Journal of Geochemical Exploration, 48 ( 1993 ) 109-133

109

Elsevier Science Publishers B.V., Amsterdam

Lithogeochemical techniques using immobile

elements
W.H. MacLean and T.J. Barrett
Department of Earth and Planetary Sciences, McGill University, 3450 University Street, Montreal,
Quebec H3A 2A 7, Canada
(Received 13 January 1992; accepted after revision 6 April 1993)

ABSTRACT
Elements of demonstrated immobility in hydrothermal alteration and metamorphism provide useful lithogeochemical parameters for mineral exploration in greenstone terranes. They yield precise
identifications of precursor volcanic rock type and magmatic affinity, and quantitative estimates of
mass, volume and mineralogical changes. Immobile incompatible elements (Zr, Y, Nb, REE) establish affinities, and monitor fractionation of compatible elements in tholeiitic and transitional volcanic
suites. Mass changes in mobile components can be determined for a homogeneous rock unit or a
continuous volcanic series. Mass change results also bear directly on the interpretation of REE profiles in altered rocks. Normative calculations allow chemical analyses to be portrayed as alteration
minerals, which are also useful in interpreting oxygen isotope data. Immobile element techniques
produce a large number of parameters that can be illustrated on maps and diagrams, and otherwise
used in exploration. Usage of these techniques brings deeper insight to the evolution of volcanic stratigraphy and the hydrothermal processes that formed the alteration zones and ore deposits.

INTRODUCTION

Unravelling volcanic stratigraphy is a major task in mineral exploration in

greenstone belts. The mineralogical, textural and chemical identities of rocks
are often obscured by hydrothermal alteration and metamorphism, leading to
incorrect identification of volcanic rock types (basalt, andesite, rhyolite ) and
rock affinities (e.g. tholeiitic, calc-alkaline). Correct identifications are particularly needed in deep drilling exploration programs where drill holes are
necessarily widely spaced owing to drilling costs. Accurate interpretation of
drill core data is necessary not only for outlining mineralization, but also for
definition of alteration patterns, between-hole lithologic correlation, and establishment of volcanic-tectonic setting.
A number of recent studies in exploration lithogeochemistry have stressed
the identification and use of elements that have remained immobile during
hydrothermal alteration and metamorphism around ore deposits (e.g.,
MacLean and Kranidiotis, 1987; MacLean, 1988, 1990; Richards et al., 1989;
0375-6742/93/$06.00

1993 Elsevier Science Publishers B.V. All rights reserved.

1 10

W.H. MacLEAN A N D l'.J. B A R R E T q

Elliott-Meadows and Appleyard, 1991; Barrett and MacLean, 1991 ). Some

immobile elements are also incompatible in igneous processes, and can be
used to monitor fractionation processes. Combinations of immobile-compatible and immobile-incompatible elements produce permanent and diagnostic imprints of fractionation lines and plots that define magmatic affinities. Usage of these imprints leads to improved lithostratigraphic correlation,
identification of altered rock precursors, recognition of alteration haloes, calculation of mass changes, and an improved understanding of oxygen isotope,
REE and trace element distributions.
TECHNIQUES

Mapping and core logging followed by petrography and lithogeochemistry

is the logical order of investigation, with new information on rock type and
affinity gained at each step. Good field and core sample identification is critical for petrographic-lithogeochemical sampling which provides the framework for subsequent chemical calculations.
Large files of lithogeochemical data are amassed in many exploration programs in greenstone belts. Data are commonly treated using well-established
geochemical discriminants, such as SiO2 content, Mg-number, differentiation
index, alkali-SiO2 and AFM plots, which were created primarily to classify
pristine igneous rocks. Most of the elements in these discriminants are igneous-compatible, and are also mobile during water-rock interaction. They
can become highly dispersed during hydrothermal alteration at moderate to
high water-rock ratios. Although their mobility actually makes them useful
in outlining hydrothermal alteration zones, it also makes them unfit for identification of precursor rock type and magmatic affinity. By contrast, treatment of the chemical data using immobile element techniques identifies rock
type and affinity, and provides a number of extra, firmly based quantitative
parameters.
Methods for determining whether certain elements have been immobile in
metasomatism and hydrothermal alteration have been discussed, among others, by Gresens ( 1967 ), Babcock ( 1973 ), Finlow-Bates and Stumpfl ( 1981 ),
Grant (1986), Kranidiotis and MacLean (1987), MacLean ( 1988, 1990)
and Elliott-Meadows and Appleyard (1991 ). In this article we review the
methods employed recently by Kranidiotis and MacLean ( 1987 ), MacLean
(1988, 1990), and Barrett and MacLean (1991). We also outline the sequence of steps required in a lithological investigation that uses immobile
elements to establish chemostratigraphic units in altered and unaltered volcanic sequences, and to calculate the mass changes that occur within the alteration zones. This mass-based approach finds direct application in exploration and drilling programs.

111

LITHOGEOCHEM1CALTECHNIQUESUSINGIMMOBILEELEMENTS

Immobile elements
Elements should be tested for immobility in each area of study, preferably
on an identifiable single volcanic flow that can be traced laterally through an
alteration zone. Using the procedures outlined by MacLean and Kranidiotis
( 1987 ) for a single precursor system, an immobile element pair in this sample
data set will form a highly correlated (r--0.90-0.99) linear trend owing to
mass gains and losses of mobile components in the altered part of the flow; at
infinite mass gain, the regressed line ideally passes through the origin (Fig.
1 ). Results of this test show that A1, Ti and the high-field strength trace elements (HFSE) Zr, Nb, Y and the REE are immobile in alteration zones
around a large number of volcanogenic massive sulphide (VMS) deposits in
greenstone belts (MacLean and Kranidiotis, 1987, MacLean, 1988 ). Within
this group of elements, Y and the light-REE are slightly mobile under some
conditions of alteration, and r-values are lower. Care must be taken to exclude
from this test pairs of element with high chemical affinity with one another,
such as K - R b and Zr-Hf.

