucogranites
shows a return to near group B distribution, while the alaskite dike
phase is even more depleted in the lighter REE. This can be explained
in terms of a change in the type of REE differentiation at the end of
phase two.
c) In the case of the Lovozero massif (Fig. 6, g) the picture is not so
simple. The massif was formed in four major intrusive phases and the
REE distribution in the second and third phases has been studied in
detail by BALASHOV and TURANSKAYA (1960, 1961). Phase two, known
as the Differentiated Complex, consists of 1,500 m of alternating foya­
ites, urtites and lujavrites, showing moderate to extreme enrichment of
the lighter REE. The rhythmical layering indicates that there were
repeated injections of magma fractions, which then formed layers
while cooling. This in situ layering resulted in strong fractionation of
the REE, particularly at the base of the massif, which tends to mask
any differences in the REE composition of the original magma frac­
tions. Comparison of the average content of REE for the complex,
computed by Balashov and Turanskaya with the average for the upper
part only, indicates, however, that the source magma for the rocks at
the top of the complex was richer in the lighter REE. If, as has been
suggested, the Differentiated Complex crystallized from the top down,
then the source magma had reached a stage of progressive depletion in
the lighter REE. Phase three, the Eudialyte complex, shows a return
to near secondary group REE distribution, which further supports the
suggestion that the reverse trend of differentiation was operating in
the source magma. Eudialytites, which on field evidence are younger
than the main mass of the Eudialyte complex, show a further contin­
uation of the trend, and are depleted in the lighter REE relative to
group B.
In a complex of this kind it is clear that any explanat ion of the
DISTRIBUTION PATTERNS OF RARE EARTH ELEMENTS
263
mechanisms involved in differentiation must be tentative; neverthe­
less, a knowledge of the degree of REE differentiation is of value in
determining, for example, to which phase of intrusion a given rock
belongs. In this connection it is also useful that curves of a given phase
frequently show a common characteristic, e.g. the rocks of phase three
in the Lovozero massif are all high in Sm, giving a marked kink in the
curve at this point.
SEDIMENTARY ROCKS
l. The nine North American sediments of HASKIN and GEHL (1962),
when plotted by this method, spread over a broad range (Fig. 7). The
curves are not so smooth as those of igneous rocks, but enrichment in
the lighter REE is again the main differentiation trend. Calcareous
rocks show a high degree of enrichment, while shales and sandstones
tend to group and are moderately enriched with respect to group B
basalts. There is no reason to omit the Precambrian Bayfield County
sandstone, which was excluded from Haskin and Gehl's average figure
for sediments because of failure to group with the rest.
2. A marble from Antarctica, also analyzed by HASKIN and GEHL
(1962), is much less differentiated than their other calcareous rocks
(Fig. 7).
3. SA of a limestone from New Mexico analyzed by GRAF (1960)
gives a distribution similar to that of Haskin and Gehl's calcareous
rocks from North America (Fig. 8).
4. SA of three carboniferous age sediments from the Russian plat­
fonn, analyzed by BALASHOV (1963), show much less differentiation,
being group B or just above (Fig. 8).
It can, therefore, be concluded that the REE distribution in
detrital sediments does not, as thought previously, provide a world­
wide crustal average, but possibly an average for the area from which
the material was derived.
The separation of calcareous rocks from sandstones and shales in
the plot of sediments of the North American continent (Fig. 7) may
be significant. It has been shown by ScHOFIELD and HASKIN (1964)
that the take-up of REE by calcareous organisms is not sufficient to
make a significant contribution to the total REE content of a calcare­
ous rock. The distribution must, therefore, be determined either by
264
BRENDA B. JENSEN AND ARILD O. BRUNFELT
detrital accumulation or by inorganic precipitation. If the former were
the case, one would expect a grouping broadly similar to that of the
sandstones and shales. We are, therefore, left with the postulation that,
during inorganic precipitation of calcium carbonate, a process of
selective scavenging takes place which results in a relative increase in
the lighter REE in the sediments. This would suggest that the pre­
cipitation of carbonate takes place in the form of aragonite, since this
structure is favourable to the substitution of large ions in the Ca
positions and could, therefore, be expected to show preference for the
lighter REE.
