Journal of Geochemical Exploration, 30 (1988) 223-242 223

Elsevier Science Publishers B.V., Amsterdam - - Printed in The Netherlands

Applications of rock geochemistry to productive

plutons and volcanic sequences*

G.J.S. GOVETT and P.R. ATHERDEN

Department of Applied Geology, University of New South Wales, P.O. Box 1, Kensington,
N.S. W. 2033, Australia
(Received August 21, 1987; revised and accepted March 29, 1988)

ABSTRACT

Govett, G.J.S. and Atherden, P.R., 1988. Applications of rock geochemistry to productive plutons
and volcanic sequences. J. Geochem. Explor., 30: 223-242.

There is no agreement on classification and recognition of productive granitoids. The S-type

and I-type classification, the magnetite-ilmenite classification, and many others do not seem to
have universal applicability. A large proportion of the periodic table has been proposed to identify
"specialized", and in particular "tin specialized", granitoids. Empirical evidence indicates, how-
ever, that a few elements - notably K, Mg, Rb, St, and Li - provide the best general indicators.
Specialization provides only an indication of the potential for mineralization, provided tectonic
and other geological conditions are appropriate. A fundamental requirement for rare metal mi-
neralization appears to be the availability of water and, in particular, wet sediments to react with
the magmatic process.
A small number of elements (notably Fe, Mn, Na, K, Mg, Ca, and base metals) give extensive
local scale responses for most volcanic-exhalative deposits. A wide variety of other elements, in-
cluding REE, have also been shown to be effective at particular deposits but appear to offer no
advantage over the conventional elements. The belief that Zn-Cu and Zn-Pb-Cu massive sulphides
are essentially confined to calc-alkaline volcanic sequences is less certain, largely because it is now
recognized that classification of volcanic rocks in mineralized areas as tholeiitic or calc-alkaline
by conventional AFM diagrams may not be reliable. The use of immobile elements (such as Ti,
Zr, Y, and Cr) appears to overcome this problem.

INTRODUCTION

The organizers of the Southern Europe Exploration Geochemistry Sympo-

sium suggested that this keynote address should review the use of exploration
rock geochemistry for mineralization associated with granitoids and subma-

* Based on paper given at Southern Europe Exploration Symposium in Athens, Greece, 9-11
November, 1986. The symposium was sponsored by the Instituteof Geology and Mineral Explo-
ration,and the Association of Exploration Geochemists.

0375-6742/88/$03.50 © 1988 Elsevier Science Publishers B.V.

224

rine volcanic rocks. Rock geochemistry - defined as the measurement of the

chemical composition of bedrock material to detect spatial element distribu-
tion patterns that can be related to mineralization - can be used on a regional
scale, and on a local or mine scale to measure geochemical responses up to 1 or
2 km from an individual deposit, or to detect wall-rock anomalies related to
individual ore shoots or horizons.
Although some common geochemical features related to deposit types are
now emerging from accumulated data, the overwhelming impression is one of
diversity of response and lack of a general geochemical prescription to detect
particular deposit types. This paper reviews regional scale geochemical re-
sponses and some aspects of local scale studies where significant efforts have
been made to find universally applicable geochemical criteria.

MINERALIZATIONASSOCIATEDWITH GRANITOIDS

Most of the early attempts to distinguish between productive and non-pro-

ductive granitoids concentrated on determining if one or more ore elements
had an abnormal concentration (in whole rock or mineral separates) that could
be used to recognize a mineralized intrusion. The data for most elements was
equivocal, and only Sn appeared to show a reasonably consistent pattern of
enrichment in Sn-bearing felsic rocks (Govett, 1983). More recent work has
concentrated on a multi-element approach, with considerable progress in de-
vising genetic classifications of granitoids that can be related to associated
mineralization.

Granitoid classifications and mineralization

The concept of S-type (sedimentary protolith) and I-type (igneous proto-

lith) granitoids in the Tasman Orogenic Zone of eastern Australia recognizes
the affinity of particular types of mineralization for particular types of grani-
toids (Chappell and White, 1974 ). Characteristically, Sn-U-rare-metal miner-
alization is associated with the S-type, and Cu (Mo) porphyry mineralization
is associated with the I-type.
A scheme proposed by Ishihara (1977, 1981 ) divides granitoids into a mag-
netite series and an ilmenite series. He suggests that the magnetite series gran-
itoids are generated at deep levels (upper mantle and deepest crust) with high
02 fugacity, whereas the ilmenite series granitoids are generated at shallower
levels in continental crust and have been mixed with carbon-bearing rocks.
This scheme does not exactly correspond with that of Chappell and White
(1974). All magnetite-series granitoids are I-type, but ilmenite series grani-
toids are not exclusively S-type (Takahashi et al., 1980)
Ivanova and Naumov (1985), using data from 30 rare-metal deposits in the
USSR and Mongolia and from published data on deposits elsewhere in the
 225