30

Phelps Dodge deposit:

altered rhyolite

25

C~

O
_

.,~

j,~e

J_.,.~"

15

/j"

s S

,,,,

I"

,y*"
,,,
0

't
I/

~.s

Alteratton hne:

Precursor

y = 0.034x + 0.579;
r = 0.993

sS

100

200

300

400

500

600

700

800

Zr pprn
Fig. 1. Effects of mobile mass gain and loss on immobile AI and Zr during alteration of an
initiallyhomogeneousrhyolite unit (singleprecursor system) at the Phelps DodgeVMS deposit
(data from MacLean and Kranidiotis, 1987).

1 12

W H . MacLEAN A N D T.J. BARRETT

Incompatible elements
A second requirement for our procedures is the presence of highly incompatible trace elements (bulk distribution coefficients Dso]id/melt < 0 . 1 ) to
monitor degree of fractionation and magmatic affinity. A pair of incompatible elements in a volcanic sample set produces a linear magmatic enrichment
trend that invariably passes through the origin (Fig. 2). Incompatible element enrichment is modelled by the Rayleigh fractionation equation:

Ci=Co FD-I

(1)

where Co and Ci are concentrations of an incompatible element in initial and

fractionated magmas, respectively; F is the fraction of remaining magma; and
D is the bulk (solid/melt) distribution coefficient. When D is small (estimated at ~ 0.05 for Zr), the element can be used to monitor the fractionation
process.
The HFSE are highly incompatible during fractionation in the range of basalt and basaltic-andesite in most tholeiitic and calc-alkaline suites, but, in
our experience, they remain incompatible in andesite, dacite and rhyolite only
in suites of tholeiitic to transitional (mildly calc-alkaline) affinity. The tholeiitic-transitional suites are low in K (generally <0.5 wt% K20) and fractionate to sodic rhyolite, with albite as the sole feldspar phenocryst phase. In
100

Host volcanics at the Ansil mine:

fractionation trend given
by least altered samples
8O

Zr/Y = 5.0
6O
~..

40

20
O0

y - 5 54 + 0.201x

100

2OO

r - 0 95

300

400

Zr ppm
Fig. 2. Incompatible Y and Zr enrichment in volcanic stratigraphy at the Ansil mine, Noranda
(data from Barrett et al., 1991 a).

LITHOGEOCHEMICALTECHNIQUESUSINGIMMOBILEELEMENTS

1 13

120

100'

80,

E
60'

40

20

100

200

300

400

500

Zr ppm
Fig. 3. Schematic Y - Z r plot used for determination of magmatic affinity.

the majority of fractionated calc-alkaline suites, where K-feldspar is also a

phenocryst phase in dacites and rhyolites, the HFSE are more compatible,
and D values are variable and may be >t I. The HFSE should be tested for
incompatibility in a rock suite, using plots such as Y - Z r or La-Yb, before
continuing with these procedures. However, calc-alkaline suites can still be
treated using immobile compatible elements, as outlined below.
Some ratios between the HFSE change with rock affinity, and thereby provide discriminants unaffected by alteration. The change is particularly large
and distinctive for Z r / Y ratios: these range from ~ 3 to 5 for tholeiites, to ~ 7
to ~ 30 for calc-alkaline rocks (Fig. 3) (cf. Lesher et al., 1986). Whereas
plots of Zr versus Y are linear for tholeiites, and exhibit steady incompatible
enrichment from basalt to rhyolite, those for a similar range of calc-alkaline
rocks produce poorly correlated trends, with depletions caused by variable
compatibility of both Zr and Y. Relative depletion is, however, greater for Y,
so that the Z r / Y value is higher for calc-alkaline rocks. We designate samples
with intermediate Z r / Y values ( ~ 5-7 ) "transitional"; they have linear HFSE
enrichment trends, but slightly steeper REE profiles and slightly higher A1contents than tholeiites.
Magmatic affinity can be confirmed using changes in La/Yb and Zr/Yb
ratios, as the heavy REE are geochemically similar to Y. Slopes of Zr versus
Nb plots coincide in some tholeiitic to mildly calc-alkaline suites, but diverge
in others (Barrett et al., 1991 a,b, 1992 ). The Z r / N b ratio is distinctly higher

1 14

W.H. MacLEAN A N D T.J. BARRETT

in anorogenic (rift-related) than in orogenic (subduction-related) alkaline

rocks, and provides a reliable discriminant for magmatic suites and tectonic
setting.
Other, less abundant HFSE (e.g., Hf, Ta, W, Th ) can also be used to determine rock affinity, but, because of their low abundances ( ~ 0.1 - 10 ppm ) and
high analytical costs, they are not as suitable as those described above. In our
experience, Zr is the most useful element to monitor fractionation; it is immobile, highly incompatible in the rock series noted above, and sufficiently
abundant ( ~ 50-1000 ppm) for precise chemical analyses. The Z r / Y ratio is
the most convenient and least expensive discriminant for tholeiitic and calcalkaline rocks, and can be applied on a single sample basis; however, affinities
should be confirmed by other tests on a portion of the sample set.
CHEMICAL ANALYSES

Chemical analyses for the HFSE must be precise and accurate in order to
distinguish the small differences between fractionation trends and element
ratios of individual samples. In our experience, only the data obtained for Zr,
Y and Nb by X-ray fluorescence using pressed rock powder pellets are presently suitable for establishment of magmatic affinity and fractionation trends.
With this technique there is neither the sample dilution problem inherent in
borate bead preparation, nor the problem of incomplete solution in acid
digestion methods. Good quality analyses for REE and less abundant HFSE
are obtained by instrumental neutron activation analyses (INAA), or a combination of induced coupled plasma and mass spectrometry (ICP-MS)
techniques.
SINGLE PRECURSOR

Alteration of a chemically homogeneous rock produces a single precursor

system. A plot of an immobile element pair in such a unit forms an "alteration line" that is linear and passes through the origin (Fig. 1 ). For immobileincompatible element pairs, alteration and fractionation lines coincide for rock
types of the same magmatic affinity (Fig. 4a). When the pairs are compatible-incompatible, or both are compatible, a separate alteration line is formed
for each chemically distinct homogeneous rock unit (Fig. 4b ). Single precursor alteration lines are therefore very useful in distinguishing homogeneous
volcanic units and correlating them between drill holes and through alteration zones.