GOLDBERG et al. (1963) have shown that the distribution of REE
in a sample of sea water from the California coast is very similar to
Haskin and Gehl's average for sediments over the range La-Tb. If
plotted together with Haskin and Gehl's California (tertiary) sandstone,
the similarity is even more striking (Fig. 9). Goldberg et al. also showed
that the distribution in phosphorite from Baja California is virtually
the same as that of the sea water (if anomalous Ce is ignored) and
deduced that the REE content is most probably the result of direct
precipitation from the water. Since, however, analyses of a number of
detrital sediments and phosphorites have shown a wide range of REE
distribution patterns, the question is raised of possible appreciable
variations in the REE distribution in sea water. Goldberg et al.
point out that the short residence time of REE in sea water would
suggest that variations might be expected from one water mass
to another.
A manganese nodule from a depth of 5,000 m at 40° 14' N 155° 52'W,
analyzed by Goldberg et al. (Fig. 9), shows a group B distribution when
plotted by this method-if anomalous Ce and Sm are ignored. lf the
REE distribution is the result of precipitation from sea water, then
such precipitation presumably involves slight REE fractionation.
METAMORPHIC ROCKS
Very little is known of REE distributions in metamorphic rocks.
SAHAMA's analyses (1945) are not so precise as modem data and give
rather irregular curves (Fig. 10). From his work, however, it would
appear that the meta-sediments and granulites of southern Finnish
Lapland all have the same degree of differentiation, although the total
DISTRIBUTION PATTERNS OF RARE EARTH ELEMENTS
265
abundance of REE differs, which suggests that, even under the ex­
treme cond.itions of metamorphism required to produce a granulite,
the REE tend to act as a coherent group.
Conclusions
Major fractionation of the members of the REE series takes place only
during igneous and metasomatic processes. There may be slight
add.itional fractionation during the precipitation of material from sea
water, but in general it would appear (from the admittedly scanty data
available) that sedimentary and metamorphic processes make little
contribution to REE fractionation.
IGNEOUS ROCKS
The main trend of REE fractionation is a relative enrichment in the
lighter REE, which occurs in igneous rocks as a result of crystal
fractionation within a melt. A reverse trend, involving relative de­
pletion of the lighter REE, is found only in rocks formed as late stage
products of the differentiation of a melt, or under hydrothermal or
metasomatic cond.itions. It can be attributed to late stage crystal
fractionation and to complexing of the REE in the melt.
The groupings and ranges of REE d.istributions which can be rec­
ognized in igneous rocks are:
Group A. A primary or near primary REE distribution which is
virtually identical with the d.istribution pattern common to all chon­
dritic meteorites. It is found not only in basalts from the mid-Atlantic
ridge and the trial Mohole, but also in an Australian eclogite, which
considerably strengthens the theory that this d.istribution is common
to all deep-seated material.
Group B. A first or early stage in the fractionation of the REE
which is shown by basalt from an oceanic volcano and also by two
continental basaltic rocks. The d.istribution is very similar to that seen
in Nakhlitic meteorites. The appearance of this pattern in oceanic
basalt suggests that partial melting of the mantle can involve REE
fractionation.
The d.ivision of basalts into two groups is upheld largely by analogy
with the meteoritic rocks for which many more data are available. It
266
BRENDA B. JENSEN AND ARILD O. BRUNFELT
could be, however, that further data on terrestrial rocks will reveal
that these are just two positions within a range of possible basaltic
distributions.
Other igneous rocks range from below group B distribution, to very
highly enriched in the lighter REE. The most extreme enrichment
occurs in certain granites and alkali syenites. Some tendency towards
grouping can be observed, thus:
l) Ultrabasic and basic rocks range from below group B to just
above.
2) Dioritic rocks probably show only slight enrichment relative to
group B, but the data are very scanty.
3) Granites and syenites cover the whole range from below group B,
to the greatest recorded enrichment in the lighter REE.
4) Pegmatites and metasomatic rocks are frequently depleted in
the lighter REE compared to group B.