world, have proposed three groups of granites: standard granite; lithium fluor-
ide granite (including the Sn-granites) which are characterized by high con-
tents of Li, Rb, Ta, Nb, and F; and intermediate granite with associated W
deposits. Trace element composition in wolframite - Ta, Nb, Sc, Y, REE (rare
earth elements) - plotted against the content of these elements in whole rock
provides effective separation of the three groups of granites containing W
deposits.
Tauson et al. (1983) and Tauson (1984) state that source rocks affect the
granitoid type and their potential for containing ore, but they suggest that the
approaches by both Chappell and White (1974) and Ishihara (1977, 1981 ) are
inadequate because of differing modes of formation of granitoids. Within ge-
netic groups there may be quite large differences in their rare-element content,
formation conditions, and potential ore content. Thus, rocks that appear pet-
rographically quite similar may have very different trace-element levels. Tau-
~on (1984) postulates a granite rare-metal index [ F ( L i + R b ) / ( S r + B a ) ]
anging from 2.5 in plagiogranite to 3460 in plumasitic (Sn and rare-metal)
ranite.
The validity of the S-type and I-type classification has been challenged by
Plant et al. (1980, 1983) who consider the model to be invalid in the Scottish
Caledonides and probably elsewhere. A group of late discordant granites of the
northern UK are enriched in granophile elements but have little associated
metalliferous mineralization, whereas petrochemically similar rocks in south-
west England form a metallogenic province. Large quantities of metals were
introduced into the Scottish Caledonian Province by late tectonic granites in
a porphyry suite (enriched in Mo-Cu-Ba-Pb-Sr or Mo-W-F) and in an alkali
granite suite (enriched in Sn-Be-Li-U-K-Rb-Th-F ). The authors demonstrate
the failure of the S-type and I-type model for these metalliferous plutons (me-
talliferous in the sense of being enriched in granophile metals but not neces-
sarily bearing metalliferous mineralization). The alkaline granite suite would,
according to the Chappell and White (1974) model, have a sedimentary pro-
tolith. Geophysical (gravity and magnetic ) evidence shows, however, that the
crust into which the Caledonian granites were emplaced was continental thick-
ness Precambrian high-grade metamorphic rocks (probably granulites at
depth ). There is, therefore, no evidence for the existence at depth of a contem-
porary mass of wet sediments which is conventionally required for S-type
granites.
In a discussion of the role of volatiles in the formation of granitoids and
mineral deposits associated with them, Tischendorf (1974) states that Sn, Li,
Rb, W, Mo, Be, F, and H20 are important components of the granitoids as
indicators of their metallogenic potential. He stresses that the relation be-
tween trace-element accumulations in granitoids and trace-element accumu-
lations in related deposits is by no means clear. Both accumulations can be
considered as results of the process of magmatic differentiation, or they can
226

represent partial results of relatively independent processes of preconcentra-

tion and lateral secretion.
According to Taylor and Fryer (1983), the diversity of mineral deposits re-
lated spatially to granitoid rocks is a direct consequence of the diverse origins
of granitic magma, but water is the single most important compositional vari-
able. Granitoid rocks of peralkaline affinity are, however, essentially anhy-
drous and other fluid types - dominated by fluorides and carbonates - appear
to be important in determining metal concentrations.

Specialized Sn and W granitoids

The term "specialized" granitoids is used to denote granitoids enriched in

granophile and other elements - such as Be, F, Li, Mo, Nb, Rb, REE, Sn, W,
Ta, Y, and Zr (Jackson and Ramsay, 1986). Comparing published geochemical
data on granites of the world, Tischendorf (1974) demonstrated that special-
ized granites have significantly higher contents of Si02 and K20, and signifi-
cantly lower contents of TiO2, Fe203, MgO, and CaO than normal granites.
Granophile elements (B, Nb, Ta, Cs, U, Th, REE) are enriched, and grano-
phobe elements (Ni, Cr, Co, V, Sr, Ba) are impoverished in specialized granites
compared with normal granites. There is a strong increase of the granophile
elements from the older to the younger intrusive phases in the specialized in-
trusive complexes.
Kwak (1986) used Rb/Sr ratios to indicate the degree of evolution or differ-
entiation of the parent magma and showed that the largest W-skarns are as-
sociated with highly evolved I-type granites with Rb/Sr ratios of about 1.0
(e.g., Mactung and Cantung in the Yukon, Canada). Most large oxidized W-
skarns (e.g., King Island, Tasmania, Australia) are related to less evolved
granites with Rb/Sr ratios of about 0.4. The largest Sn-W skarns are associ-
ated with evolved S-type granites. Some large Sn-W skarns appear to be as-
sociated with less evolved S-type granites.
Kwak and White (1982) suggest that U and REE are diagnostic of W-Sn-F
mineral association. It may be expected that associated granitoids would have
a higher background radioactivity. Data from southeastern Australia show that
radioactivity is indeed anomalous (with high U) in granitoids that host W-Sn-
F mineralization where W occurs as wolframite in veins (Collins et al., 1982;
Yeates, 1982; Yeates et al., 1982; Webster, 1984). Granitoids hosting Cu-Mo-
W mineralization, where W occurs as scheelite, are not anomalous in U. De-
tailed studies on 6 granitoids in New South Wales by Thein (1986) confirmed
the general association of high radioactivity with Sn-W mineralization. Ford
and O'Reilly (1985) showed that data from airborne gamma-ray spectrometric
surveys over Nova Scotia (Canada) also correlated with specialized granitoids
and mineralization.
 227