115

LITHOGEOCHEMICALTECHNIQUESUSINGIMMOBILEELEMENTS
100

volcanic

Ansil
o

least

rocks:

altered

. /

_.
altered

80

oe l

..~,fp

0 ,f~.,"."
o

E 8o

Q.
>"

40

~ , ' o0"~1~" ' ' u,:,

""

20

El

100

200

300

400

Zr p p m
Schematic

alteration

lines

30
T w o rhvolite units A and B

2s

/~/~
Precursor B

20

O~

D"

,tL/

/"-j"

,o

/A~..,"
5

,r

. ire''`"

Precursor A

.:2:,,2::/"
b

~.
0

100

200

300

400

Zr p p m
Fig. 4. (a) Y - Z r plot of least altered and altered samples from the Ansi] mine (see Fig. 2).
Immobile-incompatibleelement pairs in least altered and altered samples plot along the same
regression line. (b) Alteration lines for immobile compatible-incompatible element pair can
identify two distinct rhyolite units, A and B, within a mine stratigraphy.

116

W.H. MacLEAN A N [ ) T.,I B A R R E T T

MULTIPLE PRECURSORS

Fractionation trends
Once an HFSE is shown to be highly incompatible and immobile, it can be
used instead o f the mobile monitors (e.g SiO2, Mg-number, differentiation
index) which supply only semi-quantitative estimates of degree of igneous
fractionation. The HFSE are quantitative monitors because of their high
incompatibility.
It is important to establish the fractionation lines as accurately as possible,
as they form the basis o f the precursor identification and the mass change
calculations. Plutonic rocks, such as tonalites and gabbros, can be included in
the sample set if field relations indicate that they are synvolcanic. Strongly
feldspar-porphyritic rocks should be excluded from Al-bearing plots, owing
to plagioclase accumulation and resulting high A1 contents. There is always a
certain a m o u n t o f scatter in the least altered sample data used to fit the fractionation lines. With few data at the start of exploration, the line fits are ap2.0

,,e
~
ee

'

......

Schematic tholeiitic
fractionation trend
Alteration lines

1.o.

,4"
X

0.5"

/o
J

,'

,..-_
0.0

""

"''--.

x ~

....-'"
1 I""

IRhyoliteJ

_..,,..oO-.-~'~

~-'"

~0._ .0--'0" 0

..........
,

100

a
.

200

300

400

Zr ppm
Fig. 5. Idealized fractionation curves for immobile elements in a tholeiitic volcanic suite, with
superposed chemical data for altered rocks. The two well defined alteration lines represent homogeneous units within the stratigraphy. Their intersection with the fractionation curves identifies the units as an andesite and a rhyolite. Other altered samples on these plots have each a
distinct alteration line emanating from the origin. (a) TiO2-Zr: The fraetionation curve exhibits strong Ti-enrichment in the basalts (paralleling typical iron-enrichment in tholeiites),
followed by strong Ti depletion from andesite to rhyolite.

LITHOGEOCHEMICALTECHNIQUESUSINGIMMOBILEELEMENTS
20

I"

O3

I ga~LIItl

/Q

15

o~
o

117

"

~'~

AndeslteL_

/O

,.sO

/s

o.

is ~

~.,-

--

SS

s~O

10

<:

,,Z,",.,,'"
...4"~ ..9.~" ~" ~'
/

,//:,,s ,

~,I

Schematic tholeiitic
fractionation trend

- .....

Alteration lines

"

i ~,s~o,S
'~,,.',"
t'r
0

100

200

300

400

Zr ppm
20

,S,X~

/o

15

sb

,,,,

s/

5
/

Jo

q,,"

sS

$6 S

/ s SI I s o s S
//...'/"

T
I

I/

sss

~,~'..
0'
0.0

. sJ...f-..~

sS

/ ,,;-'"
t

--

,.,,,,4

Dacit e]'~/

I0

t / ~ dAndeslte e ~

IRhyo"tel ~ . , . ~
~

/,mx''$'e"

~//'/

o
#

Schematic tholeiitic
fractionation trend
......

0.5

1.0

Alterat0on hnes
1.5

2.0

TiO2 %
Fig. 5. (b) AI203-Zr: The fractionation curve is near linear. Plagioclase accumulation may produce anomalously high A1 values in some basalts and andesites. (c) A1203-TiO2: The fractionation curve exhibits a sharp turn owing to Ti-enrichment in the basalts and Ti-depletion from
andesite to rhyolite. This may lead to two intersections by alteration lines. However, this is
normally not a problem as this plot is used for calc-alkaline rocks, where basalts are not common
(and in any case show low Ti enrichment).

1 18

W.H. MacLEAN AND T.J. BARRETT

proximate, but even these are superior to having no guiding fractionation

trends at all. As exploration proceeds, and more least altered sample data become available, the line fits should improve.
In tholeiitic volcanic suites, the shapes of ideal FeO-Zr and TiO2-Zr (Fig.
5a) fractionation curves exhibit initial strong enrichments (D << 1 ) in basalts; this is the typical iron-enrichment trend for rocks of tholeiitic affinity.
The enrichment is followed by a change-over to curves with concave depletion ( D > 1 ) from andesite to rhyolite. M g O - Z r and C a O - Z r fractionation
curves are concave ( D > 1 ) over the full range of basalt to rhyolite. By contrast, AI203-Zr is near linear with a slightly negative slope ( D ~ 1 ) (Fig. 5b ).
SiO2-Zr is near linear from basalt to dacite with a positive slope ( D < 1 ), but
flattens off (D ~ 1 ) in the rhyolites due to quartz precipitation.