The observed variations in REE distribution can be explained in
terms of the two main trends of REE fractionation. Ultrabasic, basic
and intermediate rocks can be regarded as the products of differenti­
ation according to the main trend of steady enrichment of the melt in
the lighter REE, while pegmatitic and metasomatic rocks are the
products of the reverse trend. The change in trend takes place when
a melt is granitic or syenitic in composition, which could account in
part for the wide range of possible REE distributions observed in these
rocks. Formation of granites by anatexis or assimilation can similarly
be expected to result in a broad range of REE distributions (similar to,
or greater than that of sediments).
SEDIMENTARY ROCKS
Sediments do not show a uniform degree of differentiation. Detrital
sediments from a particular area and period of time appear to show a
fairly dose grouping, which possibly gives some indication of the
average degree of REE differentiation in the land mass surrounding
the basin at the time of deposition.
METAMORPHIC ROCKS
Very little is known of REE distributions in metamorphic rocks, but
there are indications, from the work of Sahama, that even very highly
DISTRIBUTION PATTERNS OF RARE EARTH ELEMENTS
267
metamorphosed rocks can reta.in the REE distribution of their parent
material.
The picture presented is undoubtedly over�simplified, but the pres­
ent rapid rate of accumulation of data should shortly add more detail.
Studies of differences in REE distribution can undoubted.ly contrib­
ute to our knowledge of the major stages in the fractionation history
of the earth and, on a different scale, provide a useful tool in studying
particular sequences of related rock types.
Acknowledgements
The work was carried out while the authors held research fellowships
granted by the Royal Norwegian Council for Scientific and Industrial
Research and the Norwegian Research Council for Science and the
Humanities.
Thanks are due to Professor Dr. A. C. Pappas and Dr. H. Neumann
for encouragement in this work and to Professor Dr. T. F. W. Barth
for constructive criticism of the manuscript.
REFERENCES
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the Earth's crust. Geochemistry (English translation), No. 2:107-24.
and TuRANSKAYA, N.V. 1960. Pattem of distribution of the rare earths
in the rocks of the differentiated complex of the Lovozero alkalic massif
and certain problems of the genesis of the complex. Geochemistry
(English translation), No. 8:845-59.
1961. Rare earths in the eudialyte complex of the Lovozero alkalic massif.
Geochemistry (English translation), No. 12:1213-26.
1962. Rare earth elements in the peridotite of the Polar Urals. Geo­
chemistry (English translation), No. 4:433-35.
CoRYELL, C. D., CHASE, J. W. and WINCHESTER,
J.
W. 1963. A procedure for
geochemical interpretation of terrestrial rare-earth abundance pattems.
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FRE Y, F. A. and HASKIN, L. 1964. Rare earths in oceanic basalts. Jour. Geophys.
Res. 69:775-80.
GAVRILOVA, L. K. and TURANSKAYA, N.V. 1958. Distribution of rare earths in
rock�forming and accessory minerals of certain granites. Geochemistry
(English translation), No. 2:163-70.
GOLDBERG, E. D., KomE, M., S cH MITT
,
R. A. and SMITH, R. H. 1963. Rare
earth distributions in the marine environments.
68:4209-17.
Jo ur.
Geophys. Res.
BRENDA B. JENSEN AND ARILD O. BRUNFELT
268
GoLDSCHMIDT, V. M. 1954. Geochemistry, Oxford University Press, 730 pp.
GRAF, D. L. 1960. Geochemistry of carbonate sediments and sedimentary car­
bonate rocks - Ill. Minor element distribution. Illinois Geol. Survey,
Circular 301:1-71.
HASKIN, L. and GEHL, M. A. 1962. The rare-earth distribution in sediments.
Jour. Geophys. Res. 67:2537-41.
1963. The rare-earth contents of standard rocks G-1 and W-1 and their
comparison with other rare-earth distribution pattems. Jour. Geophys.
Res. 68:2037-43.
KHOMYAKOV, A. P. 1%3. Relation between content and composition of the rare
earths in minerals. Geochemistry (English translation), No. 2:125-32
LEONOVA, L. L. and BALASHOV, Yu. A. 1%3. Distribution of uranium, thorium
and the rare earths in the granitoids of the Susamyr Batholith (Central
Tien-Shan). Geochemistry (English translation), No. 11: 1047-55.