Sn and Cu porphyry provinces

Tin and Cu porphyry provinces are essentially mutually exclusive - Cu is

associated with granodiorites and monzonites, whereas Sn characteristically
is associated with more acidic granites. However, some of the Bolivian Sn de-
posits (notably Llallagua, Potosi, Oruro, and Chorolque) have some similari-
ties to Cu porphyry deposits (Sillitoe et al., 1975).
Whereas it may be misleading to pursue too close a comparison between Cu
porphyry deposits and a Sn analogue, the significant point that seems to have
been overlooked in most discussions is that the Bolivian deposits described by
Sillitoe et al. (1975) occur in rocks that are compositionally comparable to the
characteristic host rocks of Cu porphyry deposits. In this context, the obser-
vation of Flinter et al. (1972) - that disseminated Sn deposits occur in more
basic granites - obviously assumes a new importance.

Recognition of specializedgranitoids

Granitoids that are host to Cu (Mo) porphyry deposits do not have a diag-
nostic geochemical signature (Govett, 1983 ). Regional geochemical recogni-
tion of porphyry deposits has generally been through reconnaissance stream
sediment geochemistry (e.g., Govett and Hale, 1967; Harkin, 1976), followed
by identification of large-scale alteration. Deposits of Sn, W, U, and rare met-
als do not generally give rise to large secondary anomalies, and individual tar-
gets are much smaller. There is, therefore, considerable incentive to recognize
potentially productive granitoids.

Use o/K, Rb, St, Mg, and Li

There is a positive correlationbetween K and Rb for non-specialized gran-
itoids.The specialized granitoids lie in a separate fielddistinguished by en-
hanced Rb relativeto K. In the porphyry granitoidsthere isa trend of increasing
K and Rb from non-mineralized to mineralized rocks in any particularregion.
The absolute level of concentration is,however, differentin each region, and
no universallyapplicablebackground can be assumed.
The specializedgranitoids,porphyry granitoids, and normal granitoids all
plot on a singletrend on the basis of K / R b and Rb/Sr ratios,but the special-
ized granites all fallin one zone with high Rb/Sr and low K / R b ratios (Fig.
1 ).The Rb/Sr ratioalways increases,and the K / R b ratiogenerallydecreases,
from non-mineralized to mineralizedrocks for non-specializedgranitoidswithin
any particular region. Again, the absolute values of these ratios are distinct
and differentin each region, and no universal background is applicable.
The Cairngorm granite of the U K (52)* and the plumasitic granite of the

* N u m b e r s in Tables 1, 2.
228

Rb:Sr
• Cu porphyry
1000:

o Cu porphyry
a~eas -- ~a~ron
23=
100: " So m i n e r a l i z e d
m
m

39 . / 8 = Miuoralizod -
. 37 = . J other
10:
^^ 52 +- +
" So areas -
barren

54 . ~ ' ~ . = •~ + Arabian Shield

m •.4H~I"
× •
•-• x Caledonides
~o÷
o Crustal averages
0. 1:

8.01 ' ~ ' ' J'"l . . . . . . . . t ~. , ' ' ..... I

IO 100 1000 10000

K:Rb

Fig. 1. Variation in K:Rb and Rb: Sr ratios in barren and mineralized granitoids. Numbers refer
to data in Table 1 (modified after Govett, 1983).

Arabian Shield (46) lie well within the Sn-mineralized specialized granitoid
field in the R b / S r - K / R b diagram in Fig. 1. Both these granitoids have Sn
mineralization (Tables 1 and 2), but in neither case is it economic (in the case
of the Arabian Shield this might be a matter of non-discovery to date).
Similarly, the Davis Lake pluton (36) that hosts the East Kemptville tin
deposit and the Lake Lewis pluton (37) that hosts the Millet Brook uranium
deposit in Nova Scotia fall close together in Fig. 1. Chatterjee et al. (1983)
showed that the specialized plutons of the area could be readily discriminated
from the non-specialized plutons by the relation between Rb and K. However,
a multivariate approach using U, Sn, Th, Li, and F was required to discriminate
between the uraniferous and stanniferous granitoids. Both plutons are en-
riched in Sn and U.
The barren Anchor granite adamellite (22) also falls within the specialized
granitoid field in Fig. 1, although it is far less specialized than the nearby Sn-
mineralized Anchor granite (23). It is evident that the more specialized the
granitoid is, the more likely it is to have significant Sn mineralization. Thus,
 229

TABLE1

Contents of K, Mg, Li, Rb, and Sr in some barren and mineralized intrusive rocks referred to in
the text or numbered in Figs. 1 and 2