Curve fitting
Using least altered samples, chemical data for compatible elements exhibiting concave depletion-type fractionation can be fit using exponential or second-order polynomial curves. Both curves commonly give similar data fits,
as expressed by r values for the curve fit. A polynomial should be fit to the
immobile element profile (Al203-Zr or TiO2-Zr) used to establish the precursor Zr monitor values for altered samples (see below). With this form of
equation, it is simpler to calculate the intersection of fractionation and alteration lines.
TiO2-Zr and F e O - Z r data for least altered basalts can be fit with a separate
set of curves. Fractionation trends for tholeiitic rocks rise steeply in the basalt
to basaltic-andesite range, but follow a depletion trend from andesite to rhyolite. In the basalt to basaltic-andesite range, the trends are sub-parallel to
alteration lines emanating from the origin and, therefore, not useful in mass
change calculations. In this compositional range, it is simpler to use the A1203Zr fractionation curve to calculate mass changes, as alteration and fractionation lines intersect at high angles.

Multiple fractionation curves

In some volcanic sequences, two or more fractionation trends can be recognised on a TiO2-Zr plot, even though separate trends are not apparent in
plots of other major oxides versus Zr. Usually, the separate trends are also
evident in Y - Z r and other HFSE plots, and indicate the presence of more
than one magma type as the source of the volcanic rocks in the stratigraphy.
In all such cases, the sample set should be divided first into subsets based on
these trends. It is for the HFSE plots, in particular, that high quality chemical
analyses for Zr, Y and Nb are required, especially in the basalt range where
their contents are low and the fractionation lines converge.

LITHOGEOCHEMICAL TECHNIQUES USING IMMOBILE ELEMENTS

1 19

When altered samples are superimposed on the TiO2-Zr and Al203-Zrplots,

their locations must be considered in relation to the appropriate fractionation
curve, or mass change calculations will be in error. This emphasizes the importance of separating the altered samples into their proper affinity groups.

Anomalous Zr and other HFSE behavior

In some tholeiitic-transitional suites, Zr becomes moderately depleted in
the rhyolites, while the other HFSE mostly remain incompatible (Kranidiotis, 1985 ). This is usually detected on the Y - Z r plot, although the scatter of
data could be interpreted as either Zr loss or Y enrichment. The problem is
resolved using plots of N b - Z r and Y-Nb, which isolate the depleted component. Zr-depleted rhyolites are locally present at the Phelps Dodge (Kranidiotis, 1985 ) and Aldermac (Barrett et al., 199 lb) VMS deposits.
ALTERATION LINES

In plots of immobile compatible-incompatible element pairs, samples that

initially lay along a fractionation curve may be diluted or concentrated by
mobile mass change. All such sample points will be displaced from the fractionation curve and each will create a linear "alteration line" that passes
through the origin (MacLean, 1990). The precursor composition for each
sample lies at the intersection of the alteration and fractionation lines in each
plot using an immobile compatible-incompatible element pair.
In plots with mobile elements versus Zr (e.g. SiO2-Zr, FeO-Zr, CaO-Zr,
etc.), the mobile elements do not behave in an orderly fashion. Their displacement from the fractionation trend is random, and their precursor compositions cannot be determined directly from their location relative to the
fractionation curve. Instead, the established precursor Zr-value (from A1203Zr or TiO2-Zr) is substituted into the mobile element-Zr fractionation curve
equations to solve for the precursor content of each mobile element. A
spreadsheet computer program is convenient for these calculations.
The high angle of intersection of the alteration and fractionation lines for
immobile compatible-incompatible element pairs provides a very useful tool
for identifying distinctive rock units in alteration zones (Fig. 5b). As the
number of samples in the data set is built up with continued exploration, alteration lines for these units become more evident. Individual alteration lines
identify distinctive rock units and provide a powerful tool for lithostratigraphic correlation.

AI-Ti plots for calc-alkaline rocks

In calc-alkaline rock suites, where the HFSE commonly are compatible and
do not monitor fractionation well, an alternative procedure is adopted that

120

W.H. MacLEAN A N D T.L B A R R E T T

utilizes immobile, compatible elements. Etheridge et al. ( 1983 ) and Richards

et al. ( 1989 ) assumed that Al, Ti and Zr were immobile during alteration and
metamorphism, and used these elements to estimate mass changes in rock
systems they assumed to be homogeneous (i.e. single precursor). Bernier and
MacLean (1989) and Liaghat and MacLean (1992) employed Al203-TiO2
plots to establish the immobility of A1 and Ti in single homogeneous precursor units, and then used these elements to construct fractionation trends for
multiple precursor systems in associated tholeiitic and calc-alkaline suites.
On a plot of A1203-TiO2 (Fig. 5c), volcanic rocks show Ti enrichment in
the basaltic range of fractionation, which is followed by Ti depletion from
andesite to rhyolite. This produces a sharp reversal in the fractionation line.
As a result, strongly altered basalts are not easily distinguished from other
lithologies in this plot. This is generally not a serious problem for calc-alkaline
volcanic rocks which are mostly in the andesite-rhyolite range. It would be
troublesome in the bimodal tholeiitic volcanic suites, but this plot generally
is not used for such rocks. Calc-alkaline rocks may have more scatter in Al
along the A1203-TiO2 fractionation line than tholeiitic-transitional rocks,
which produces larger error in mass change calculations.
MASS CHANGES

Mass changes can be calculated for each mobile element based on the dilution or concentration of an immobile component (MacLean and Kranidiotis,
1987 ). The calculations have some similarities to those of Gresens (1967 )
and the modifications by Babcock ( 1973 ) and Grant ( 1986 ), who used various elements to estimate mass and volume changes in single precursor systems. Regardless of the method employed to establish immobility, certain elements can be used as the basis for mass change calculations in both single and
multiple precursor alteration systems. In the immobile element procedures
we use (outlined below), volume changes do not enter into mass change calculations. Volume changes can, however, be calculated from mass change
results.
The mass of a sample after alteration (reconstructed composition, R.C. ) is
calculated from the initial chemical analysis on the basis of 100 mass units
(mass units and wt% values are interchangeable ) of precursor rocks, using Zr
as the immobile monitor:
R.C. = Zrprecu. . . . /Zraltered X O/ocomponentaltered

(2)

Total mass change and mass changes for each element are calculated as:
Mass Change = R.C. - Precursor Composition

(3)

Immobile components in the chemical analysis of the altered sample in Fig.