LOVERING, J. F. and MoRGAN, J. W. 1963. Uranium and thorium abundances
in possible upper mantle materials. Nature, 197:138-40.
MINEYEV, D. A. 1963. Geochemical differentiation of the rare earths. Geo­
chemistry (English translation), No. 12:1129-49.
MoELLER, T. and KREMERS, H. 1945. The basicity characteristics of scandium,
yttrium and the rare earth elements. Chem. Rev. 37:97-159.
SAHAMA, T. G. and VXHÅTALO, V. 1941. X-ray spectrographic study of the rare
earths in some Finnish eruptive rocks and minerals. Bull. comm. geol.
Finlande XIV:50-83.
SAHAMA, T. G. 1945. Spurenelemente der gesteine im siidlichen Finnisch­
Lappland. Comm. geol. Finlande Bull. No. 135, 86 pp.
ScHMITT, R. A.,
SMITH, R. H., LAscH, J. E., MosEN, A. W., OLEHY, D. A.
and VASILEVSKIS, J. 1963. Abundances of the fourteen rare-earth ele­
ments,
scandium and yttrium in meteoritic and terrestrial matter.
Geochim. et Cosmochim. Acta, 27:577-622.
SCHMITT, R. A. , SMITH, R. H. and 0LEHY, D. A. 1964. Rare-earth yttrium and
scandium abundances in meteoritic and terrestrial matter - Il. Geochim.
et Cosmochim. Acta, 28: 67-86.
ScHOFIELD, A. and HASKIN, L. 1964. Rare-earth distribution pattems in eight
terrestrial materials. Geochim. et Cosmochim. Acta, 28:437-46.
SEMENOV, E. I. and BARINSKII, R. L. 1958. The composition characteristics of the
rare earths in minerals. Geochemistry (English translation), No. 4 :398-419.
TAYLOR, S. R. 1%4. Abundance of chemical elements in the continental crust:
a new table. Geochim. et Cosmochim. Acta, 28: 1273-86.
VINOGRADOV, A. P. 1961. The origin of the material of the earth's crust -
Communication I. Geochemistry (English translation), No. l :1-32.
ZLOBIN, B. L. and BALASHOV, Yu. A. 1961. Distribution and ratios of the rare
earth elements in alkalic plumasitic series: essexite - nepheline syenite.
Geochemistry (English translation}, No. 9:784-88.
Accepted for publication January 1965
Printed June 1965
269
DISTRIBUTJON PATTERNS OF RARE EARTH ELEMENTS
Table l. Data used as the average for group B basalts
l
La
l.
The average of Kilauea basalt, Columbia
plateau basalt and W- 1,
to the base Tb=l.OO
used when plotting NAA
data
15.8
l
Ce
l
Pr
l
l
Nd
Sm
l
Eu
l
Gd
l
Tb
l
42. 4
5.26
5. 9 3
2 3.5
2. As above, to the base
Gd= 1.00, with a slight
change in the figure for
Ce (see p. 256) used
when plotting SA data
2.47
5.64
.823
3.68
.928
3. Gabbro and dolerite
of southern Finnish
Lapland to the base
Gd=l.O, u sed when
plotting the data of
Sahama (see p. 256)
l. O
2.0
.5
2.5
.5
1.62
6. 3 9
1.00
-
1.00
-
1. 0
-
-
Table 2. Analyses used in Figs. 4-10
Rock
Basalt, Kilauea Iki 2 3
Basalt, Columbia Plateau
Dolerite, W-1
Basalt, Atlantic Ridge GE 15 9
GE 160
-t-GE260
-t-Basalt, Experimental Mohole
Gabbro-diorite, Tien Shan, Susamyr
Tien Shan, Sandyk
dolerite, Finnish Lapland
Alkalic gabbroid,
Gabbro and
Analytical
Method
Author and year
NAA Schmitt et al. 1 963
t-»
))
Haskin and Gehl 1964
l)
Frey and Haskin 1964
t-»
»
-t--t-»
SA Leonova and Balashov
1963
Zlobin and Balashov1961
»
-
-
»
Sahama 1945
Figs.