Sample Rock type, location K Mg Rb Sr Li

No. (number of samples ) (% ) (% ) (ppm) (ppm) ( ppm )

1 average low-Ca granite 4.2 0.16 170 100 40

2 average granote 3.47 0.33 145 240 30
3 average granodiorite 2.55 0.95 110 440 25
22 b. Anchor Mine, GA (6) 3.9 0.22 365 75 46
23 m. Anchor Mine, G (6)* 3.8 0.04 1035 5 186
24 b. Queensland, Dido, G (12) 1.25 1.16 45 812 7
25 b. Queensland, Dumbeno, G (19) 2.78 0.21 127 374 6
26 m. Queensland, Elizabeth Creek, G (73) 3.93 0.07 427 26 31
27 m. Queensland, Finlayson, G (6)* 3.98 0.25 388 43 94
28 m. Queensland, Mareeba, G (23)* 3.53 0.26 356 88 69
29 m. Queensland, Esmeralda, G (30)* 4.16 0.17 291 78 39
30 m. Queensland, Almeden, G (15) 2.47 1.44 146 196 19
31 m. Queensland, Herbert River, G (40) 3.47 0.25 233 101 29
32 m. St. Austell, G {35)* 3.84 0.18 886 51 31
33 m. Carnmenellis, A ( 1 )* 4.3 0.28 400 80 400
36 m. Nova Scotia, Davis Lake, G (94)* 3.39 0.11 700 31 146
37 m. Nova Scotia, Lake Lewis 3.64 0.03 769 38 517
GRD-D (136)
41 m. Ririwai, Nigeria, G {15)* 4.14 0.13 580 8 130
42 m. Ririwai, Nigeria, G (10)* 4.22 0.01 800 3 180
43 b. Arabian Shield, AG 3.81 0.05 110 38 21
44 (m.) Arabian Shield, AG 3.83 0.05 169 20 51
45 b. Arabian Shield, AFG 3.75 0.07 151 47 18
46 m. Arabian Shield AFG* 3.74 0.05 386 38 184
48 b. Arabian ShieldMG, GRD 3.22 0.65 107 446 21
50 b. Foyers, G (59) 3.32 1.03 95 1010 20
51 (m.) Helmsdale, G (15) 3.93 0.22 221 495 12
52 (m.) Cairngorm, G (69)* 4.15 0.08 455 67 75
53 (m.) Barrytown, G (1) 4.20 0.43 314 68 124
54 (m.) Doctor Falls, G (1) 3.59 0.38 211 102 78
55 (m.) Bateman, G (1) 0.87 0.12 150 37 15

* = tin-bearing granites.
b. = barren; (m.) = minor mineralization; m. = significant mineralization; G = granite s.s. and
s.1.; AG = alkali granite; AFG = feldspar granite; MG = monzogranite; GRD = granodiorite; GA =
granite-adamellite; A = adamellite. Sources of data: 1 = S.R. Taylor (1968); 2, 3 = Turekian and
Wedepohl (1961); 22, 23= Groves (1972); 2 4 - 3 1 = Sheraton and Black {1973); 32= Exley
(1958); 33= Butler (1953); 36, 37= Chatterjee etal. {1983); 41, 42= Imeokparia, 1983; 43-46,
48 -- Jackson and Ramsay, 1986; 50 - 52 --- Plant et al. ( 1980 ); 53 - 55 = Tulloch and Mackenzie,
1986.
230

TABLE 2

Summary of mineralization in granitoids listed in Table 1.

No. Name and location Mineralization

23 Anchor Mine (Australia) Sn
26 ElizabethCreek (Herberton Tin Field,Australia) Sn
27 Finlayson (Annan R. Tin Field,Australia) Sn
28 Mareeba (Australia) W, Sn, Cu
29 Esmeralda (Australia) Au, Sn
30 Almaden (Australia) Cu, Ag, Pb, Zn
31 Herbert River (Australia) (Cu, Pb, W)
32 St. Austell(U.K.) Sn
33 Carnmenellis (U.K.) Sn
36 Davis Lake, Nova Scotia (Canada) Sn
37 Lake Lewis,Nova Scotia (Canada) U (Sn)
40 Mt.Pleasant,New Brunswick (Canada) W, Mo, Bi, Sn
41 Ririwai (Nigeria) Sn
42 Ririwai (Nigeria) Sn
44 Arabian Shield,agpaiticgranite Nb-Zn-REE-U-
Th
46 Arabian Shield,plumasiticgranite Sn, W, Ta, Nb,
Pb, Zn, Ag
51 Helmsdale (U.K.) U, Pb
52 Cairngorm (U.K.) Sn, Nb, Pb, Zn,
Ag
53 Barrytown (New Zealand) W
54 Doctor Falls (New Zealand) W
55 Bateman (New Zealand) W