121

LITHOGEOCHEMICAL TECHNIQUES USING IMMOBILE ELEMENTS

6 have apparently been decreased by one-third relative to the precursor analysis. The reconstructed composition after alteration, with the immobile components now restored to their initial abundances, is 150 units. This yields a
mobile mass gain of 50 units (i.e., 50 wt%).
In a multiple precursor system, each altered sample is related to its particular precursor as part of the mass change calculation. In small data sets, error
is introduced into the calculation if the igneous fractionation curve is not well
defined, or if a single precursor is taken as representative of a group of samples that initially had slight compositional variation (i.e., ranged along a narrow section of the fractionation curve). New data supplied by ongoing exploration refine the curve equations, sharpen the compositional ranges of volcanic
formations, and define the alteration lines in greater detail.
Increases in mass mostly result from silicification or carbonitization as void
Reconstructed
composition

i::i:i,:;!i::/i ~ ii:i:

MASS

Analysis of
unalteredrock
(precursor)

GAIN

Analysis of
alteredrock

i:i:iiii iiii:
:!i::ii:!:ii:: :iiii:ii

100 . . . . . . . . . . . . . . . .
units
!iiiii!iiiiilili!i!i!i!~!i!i!i
...........
i:::iiiiii!i!i!!!::
!ii!!~ii!iiii!iiiiiiii!ili!i

.-ii;i~,.:i~

:i~i.......
i

iiiiiiiiiiiii!i!iiiiiiiiiii!!i

: iiii

::~::

iiiiiiiiiii!iiiililiiiii!i
ii!iiiii~!i!ii!iiiiiiiii
iiiiiiiii!iiiiiiii!iiiiiii~i

i!i:

....

: . . . . . . . . . . . .
:: :~:::!
:~: ::::

Mobile
::~:: ~::!:
~:~i~i~:~
componentsi.iii!!i~.i!!!!!!i!.i!!ii .
:iiiiiii:iiiiiiiiii:iiii!iiii

::

iiiiiiiiiii!!iii!ii!iiiiiiii

....

i!iiiiiiiiiiiii!iliiii!!iii;iiiiiiiiiii!iiiii
iiiiiiiii!iiiiiiiiii~!!iiiii

::

:::::
~::: .

:::~

~ii ,!~ii i i i ~,~ii i ~i i i

.

"~.~ '1",,~'5~

. . . . . . .

-"

,n~.~O~l~
components
----~
,;,,|

Fig. 6. Illustration of mass change calculations for an altered rock sample, based on 100 units of
precursor. The amounts of immobile elements in the chemical analysis of the altered rock appear to have decreased, but simply have been diluted by added mobile mass. Since the immobile
elements have not lost mass, they must be restored to their initial content, with the other components restored by the same factor. This produces the reconstructed composition ( R . C . ) . Mass
change for each component is the difference between R.C. and the precursor composition.

122

W.H. M a c L E A N A N D T.J. B A R R E T T

Mass changes in host volcanics, Corbet mine

6

I Flavrian andesite
o N o r t h w e s t rhyolite
+ Rhyolite dykes in FA

4
2

o~
0

O
q

o
Z

o~

4-

Feldspar

o~,

-6

-8
-10

~ee

breakdown Silica

~i_.

olo -

leaching

a
i

2O

-10

10

20

AFeO+MgO

Mass changes in felsic host volcanics, Horne mine

Total serlcltlzatlon
of plagloclase In rhyolite

,~

'
,

Serlclte
+ silica

t
i

Serlcite
+ chlorlt~

<~

"I~
"~

,%.

O0 0 e~ e y e e
0 d~e/~4r
.
. . /

,~., -/-".
', ~

SlllCificatlon

~,..: ..............................

' F
b
-

No alteration
i

40

-20

20

ASi02 (%)

40

60

80

LITHOGEOCHEMICALTECHNIQUESUSINGIMMOBILEELEMENTS

123

fillings (amygdales, veinlets, and matrix to breccias, tufts and sediments ). In

these case, the overall volume o f the volcanic units generally is retained. Mass
loss is c o m m o n l y due to leaching o f Si, N a and Ca during chloritization and
sericitization, but can involve Fe, Mn, Mg or K loss as well. The loss is recognised by increased proportions o f inert minerals such as chlorite and sericite,
shrinkage cracks, and slight arcuate depressions o f the ore-footwall contact
over alteration pipes. Mass loss m a y be difficult to visually recognise on a
meter-scale (pillows, flows). For example, a 10% volume loss produces only
a 3% decrease in the radius o f a spherical basalt pillow.
Some mobile components (Si, K, Ca) removed from zones of mass loss are
transferred to the outer parts of alteration zones, some contribute to the orebody (Fe, S, base metals) and mineralized chert beds (Si, Fe, S), and others
(Ca, N a ) are widely dispersed in seawater. Much of the alteration in pipes,
particularly in rhyolite, represents alteration o f volcanic glass, which is very
reactive (the solubility o f silica in the amorphous state is m u c h higher than
for quartz). Depletion of silica in the cores of alteration pipes results from
the high solubility o f amorphous silica, as well as from increases in temperature and w a t e r / r o c k ratios.
Mass changes can be readily illustrated on binary and ternary plots. A useful diagram for monitoring alteration is A (FeO + MgO ) vs. A (CaO + N a 2 0 ) ,
which shows increasing chloritization and Fe + Mg addition as the feldspar
c o m p o n e n t o f the rock is destroyed (Fig. 7a ). A plot o f ASiO2 vs. AK20 (Fig.
7b ) distinguishes sericitized rocks with silica addition from those with silica
loss. In both types o f plots, silica loss is important as a guide to hydrothermal
leaching, which occurs in the most intense parts o f the hydrothermal system.
Calculated mass changes can be examined along individual drill holes, or contoured in vertical and plan sections if sufficient data are available. The mass
changes also reveal differences within broad alteration zones that are mineralogicaUy similar (e.g. sericitized zones). Trends in mass changes across lithological units or on a property scale are thus useful in focusing exploration
programs.
ALTERATION MINERALOGY
Abundances o f alteration minerals in drill core provide a simple and direct
means to portray the extent and intensity of hydrothermal alteration. It is,
Fig. 7. Plots of mass changesfor selected elements. (b) Correlation of mass changesin K20 and
SiO2 in the alteration at the Home mine (data from MacLean and Hoy, 1991). The dominant
alteration was a sericitization accompanied by silicification. Small zones of chlorite-sericite
alteration, accompanied by leaching of silica, occur adjacent to the Cu-bearing VMS ores. (a)
Large losses of CaO + Na20 mass during chloritization of andesite in the footwall of the Corbet
mine are accompanied by major additions of FeO + MgO mass.