4
4
4
4
4
4
4
6 b, f
6b, e
lO
270
BRENDA B.
JENSEN AND ARILD O.
BRUNFELT
Table 2. (cont.)
Rock
Pyroxenite, Kola Pen., Monche Tundra
Peridotite, Polar Urals, Marun Keu
•
S. Africa, Wesselton mine
Eclogite, S. Africa, Roberts Victor
mine
Eclogite, N.S.W., Delegate
Granite,
»
Tuva, Agash
»
•
Nizhne-kadraus
Balashov 1963
Balashov and Turanskaya 1962
NAA Schmitt et al. 1963
-
•
- -
SA
•
Rapakivi granite, Ukraine, Ustinovskii
Granite, Ukraine, Kirovograd
•
Tuva, Kadyross
•
•
Granodiorite, Tien Shan, Susamyr
•
Alaskite, Tien Shan, Kzyl-Ompyl
Riebeckite granite, Kazakhstan
Albitite, Kazakhstan
Alaskite, Tien Shan, Susamyr
•
Granite, Tien Shan, Susamyr
•
Finnish Lapland
Gneissose granite, Finnish Lapland
Syenodiorite, Georgia, Adzharia-Merisi
Granosyenite, Tien Shan, Kzyl-Ompyl
Syenite, Tien Shan, Kzyl-Ompyl
Alkali-syenite, Tien Shan, Sandyk
Granosyenite, E. Tuva, Dudino
Calcic syenite, Tien Shan, Sandyk
Leuco-calcic syenite, Tien Shan,
Sandyk
t-·
•
»
E.
Figs.
6b
»
Leuco-granite, Tien Shan, Susamyr
•
Author and Year
SA
•
G-1
E.
Analytical
Method
»
»
•
»
•
•
»
•
•
»
•
»
»
1964
Haskin
and Gehl 1963
Pavlenko and Turanskaya*
Pavlenko and Turanskaya*
Leonova and Balashov
1963
Balashov 1963
Gavrilova and Turanskaya 1958
Pavlenko and Turanskaya*
Leonova and Balashov
1963
Balashov 1963
Mineyev 1963
t-Leonov a and Balashov
1963
Leonov a and Balashov
1963
Sahama 1945
-
__..._
6b
4
4
4
4
6c
6c
6 c, f
6c
6c
6c
6C , f
6c
6a
6a
6 a, f
6f
10
10
Balashov 1963
6d
6d
6d
-t-Zlobin and Balashov 1961 6d, e
Pavlenko and Turan6d
skaya*
Zlobin and Balashov 1961 6e
__..._
-t-
6e
271
DISTRIBUTION PATTERNS OF RARE EARTH ELEMENTS
Table 2. (cont.)
Analytical
Method
Rock
Kakortokite, Greenland, Ilimaussak
Aegerine lujavrite, Greenland,
Ilimaussak
Nepheline syenite, Alai mts., Turpi
Khibinite, Kola Pen., Khibina
Miaskite, Urals, Vishnevyye mts.
SA
&
-
&
-
•
-t--
•
Nepheline syenite, Tien Shan, Sandyk
Eudialytite, Kola Pen., Lovozero
»
-t--
Balashov 1963
»
Melano-lujavrite, Kola Pen., Lovozero
Foyaite,
Urtite,
Lujavrite,
Sodalite syenite,
Author and Year
•
•
-t--
•
-
t--
•
-t--
•
t--
t--
Balashov and Turan6d, g
skaya 1961
Zlobin and Balashov 1961 6e
Balashov and Turanskaya 1961
6 C, g
6g
-t--t-6g
-6g
-t-6g
»
-
7
7, 9
7
7
7
•
-
7
•
-t--
»
-t--
NAA Haskin and Gehll 962
Sea water, coast of California
Phophorite,
-t-Manganese nodule
NAA Goldberg et al. 1963
-
29 meteoritic rocks
6d
6d
6d
6d
6d
t--
Sandstone, Berea, Kentucky
-t-Kettleman Hills, California
t-Bayfield County, Wisconsin
Shale, Muncie Creek, Kansas
Quartzite, Rib mtn., Wisconsin
Limestone, Leavenworth, Kansas
-t-Redfern Lake, B.Columbia
Carbonate sedt., Florida Bay
Marble, Marble Pt., Antarctica
Clay Cl, Russian Platform Malinovskii
t-Tovarkovo
Sandstone Cl, Povarovka
Limestone, New Mexico
Granulite, S. Finnish Lapland
Shale,
-·Quartzite,
__, _
-
Figs.