although the Esmeralda granite (29) is classified as a Sn granite, gold has been
the only important mineral recovered.
The W-bearing granites of New Zealand {53-55) appear to lie at the lower
end of the zone of specialized granites on Fig. 1. It is noteworthy that the Ma-
reeba granite (28), which is classified as a Sn granite, also lies in this zone and
is host to the Mount Carbine wolfram mine.
Govett (1983) pointed out that on the basis of published data, Sn-bearing
granitoids may be recognized by one or more of the following relations:
-low ratios for K/Rb, Mg/Li and B a / R b
-high ratios for Rb/Sr.
Because not all Sn granites are anomalous in all four ratios, he suggested that
a multiplicative ratio of (Rb ~X Li) / (Mg X Ba X Sr X K ) offered the prospect
of a discriminator giving high values for Sn granites and low values for barren
granites. A modification of this relation to accommodate the frequent lack of
Ba analyses in published data is ( Rb 2 X Li ) / (K X Mg X Sr).
Figure 2 gives some examples of this calculation. The ratios have a range of
 231

23.Anchor-
42.Ririwai
37.Lake Le~is ~ / / / / / / / / / / / / / / / / / / / / ~
41.Biriwai-
33.Carnmenellis- i
36.Davis Lake-
46.Arabian Shield-.llllllll~l~r1111111111111111.
26.Elizabeth Creek-

32.St. Austell
4 4 . A r a b i a n S h i e l d ' ! : ~ : ~ ~5~;:;:;:~:~!~:~:~:;:;:;:;~:~;:;:1
ZT.Finlavson
28.~ar~eba
53. Barr'vtl
zg. Esmera
45. A r a b i a n Shiq
43. A r a b i a n Shiq
5 4 . D o c t o r Fa
3 1 . H e x ' b e r t :::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
1 . A u . l o w - C a gz, a n i ' c e I
B Sn d e p o s i t s

Z . A v . 9r'a~ i~o J ~U deposits

5 1 . He I ms d a I e ::::::::::::::::::::::::::::::::::::::::::::::::
38. Almaden ::::::::::::::::::::::::::::::::::::::::: I Se occurrehces
25. Dumba.o I I
3.Av. 9ranodior ire ~Other mineralization
48. A r a b i a n S h i e l d
58. F o y e r s [-lBarren
24. Dido , ,,,.. , , ,,,,,~ ....... i iI..d i i . . . i Ji.ull i ~l.l. , i..id
i i I

8. 0888881 8. 88081 O. 881 O. 1 18

(Rb2xLi)/(KxM9xSr)

Fig. 2. Discrimination between barren and mineralized granitoids on the basis of K, Mg, Rb, Sr
and Li contents. Numbers refer to data in Table 1.

7 orders of magnitude. Values greater than about 1 × 10 -3 are indicative of

specialized granitoids - mostly Sn, on the basis of available data. The essential
conclusions are the same as those derived from Fig. 1. Highly specialized and
evolved granitoids are Sn-bearing or U-bearing but are not necessarily host to
significant mineralization. Granitoids that are less specialized than the Sn and
U granites, but more specialized than porphyry and normal granites, are po-
tentially mineralized in W or base metals.

Local-scale exploration case histories

There are relatively few case histories of rock geochemistry surveys for in-
dividual deposits associated with granitoid bodies, apart from studies on por-
phyry deposits. The latter include those in Canada (Brabec and White, 1971;
Wolfe, 1974; Gunton and Nichol, 1975; Olade and Fletcher, 1975,1976a,b; Olade,
1977, 1979) and in the US (Nash and Theodore, 1971; Theodore and Nash,
1973; Putman, 1975; Chaffee, 1976a,b; McCarthy and Gott, 1978; Pride et al.,
232

1979). Others are Chile (Oyarzan, 1975; Armbrust et al., 1977), and Finland
(Nurmi, 1985).
The porphyry deposits have associated Cu and S anomalies. Alteration zones
are reflected by enhanced K and Rb and depleted Ca and St. Generally, Cu,
Rb, and K have peak values over the ore zone; S has maximum values at the
periphery. A large number of other elements - As, Sb, Te, Au, Ag, Mn - are
useful in particular cases. Halos are generally large (1 km), and zoning of ele-
ments is common.
A recent example of a geochemical survey for Sn is the study by Arrykul
(1985) around the Taronga (New South Wales, Australia) low-grade sheeted
vein deposit in hornfelsic siltstone and sandstone intruded by the Mole
"tin"granite. The deposit is clearly defined by halos of about 1 km × 2.5 km for
Sn, As, Li, and F in surface rock chip samples collected at a sample interval of
150 m along traverses 1.5 km apart over an area of about 100 km 2.