124

W.H. MacLEAN A N D T J , BARRETT

Horne volcanics
Quartz

, ~

Quartz

',..'kgai~
." 2', \

~ t

20

40

60

80

100

Sericite

Albite

Montbrav

rhyolite

Quartz

altered
o3
c
O

/,,,,,,,f"e\"l\~ atelyaltered
~"

Sericitite
i

20

Sericite

e
i

40

"~

i0

60

",
-" ~"

""\o\

Strongly altered

/~k~
I ~'~

80

ch.lOritite
wl~=

100

Chlorite

LITHOGEOCHEMICALTECHNIQUES USING IMMOBILE ELEMENTS

12 5

however, difficult and time consuming to measure the modal proportions of

alteration minerals in thin-section, or by expensive methods such as X-ray
diffraction or X-ray imaging. An equally good estimate can be made by calculating normative alteration mineral abundances from bulk rock chemical
data.
In principle, a mineral assemblage portrays the chemical composition of a
rock formed under specific physio-chemical conditions. Alteration around
VMS deposits forms under low pressure (seafloor) greenschist facies conditions ( 2 0 0 - 4 5 0 C ) , producing alteration mineral assemblages consisting
mainly of quartz, chlorite, sericite, albite, epidote, calcite and sulphide. We
use the Niggli-Barth cation normative calculation procedure (Barth, 1962),
which is readily adaptable to a computer spreadsheet, and represents modal
percentage more closely than a weight percent normative calculation. Carbonate and sulphide are computed when CO2 and S analyses are available, or
are assigned as residuals. Alumino-silicate clays, talc, and other minerals are
computed when appropriate. Comparison of normative results with modal
estimates indicates the method is reliable. The normative data are then used
to construct ternary alteration mineral plots (Fig. 8a,b), or to produce contoured alteration mineral intensity maps. Normative mineral abundances are
also useful in the interpretation of oxygen isotope data (MacLean and Hoy,
1991, Barrett and MacLean, 199 ! ).
Hydrothermal alteration minerals do not readily interact or recrystallize
during subsequent regional greenschist facies metamorphism, which occurs
under similar temperature conditions. Bulk chemistry, other than loss of volatiles (water, CO2, S), does not appear to be noticeably changed by amphibolite facies metamorphism, which converts alteration mineralogy to cordierite-anthophyllite-garnet-biotite assemblages (Riverin and Hodgson, 1980;
Bernier et al., 1987; Bernier and MacLean, 1989 ). Normative alteration minerals provide a convenient means to compare alteration zones in greenschist
facies and higher grade metamorphic terranes.
NORMATIVE MINERAL DIAGRAMS
Hydrothermal alteration of sodic rhyolite at the H o m e Mine is illustrated
in Fig. 8a. As alteration progressed, Na and Ca were leached from albitic feldspar and rhyolite glass, and the A1-Si residue combined with Fe + Mg and K
from the rock and hydrothermal fluid to form chlorite and sericite, respecFig. 8. Triangular plots of cation normative alteration minerals. (a) Quartz-albite-sericite: The
diagram illustrates the sericitization and silicificationof rhyolite in the alteration zone at the
Home mine (from MacLean and Hoy, 1991). (b) Quartz-chiorite-sericite: Chlorite and sericite, formed by alteration of plagioclase components in Montbray rhyolite, were subsequently
concentrated by wholescaleleachingof silica (from Barrett and MacLean, 1991).

126

W.H. MacLEAN AND T.J. BARRETT

Horne volcani~ ro~ks

50
Sericite

40

o~
cO
~

30
Ch

a~

20

<
D

10

Precursor r

40

6O

8O

O0

Si cation %
Montbrav

rhvolites

Quartz

I00{

b
80'
ee

0 ........
Precursor
0

~
Weakly to moderately
~"
~
altered rhyolites
-... ~ , ~

60

, m

401

~"

hlorite

altered rhyolites
20
0

10

20

30

40

(Fe+Mg) cation %

Quartz

50

LITHOGEOCHEMICALTECHNIQUESUSINGIMMOBILEELEMENTS

127

tively. Because A1 was immobile, the abundance of chlorite and sericite (both
Al-bearing) was limited to the initial Al-content of the rhyolite. The least altered rhyolite samples plot close to the albite-chlorite tieline, but alteration
has shifted other samples towards the sericite-chlorite boundary, with a majority of them near the sericite apex. A plot ofquartz-sericite-chlorite reveals
that the dominant alteration assemblage is quartz-sericite (MacLean and Hoy,
1991).
In the early stage of alteration of albite to chlorite and sericite at low water/
rock ratios, rhyolite retains most of its initial quartz content ( ~ 50%). With
increased alteration, this assemblage can be reduced to sericite and chlorite,
as occurs in alteration zones in the Montbray rhyolite near Noranda (Barrett
and MacLean, 1991 ). Residual concentration of these two minerals is caused
by wholescale hydrothermal dissolution of quartz at high water/rock ratios
(Fig. 8b). Extremely altered rhyolites plot along the chlorite-sericite tieline.
Chlorite and sericite are stable under the alteration conditions of VMS deposits in greenstone belts (Riverin and Hodgson, 1981 ), whereas AI-Si clay
minerals are not. Other stable phases include rutile, zircon and REE-bearing
minerals.
BINARY CATION DIAGRAMS