-t--
•
t--
•
-
•
-t-t-t--
7
7
•
-t--
7
»
Balashov 1963
8
8
8
8
»
-
»
-
•
•
t-t--
Graf 1960
Sahama 1945
»
•
lO
t--
lO
-
•
-t--
»
-·-
•
Schmitt et al. 1963, 1964
* Unpublished data quoted by Balashov 1963.
lO
t--
-
9
9
9
5
Fig.
:;;
a
a::
o
.......
s:
..c
o
(11
'
�
o
o
'-
l
La
9
4. REE
o
(11
m
a
r..
(11
>
<{ 1,0
�
a
.a
aJ
o.
:l
o
r..
m
r..
�20
,
�
.......
Cl)
Pr
distribution in igneous rocks analyzed by NAA (normalized to
Ce
10 Gl-granitc
3
Eu + Gd + Tb
Group
B
Group
A
=
1. 0 0 ).
l Mid-Atlantic ridgc
basalt
2 11
••
u ..
3 Tri al Mohole basalt
4 Delegat« eclo g i te
Kilauea basalt
6 Columbia Plateau
basalt
7 Wl- dolerite
8 5. African eclogitc
.peridotite
''
9
{
\5
1'-:)
ti
l:d
::d
c:
z
"1
t>1
9
t:l
.....
t-<
�
>
z
t:l
t>1
z
(JJ
t>1
z
._
l:d
l:d
::d
t>1
z
t:l
>
�
/
/
'
'
-
·
�
=
1.0 0 ).
-·
10 Pallasite, o l ivine phase - Thie! mts.
.....
8 Nakhlite- Nakhla
9 Nakhlite- Lafayette
�
tv
(fl
is:
t>1
z
o-l
�
t>1
��
t>1
�
>
�
t>1
o
"1
(fl
�
z
�
o
z
�o-l
.....
A..
{
�
'�
!
6 Mesosideri te- Ester ville
7 Pallasite, olivine phase- Brenham
(partial analysis on ly)
4 Ca poor achondrite- Shalka
(partial analysis only)
5 Mesosiderite -Veramin
�+�+Th
.
Fig. 5. REE distribut10ns in meteorites analyzed by NAA (normalized to
o
/
/
Gr up
�
A
Group
Average of 17 chondri les
2 Ave rage of 4 Ca rich achondri les
3 Ca poor achondrite - Norton Count y
(l
274
BRENDA B.
!1
�a
Il
m
Q.
"
o
c.
Cl
JENSEN AND ARILD O.
1
Kazakhstan ri2b2ckit2 gran it2
.2
2,0
BRUNFELT
"
a l b it it2
3
Ti2n-S han
4
Lovazero 2udialyti t2
Susamyr
a l as k it2 dyk2
�
.e
..
Cl
!!
� 1,0
'
...
4
o
�
..
o
.c
3:
o
a
a:
Lo
Fig.
Ce
Pr
Nd
Pm
Sm
6a. REE distributions in igneous rocks analyzed by SA - Dike rocks,
pegmatites and metasomatic rocks (normalized to Gd-1. 00).
-;;)' 3,0
�
1
o
Ill
o
.Q
Kola peninsula p yroxcn itc
2
Urals mountains peridotite
4
Susamyr gabbro-diorite
3 Sandyk alkali gabbroid
ro
a.
:::J
o
'0120
''
�
Ill
OI
f
Ill
�
'
�
�
1,0
Ill
o
..r:;.
�
o
+'
o
a:
Lo
Ce
Pr
Nd
Pm
Sm
Eu
Gd
Fig. 6b. REE distributions in igneous rocks analyzed by SA- Mafic and ultra­
mafic rocks (normalized to Gd-1.00).