MINERALIZATIONASSOCIATEDWITH VOLCANICROCKS

Volcanic associations of Zn-Pb-Cu massive sulphides

The pyritic Cu sulphides (with variable, but normally lesser, amounts of Zn)
occur in generally mafic and tholeiitic lavas. Stanton and Ramsay (1980) point
out that Zn tends to increase relative to Cu as volcanism progresses to andesitic
and dacitic; Pb becomes abundant as the rhyodacitic and rhyolitic stage of
volcanism is attained.
Govett (1983) stated that Zn-Cu and Pb-Zn-Cu exhalative volcanic deposits
are reported to occur dominantly in calc-alkaline rocks (see especially Sangs-
ter, 1972; Descarreaux, 1973; Cameron, 1975). However, there were some in-
dications to the contrary. Fox (1979), for example, concluded that Kuroko-
like Zn-Cu massive sulphides can be hosted by sub-alkaline rocks showing a
range of petrochemical affinities from strongly tholeiitic to strongly calc-al-
kaline. Sopuck et al. (1980) noted that the felsic volcanic rocks from the areas
of Zn-Cu deposits of Uchi Lake, Sturgeon Lake, Noranda, and Normetal on
the Canadian Shield straddle the tholeiitic-calc-alkaline boundary, whereas
felsic to intermediate rocks from unproductive areas are generally calc-alka-
line. Regardless of whether the rocks fall in the tholeiitic or calc-alkaline field,
both productive and non-productive rocks may display a calc-alkaline trend in
particular areas.
The productive Confederation Lake cycle at Uchi Lake has a tholeiitic trend,
whereas the barren Woman Lake cycle has a calc-alkaline trend (Fig. 3). So-
puck et al. (1980) also made the point - rightly - that distinction between
tholeiitic and calc-alkaline rocks on the basis of AFM diagrams could be thor-
oughly misleading in areas of exhalative volcanic sulphide deposits. The char-
acteristic depletion of Fe and Mg in calc-alkaline volcanism relative to tholeiitic
 233

FeO

Na20+K20 (:~.,
. . . . . .,~) productive cycle MgO
~]'~..[T~ barren cycle

Fig. 3. Schematic representation of composition of barren Woman Lake cycle and productive
ConfederationLake cyclevolcanicrocksof the Uchi greenstonebelt, Ontario, Canada (compiled
from Sopucket al., 1980).

rocks may be obscured by the common and widespread Fe and alkali metaso-
matism associated with massive sulphides.
Davies et al. (1979) emphatically cast doubt on the usefulness of AFM dia-
grams for classifying Archaean volcanic rocks. Based on studies of volcanic
rocks in the Timmins area of Ontario, Canada, they point out that the major
elements (K, Na, Fe, and Mg) are mobilized during metamorphism and by
metasomatism, whereas the trace elements Y, Zr, Ti, and Cr remain relatively
immobile. Plots of Y + Z r (ppm), TiO2Xl00 (wt,%), and Cr (ppm) (YTC
plots) provide a clearer distinction between magnesian, tholeiitic, and calc-
alkaline rocks.
The relative immobility of Ti and Zr is substantiated by Dudas et al. (1983)
and Petersen (1983). The latter author suggested that Zr/TiO2 ratios could be
used to determine the primary petrologic character of metavolcanic rocks af-
fected by alteration and metamorphism. Mineralogically and petrologically
similar rocks produced by metamorphism of mafic rocks and hydrothermal
alteration of felsic rocks associated with massive sulphides could be discrimi-
nated by Zr/TiO2 ratios.
The evidence for a genetic association between various massive sulphide
types and specific volcanic associations is equivocal. The early presumption
that the Zn-Pb-(Cu) deposits occur exclusively in calc-alkaline rocks must
now be questioned for those classifications based wholly on AFM diagrams.

Recognition of productive volcanic horizons and regional surveys

Regional exploration would clearly be facilitated if productive cycles of vol-
canism could readily be distinguished from non-productive cycles in a partic-
234

ular volcanic sequence. The most comprehensive studies have been undertaken
on Archaean massive sulphides by Nichol and his co-workers (e.g., Davenport
and Nichol, 1973; Nichol, 1975; Sopuck et al., 1980). Although productive cycles
are generally distinguished by higher Fe and Zn, there is considerable overlap,
and single-element differences are not reliable. Insofar as both major and trace-
element contents follow differentiation trends, variations due to this are likely
to be more significant than small differences due to mineralization.
Geochemical data must therefore be normalized to account for differentia-
tion. Sopuck et al. (1980) used the Si02 content to measure differentiation; all
elements were regressed against SiO2 for the Noranda (Canada) area and used
to calculate residuals for other areas. Whereas the distinction between pro-
ductive and non-productive horizons became clearer with this procedure, sin-
gle-element comparisons did not give entirely consistent results. A discriminant
function based on Fe and Zn residuals, however, gave a better than 70% correct
classification for most samples. Gibson et al. (1983) and Lavery (1985) indi-
cate that some massive sulphides are associated with significant silicification;
this casts doubt on the general use of SiO2 to correct for fractionation.
Campbell et al. (1982) argue that if the distinction between productive and
non-productive volcanic rocks is related to the genetic history of the rocks, this
should be reflected in REE geochemistry. They compare the REE geochemis-
try of barren felsic volcanic rocks with similar rocks host to massive sulphide
deposits (Fig. 4). The felsic rocks associated with ore deposits have a charac-
teristic flat pattern (low L a / L u ratios) and well-developed negative Eu anom-
alies. The REE pattern in the barren felsic volcanic rocks shows light REE
enrichment and weak or absent Eu anomalies.
Whitford (1983) commented that large Eu anomalies and flat REE patterns