Alteration of volcanic rocks is also well portrayed on binary cation diagrams. Quartz, albite, chlorite, sericite and other minerals can be plotted as
mineral formulae along with cation percent values of elements in the altered
rocks. Samples of silicified rhyolite at the Home mine plot between the precursor and quartz on an A1-Si diagram (Fig. 9a). Rhyolites affected by strong
silica-leaching migrate towards the sericite-chlorite tieline.
The S i - ( F e + M g ) diagram (Fig. 9b) is useful in revealing quartz loss and
the inertness of chlorite and sericite. Initial alteration of the Montbray rhyolite spread samples along an approximately constant Si trend, limited by the
quartz-sericite and quartz-chlorite tielines. Loss of Si then shifted the samples to the sericite-chlorite tieline where they formed stable residues.
VOLUME CHANGES

Generally we examine alteration in terms of absolute changes in the amount

of mass transferred into or out of a rock by hydrothermal fluids. This is more
Fig. 9. Plots of percentages of cations in bulk rock chemical analyses. Mineral formulae are also
shown in terms of cation components. (a) A1 vs. Si plot illustrating alteration of rhyolite at the
Home mine. Silicified samples plot between precursor and quartz. The sericite-chlorite tieline
forms a barrier to further alteration (data from MacLean and Hoy, 1991 ) (b) Si vs. (Fe + Mg)
plot illustrating alteration of the Montbray rhyolite. Sericite and chlorite formed by alteration
of plagioclase are concentrated along the sericite-chlorite tieline by wholesale leaching of quartz.

128

W.H. MacLEANANI)1 .J. BARRETT

important than volume changes as a parameter to examine and interpret hydrothermal processes. Of course, volume will usually change as mass of the
rock changes, but an extra step is required to calculate this variable.
Changes in rock volume owing to alteration can be estimated from measured precursor and altered rock densities and the measured ratios of an immobile element, e.g., Zrprecursor/ Zraltered (Shriver and MacLean, 1993 ). Rock
densities and volume changes can also be estimated closely from normative
mineral contents of precursors and reconstituted samples, and mineral densities. Absolute volume of a rock unit may not change as a result of void filling
or void formation, although the volumes of individual minerals change. Many
alteration minerals have fixed or narrow ranges in density (quartz, albite,
sericite, epidote), but chlorite has a wider range because of Fe-Mg substitution (chlorite densities can be estimated from microprobe mineral analyses ).
Volume loss in strongly chloritized rhyolite at the Phelps Dodge VMS deposit was as much as 60% (MacLean and Kranidiotis, 1987). By contrast, a
10% volume increase was estimated for the bulk of the Horne mine alteration
zone, where silicification was widespread (MacLean and Hoy, 1991 ).
EFFECT ON <5180 VALUES

Mass changes also affect the interpretation of bulk c~80 data for altered
rocks (MacLean and Hoy, 1991; Barrett and MacLean, 1991 ). Not all whole
rock c$180 variation is caused by changes in temperature and ~t80 of the hydrothermal fluid. For example, the bulk c$180 of an altered rock composed of
quartz (~ 180 ~ 10%o) and chlorite (c5180 ~ 20/00) will be lowered by leaching
of quartz at constant T and ~t 80 ~ 0%0 (fluid) (see MacLean and Hoy, 1991
for calculation procedures). Complete leaching of the quartz under these conditions would produce a chloritite rock with a bulk ~ 180 ~ 2%0. Similarly, silicification increases bulk c~180 values, with the higher values produced at lower
alteration temperatures. As a result of these effects, c$180 values of altered
rocks should be assessed in light of mass changes as well as temperature and
fluid 6180 values.
MOBILITY OF THE REE

The REE are commonly incompatible in igneous processes, particularly in

tholeiitic-transitional suites, but only the heavy REE (Lu and Yb) are consistently immobile during hydrothermal alteration (MacLean, 1988 ). The heavy
REE produce linear alteration lines with Zr and other immobile elements, but
the light-REE data frequently scatter, indicating some mobility. Such mobility may cause changes in the slopes of chondrite-normalized REE profiles (e.g.
LaN/YbN ratios), and thus introduce errors in the determination of magmatic affinity. For this reason it is essential to first demonstrate immobility

LITHOGEOCHEMICAL TECHNIQUES USING IMMOBILE ELEMENTS

129

of all the REE in a suite of altered rocks before using the slopes of the REE
patterns to obtain petrogenetic information. This is done by plotting each
REE against an immobile element such as Zr.
If the REE have been immobile, the addition of mass to a rock causes REE
profiles in a single precursor alteration system to shift vertically down on
chondrite-normalized diagrams, whereas the removal of mass causes REE
profiles to shift vertically upwards. If the REE also have been mobile, it is
difficult to distinguish these various effects. To evaluate these changes, the
profiles are restored (normalized) to the original Lu (or Yb) value of the
precursor. In some alteration zones, as at Phelps Dodge (MacLean, 1988)
and Ansil (Barrett et al., 1991a), this produces a fan-shaped array of profiles
with Lu as the hinge. La is the most mobile of the trivalent REE, with the
others decreasing uniformly in mobility towards immobile Lu (MacLean,
1988 ). A fan of profiles results from REE mobility, which ranges from uniform addition of the lighter REE relative to the precursor, to uniform depletion of the lighter REE.
Mobile REE depletion is encountered in the most intensely chloritized parts
of alteration zones below VMS deposits (Campbell et al., 1984; MacLean,
1988, Barrett et al., 1991 ). Hydrothermal fluid temperatures are highest ( 300400C) in these zones, which were subjected to silica depletion and commonly contain stringer-copper mineralization. REE addition is mostly in
nearby zones of sericite alteration and silicification, where fluids were cooler
and precipitated REE minerals. Light-REE depletion anomalies encountered
in altered rock during mineral exploration are indicative of centers of high
temperature hydrothermal fluid flow. REE anomalies of either type are important to document from an exploration viewpoint.
DISCUSSION
A hypothetical example of a sequence of greenstone volcanic rocks ranging
from basalt to rhyolite being explored for VMS deposits is illustrated in Fig.
10 to highlight routine procedures used for lithological identifications and the
imprints of alteration provided by immobile elements. One drill hole encounters relatively unaltered (least altered) stratigraphy, and from sampling data,
the volcanic units are divided into two volcanic affinity groups, one tholeiitic
and the other mildly calc-alkaline, using a Y - Z r plot. The main lithologies
(basalt-andesite-dacite-rhyolite) are identified for each affinity type using
least altered samples and TiOE-Zr and A12Oa-Zr plots; fractionation lines are
fitted to each plot.
Geochemical data for the least altered rocks (Fig. l 0) reveal that a tholeiitic basalt to rhyolite sequence is overlain by mildly calc-alkaline rhyolite to
basalt units. Rhyolite-rhyolite contacts of two types are present: between
tholeiitic rhyolites A and B (B is more fractionated than A), and tholeiitic