DISTRIBUTION PATTERNS OF RARE EARTH ELEMENTS
275
1 E. Tuva, Agash gran i t e
2 E . Tuva, Nizhnc-Kadraus granitc
3 Ticn-Shan, Susamyr, lcucocratic granite
4 Ukrainc, Ustinovskii, rapakivi gran i te
5 Ukrainc, Kirovograd, gran it e
6 E . Tuva, Kadyross gran i t e
7 Ticn-Shan, Susamyr, granodioritc
5,0
8 Tien-Shan, Kzyi-Ompul alaskitc
4,0
.......
Ill
�
o
Ill
o
.o
m
a.
:::J
f
OI
3, 0
4
'-
o
....
61
OI
o
'61
>
�
' 2,0
X
u
o
'-
61
o
.c
�
o
:;; 1,0
o
a:
Fig. 6c. REE distributions in igneous rocks analyzed by
granodiorites (normalized to Gd-1.00).
SA
-
Granites and
276
BRENDA B.
5�
10
JENSEN AND ARILD O.
11
\
\
5,0
\
BRUNFELT
l Georgia Acfzharuja-Merisi syenodiorite
2 Tien Shan Tzyl-Ompul granosyeni te
3
"
syenite
"
4 Sandyk alkali syenite
5 E.Tuva Dudino gronosyenite
6 Greenland llimaussak kakortokite
7
"
"
aegerine lujavrite
8 Alai mts.Turpi nepheline syenite
9 Kola pen. khibina
khibinite
10
Urals, Vishnevyye mts. miaskite
11 Lovozero massif melanocratic lujavrite
4,0
......
Ul
...
o
Ul
o
..a
ID
g- 3,0
o
'­
OI
'-
�
61
o
'-
OI
l
'
�
o
o
'61
o
.s:.
�
o
...
o
a:
1,0
lo---
La
Fig. 6d.
REE
-o--- -o.. __ _
Ce
Gd
distributions in igneous rocks analyzed by SA - Syenites and
nepheline syenites (nonnalized to Gd- 1. 0 0).
DISTRIBUTION PATTERNS OF RARE EARTH ELEMENTS
5,0
5
Phas� l
Phase 11
277
Alkalic gabbroid
{1�
Calcic s y �nite
{45
Hornblende alkalic syenite
Nepheli n� syeni te
Leucocratic calcic syenite
4
4,0
'\
11)
....
Cl
11)
_g 3,0
m
a.
:l
o
3
'\
'\
\
'CII
'-
�
�2.0
Cl
'­
til
>
<(
.....
�
o
o
'­
til
o
.s::
1,0
�
......
o
:;;
Cl
a::
Fig. 6e. REE distributions in rocks of the Sandyk massif, analyzed by SA
{normalized
to
Gd-1.00).
278
BRENDA B.
3
5,0
JENSEN AND ARILD O.
4
Phase
l
Phase 11
Phase Ill
Phase IV
l
n
n
8
BRUNFELT
Gabbro+ dior ite
Gran i te
Granod i ori te
"
Leucocratic gran ile
"
11
11
11
Alas k i t e
4,0
.......
VI
..
o
VI
.8
ID
o.3,0
�L
OI
L
.2
&
f"
� 2,0
'
.::tf.
u
f
"
o
.s::.
!
o 1, 0
...
o
a:
Fig. 6f.
REE
distributions in rocks of the Susamyr batholith , analyzed by SA
(normalized to Gd-1.00).
279
DISTRIBUTION PATTERNS OF RARE EARTH ELEMENTS
21
5 ,0
�
t
l l
l l
t?l ll
l
l l
l l
l l
\l
\l
\l
\l
li
\l
li
li
\l
li
Cl)
,,
,,
�
o
"'
o
..c
ID
a.