500 productive felsic volcanics

rT~ barren felsic volcanics
200
100
"~- 50
g
~ \ , - ~ , ~A/.~.~
: ~ . . / . .~. ~- . ~.,. . .~. .~. .. .. .. ........ .
o

-g 20
~/ /',/ / / / /
~ 5

, , , , , , , , , , ,
"2
, , ,

La Pr Nd Sm Eu Tb Oy Er Tm Lu

Fig. 4. Range of distribution of chondrite normalized REE in barren and mineralized felsic vol-
canic rocks. The barren range is based on samples from Canada, Australia and South Africa; line
2 is the actual trace of the Middle Marker porphyry, South Africa. The mineralized range is based
on samples from the Kam-Kotia, South Bay, Kidd Creek, Sturgeon Lake, and Matagami deposits
(Canada), the Golden Grove deposit (Australia), and Kuroko (Japan); line 1 is the actual trace
from Kidd Creek (compiled from Campbell et al., 1982).
 235

are more likely to be due to alteration and not primary features of the felsic
rocks. Based on later detailed studies at South Bay Mine (Uchi Lake ), Mattabi
Mine (Sturgeon Lake), and Kidd Creek Mine, Campbell et al. (1984) con-
cluded that REE show little or no evidence of mobility in the pervasively al-
tered zone around the massive sulphides. In the alteration pipes of the deposits,
however, REE are mobile. Moreover, there is fractionation of light and me-
dium REE from heavy REE. There is little mobilization of REE around the
small South Bay mine deposits, and the greatest mobilization of REE occur at
Kidd Creek (the largest deposit).

Exploration case histories

There are relatively few regional scale rock geochemical surveys for massive
sulphides described in the literature. A survey of the Troodos volcanic series
of Cyprus - well documented by Govett and Pantazis (1971) and Govett (1972,
1983) - showed that regionally the cupriferous pyrite deposits are located in
basalts that are relatively depleted in Cu and enriched in Zn. A large scale
survey of the Bathurst area of New Brunswick (Canada), based on an average
of 1 rhyolite sample/5 km 2 over an area of 2000 km 2, showed that the Palaeo-
zoic Zn-Pb massive sulphide deposits are also largely confined to areas where
the Cu content rhyolite is depleted (Govett and Pwa, 1981; Govett, 1983 ). Past
and present producing mines and all significant deposits (Pb + Zn > 3.0%; >
1× l0 s tonnes) lie within areas where Z n / C u > 7.0, Zn/Pb--2.0-2.8, P b /
Cu > 3.0 and Cu < 10 ppm.
In a more detailed regional scale survey (4 samples/kin2), analysis of the
heavy mineral fraction of rocks from around the South Bay massive sulphide
deposit (Superior Province, Canada) detected anomalous values for Cu, Pb,
Zn and Ag up to 10 km along strike from the deposit (Allen and Nichol, 1984).
The most coherent anomaly appeared to be given by Pb, Anomalies for Pb, Zn,
and Ag in whole rock extended for only 1-2 km from the deposit.
There may be regional-scale anomalies in situations where there are exten-
sive sediments and exhalites stratigraphically close to the ore horizon (Coope,
1977; Coope and Davidson, 1979). Scott et al. (1983) refer to "tuffaceous ex-
halites" - a mixture of tuff and chemical exhalites - to describe ferruginous
chert, cherty tuff, and sulphide iron formation commonly associated with mas-
sive sulphide horizons that are good indicators of ore. They report geochemical
and mineralogical signatures indicative of ore, including variations in chlorite
composition, alteration of ilmenite, and variations in Mn content; the trace
elements are, however, erratic and inconsistent from district to district.
There is an abundance of published case history on local and mine scale
exploration for massive sulphides. Anomalous aureoles are extensive - 500 m
or more stratigraphically vertically and 1-2 km laterally. Footwall anomalies
236

around proximal deposits are more intense than hanging-wall anomalies ( sig-
nificant hanging-wall anomalies seem to be absent in Archaean deposits).
A generalized summary of element response is given in Fig. 5 for 28 deposits
from Canada, Australia, Japan, Europe, Cyprus, Turkey, and Fiji which range
in age from Archaean to Cenozoic. The responses are remarkably consistent.
In nearly all cases Fe and Mg are enriched, and Na and Ca are depleted. Dif-
ferences that do occur are generally attributable to variation in host rock {vari-
ation in lava fractionation, texture of rock, proportion of sediments, whether
deposits are proximal or distal, and differences in ore composition). Some case
histories from deeply weathered terrain in Australia show that even under these
circumstances similar characteristic geochemical responses are obtained
(Dunlop et al. 1979; Rugless and Govett, 1984; Fedikow and Govett, 1985).
The ore elements - especially Zn - are commonly enriched. Cu is depleted
around the Cyprus deposits. P is enriched around the Heath Steele deposits in
New Brunswick {Wahl, 1978) and variably enriched or depleted around Pre-
cambrian massive sulphide deposits in Finland (Rehtijarvi, 1984). Data from
a few deposits indicate that Rb, H20, and CO2 are enriched, and Sr is depleted
(Govett, 1983).
Differences also arise between hanging wall and footwall. For example, Cu