130

W.H. MacLEAN AND T.J. BARRETT

Chemostratigraphy based on
least altered samples from
surface and drilling transects

Mildly

calc-alkaline

TIO2%

volcanic

AI203%

sequence

Y ppm

15- ~'Xoo~.~y

1"5"1 B a s ~ A nDac
d
=7'

Zr
Contact

of

500

Interef

Zr

Tholeiitic
TIO2%

Zr

500 ppm

sequence

Y"ppm

15-

Zr

volcanic

AI203%

1.5-

Basalt to andesite

500

500

Zr

I Rhyolite

Dacite

500

Zr

500 ppm

Synvolcanic felsic
intrusion (tholeiitic)

~,, Fractionation trends

.............
Strongly altered rocks
near massive sulfide lens

Alteration lines
Altered

mildly

TIO2%
]

AI203%

15

TiO2

calc-alkaline

volcanic

sequence

Y ppm

15

/ ' ,' '?~

/ ~"s .And
l',"

~ll""~=.RhyC l',~ '~

Zr

500
Altered

:-_- ~

TIO2%

'a'k\1
Zr

tholeiltic

500

Zr

volcanic

AI203/o

500 ppm

sequence

Y ppm

~o O

,O~RhyA

F-~

'

Zr

500

Zr

500

Zr

(~)- (~) Rhyolite units

5(~0

Zr

500

Zr

500 ppm

LITHOGEOCHEMICAL TECHNIQUES USING IMMOBILE ELEMENTS

131

rhyolite B and mildly calc-alkaline rhyolite C. Both types of contact are sites
of felsic-hosted VMS deposits in the Noranda district, Quebec: the former for
the Aldermac ores (Barrett et al., 199 l b), and the latter for the Mobrun and
Delbridge ores (Barrett et al., 1991, 1993). A number of VMS deposits at
Noranda also occur at andesite-rhyolite contacts (e.g., Ansil, Norbec, Millenbach: Gibson and Watkinson, 1990; Chartrand and Cattalani, 1990). Using
the lithogeochemical fractionation-alteration relations outlined earlier, lithological contacts can be traced from least altered stratigraphy through alteration zones, and correlated across faults.
The possibility of a genetic relationship between the volcanic rocks and
intrusive bodies (Fig. 10 ) also can be established with maj or (Goldie, 1978 )
and trace (Paradis et al., 1988) elements, using the fractionation relations
and elemental ratios described above. A co-magmatic intrusion in the upper
levels of a volcanic pile will provide an important source of heat to drive
hydrothermal circulation.
It is possible to identify the precursors lithologies of volcanic rocks that
have been intensely hydrothermally altered and mineralized to the point of
being unrecognizable. The immobile element imprint not only yields the precise rock type, but also the magmatic affinity. In the Noranda VMS deposits,
the paths of alteration can be followed by mass change and normative alteration mineral plots. For example, silicification and sericitization are dominant
processes in rhyolite at the Horne mine (Figs. 7a, 8a, 9a; MacLean and Hoy,
1991; Barrett et al., 1991a); at the Corbet mine plagioclase breakdown in
andesite is combined with chloritization and silica leaching (Fig. 7b; Barrett
et al., 1993 ); and in the Montbray rhyolite extreme mass loss, chloritization
and residual buidup ofsericite occurs in mineralized zones (Fig. 8b, 9b; Barrett and MacLean, 1991 ).
SUMMARY

Immobile elements provide new lithogeochemical tools for mineral exploration. Immobile HFSE are employed to distinguish between tholeiitic and
Fig. 10. Schematic example of lithogechemical procedures applied to an exploration drilling
program. In the upper figure, a drill hole intersects relatively unaltered volcanic stratigraphy.
Samples are first divided using Zr/Y ratios into an upper mildly calc-alkalinegroup and a lower
tholeiitic group (magmatic affinities should be confirmed with further trace element and REE
data). Fractionation curves in TiO2-Zr and A1203-Zr space are then established for each magmatic group. Core is generally sampled every 10-20 m. In the lower figure, a drill hole penetrates a strongly altered (light gray) part of the same stratigraphy in the vicinity of a VMS
deposit (black lens). Mass changes due to alteration displace samples of each volcanic unit from
the fractionation curves along distinct alteration lines. Three rhyolite types (A-C) are present,
as in the unaltered sequence, but the three rhyolites are more readily recognized in the altered
rocks. The felsic intrusion in this example is of tholeiitic affinity and would be related to the
lower volcanic sequence.

132

W.H. MacLEAN AND T J BARRETT

calc-alkaline affinities in fresh and altered rock suites, and to monitor fractionation of the compatible elements. The HFSE, AI and Ti form the basis for
quantitative estimation of mobile element mass changes. Severely altered rocks
that have lost primary textural, mineralogical and chemical identity can be
confidently classified as to initial rock type and magmatic affinity.
Major element chemical data required for the calculations and plotting procedures are available from routine bulk rock chemical analyses, generally
available in mineral exploration programs. However, precise and accurate
trace element analyses are necessary for the establishment of rock affinities,
and fractionation and alteration lines. The lithogeochemical parameters produced by these techniques can be plotted on exploration maps, cross-sections
and discrimination diagrams. The exact identification of rock types and rock
affinities allows correlation of volcanic units between drill holes and across
zones affected by hydrothermal alteration and faulting. This information generates a comprehensive insight to volcanic lithostratigraphy, hydrothermal
alteration and ore-forming processes in greenstone belts.

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