�
�
3,0
:J
L
�
"
OI
�
l
l
l
l
3
4
} l��n
F��}
Lujovrlte
es
5
Urttte
Upper
zones
Lujavrlte
Cl
Porphyrltlc
lujavrites
contact
7 lujavrlte lawer zone
Phasc Ill
l
\
l Eudiatyte
\
l c:omplex
l
l
\
\
l
l
l
l
\
l
l
\
l
\
l
\
l
l
l
\
l
\
l
\
l
\ l
\ l
\
l
\ l
\ l
\
\ l
\
l l
\
\ l
\
\ l
\
\
\ l
8
g
10
11
upper zone
10
Sodalite syenlte
segregation
Eudl a lytite
segregatlan
�\
o
L
IJI
�
D i ffer entiati on
c:omptex
l
l
l
q\
t
Foyaite
2
11
Phase
l
l
\
lg,
..
l
l
l
l
l
l
l
\
l
l
\
\
l
l
l
l
l
l
l
4,0
15l
2,0
g
......
.;:,(.
o
�
\
\
\
\
\
l
\�
\ '
l
\
\
\
'
\
'
'
\
'
'' '
..... ..... '\
" ',
"
o
.s:
�
o
...
o
Ir
Fig. 6g.
REE
distributions in rocks of the Lovozero massif, analyzed by SA
(normalized to Gd-1.00).
280
BRENDA B.
JENSEN AND ARILD O.
5,0
l
2
3
BRUNFELT
4
Bayfi�ld count y sandston�
B�r�a sandston�
M un ci � Creek shal�
K�ttl�man hill s sandston�
6
7
8
Leavenworth li m�ston�
Florida boy carbonat� s�dim�nt
R�df�rn Lak� lim�ston�
9
Marbl� point marbl� (Antarctica)
5 ·Ri b Mountai n quartzi t�
4,0
,...
en
....
o
en
o
.Q
m
o.
g
'­
OI
3,0
'-
�
�
sK..-----'-<
o
'-
61
�
'2,0
-"'
o
f
.!!
o
.r=
3::
�
o
Fig.
7.
distributions in sediments analyzed by NAA (normalized to
+ Gd + Tb
1.0 0 ) . O calcareous rocks, e other sediments.
3
REE
Eu
=
DISTRIBUTION PATTERNS OF RARE EARTH ELEMENTS
281
5,0
1
Russian platform, Malinovskii, clay C1
2
11
11
, Tovarkovo, clay C1
3
11
11
, Povarovka sst. C1
4 New Mexico limestone
4
4,0
."
..
o
."
o
..a
CD
o.
::J
o
'en
3,0
'-
�
al
en
o
'-
al
>
<( 2,0
'
.X
o
o
'-
al
o
.r.
3:
o
:;::;
o
a:
2
o.
....,
....
'o. ....
....
.... 0...
-.... _ "'0- -- --
>
== =o-----
Fig. 8. REE distributions in sediments analyzed by SA (normalized to Gd-1.00).
282
BRENDA B. JENSEN AND ARILD O. BRUNFELT
4,0
......
Ill
...
o
Ill
c
.Il
m
o.
5 3,0
l
Mangancsc nodulc (40'N 155'W)
2
Phosphonite, Baja, California .
3
Sea water, Sa n Di ego, California.
4
Tertiary sandstonc , Kcttlcman Hills,
California.
'Cl
'-
�
tl
Cl
c
'tl
>
c{ 2,0
'
�
o
o
'-
2
tl
o
..r::
�
o
:;;
1,0
c
a:
La
Ce
Pr
Nd
Pm
Eu
Sm
Gd
Tb
Fig. 9. REE distributions in sea water, phosphorite and a manganese nodule
analyzed by NAA (normalized to
Eu
+
Gd
3
+
Tb
=
1.00).
DISTRIBUTION PATTERNS OF RARE EARTH ELEMENTS
4,0
283
5
1
Gneissose granite and granite gneiss
Younger granite
Granulite ( Granulite formation)
4 Shale ( Lapponium formation)
5 Quartzite (Lapponium formation)
2
3
"
c:
D
a.
o.
.3
�
3,0
c:
c:
G:
uj
.....
o
"
....
"i:
.!!
2• o
o
"
l
o
'­
.Q
.Q
D
(!)
'
.X
g
1,0
'"
o
.s=
!!=
o
:.:;
D
oc
o��L____L____L____L____�--�----�----L---�
Sm
Eu
Pm
Gd
Fig. 10. REE distributions in rocks of southern Finnish Lapland, analyzed by
SA (normalized to Gd-1. 0) .