Id9(25)

Ca(23)

1{(15) hment

Ha(24) tion

[] variable
Mn( 11 ) ~,:.:.:.:.:.:.:.:.:.:
1 "

Fe(28)

Co(?) / ~

Hi ( 5 ) /lllllllllllllllllllllllllllllllllllllllllllll/llllll//l~
1 1

Zn(15) ,h-A

P b ( 18 )

Cu ( 13 ) "lllllll~

I I J I I I I I I I
8 18 28 30 48 5B 68 70 B8 98 188
x OF CASES
Fig. 5. E l e m e n t s showing e n r i c h m e n t , depletion, or variable behaviour in rocks host to massive
sulphide deposits. N u m b e r s in parenthesis after element symbol indicate total n u m b e r of deposits
for w h i c h data are available for t h a t element. Total n u m b e r of cases considered is 28 from Aus-
tralia, Europe, a n d N o r t h America.
 237

is generally relatively enriched in the footwall and depleted in the hanging wall
in the Palaeozoic deposits of New Brunswick; Mn is relatively depleted in the
footwall, but it is enriched in the hanging wall. Complications also arise as a
function of lateral distance from the source of mineralizing fluids. The low pH
and Eh of the sulphide solutions tend to maintain Mn in solution; it is precip-
itated as solutions become more alkaline and oxidizing, and peak values occur
lateral to the sulphide zone (Whitehead, 1973). In specific situations Mg and
Fe may be depleted close to the ore zone and enriched further away. K also
commonly shows this behaviour.

CONCLUDINGDISCUSSION

It has long been recognized that Cu (Au)-Mo porphyry deposits are associated
with granodiorite-quartz monzonite-quartz diorite granitoids and that Sn-W-
U and rare metals occur in more felsic varieties; however, disseminated Sn
deposits may occur in the more basic granitoids. The petrological distinction
has been related to a number of genetic classification systems, but none is
totally successful.
The specialized granitoids have absolute enrichments of Rb and Li and en-
richment of Rb relative to K; they are also depleted in Mg, Ba, and Sr. Broadly,
the greater the degree of specialization, the more likely the granitoids are to
have associated Sn or U mineralization. Nevertheless, it appears that for Sn-
U-W specialized granitoids to have associated metalliferous mineralization (as
distinct from enrichment in metals) they must have been intruded into w e t
sediments. W (and base and precious metal) mineralization is associated with
relatively less specialized granitoids. Local reconnaissance and deposit scale
geochemistry generally show responses for the same elements that character-
ize the granitoid as specialized plus ore and associated pathfinder elements.
There is no agreement on a genetic volcanic association for massive sul-
phides, largely because of uncertainties of classification of host rocks on the
basis of AFM diagrams. A re-evaluation using immobile elements should help
to resolve the problem. Limited data indicate that productive horizons may be
distinguished from barren horizons in any particular area on the basis of multi-
element discriminators, provided the effect of differentiation is eliminated. On
the basis of a few empirical studies, prospective areas appear to be well defined
geochemically on the basis of the ore elements.
Deposit scale responses for massive sulphides are remarkably uniform. In
most cases Fe, Mg, and Zn are enriched, and Na and Ca are depleted. REE
geochemical data are limited and equivocal.
Part of the problem of recognizing productive granitoids and volcanic se-
quences derives from the multiplicity of possible sources of an element in any
particular sample. In surface samples the situation is further complicated by
the effects of weathering.
238

T h e statistical reliability o f samples ( e v e n a s s u m i n g t h a t a n a l y t i c a l c o n t r o l

is always good) is p a r t i c u l a r l y i m p o r t a n t , especially in regional surveys. It is
essential to collect a n a d e q u a t e n u m b e r of samples, o f a n a d e q u a t e physical
size, for r e c o g n i t i o n o f significant a n o m a l o u s e l e m e n t d i s t r i b u t i o n s for a de-
fined degree o f confidence. S a m p l i n g p a r a m e t e r s will v a r y b e t w e e n e l e m e n t s
d e p e n d i n g u p o n t h e m o d e o f o c c u r r e n c e o f t h e e l e m e n t a n d its relative enrich-
m e n t or depletion.
T h e aim o f e x p l o r a t i o n g e o c h e m i s t s - to discover a u n i v e r s a l c h e m i c a l i n d e x
t h a t will clearly i d e n t i f y a S n - b e a r i n g granite or a volcanic u n i t h o s t to a mas-
sive sulphide deposit - c a n n o t be realized w i t h p r e s e n t d a t a a n d knowledge. It
is o n l y m i n e - s c a l e r e s p o n s e s to massive sulphide deposits t h a t show a n y sem-
b l a n c e o f geographic a n d s t r a t i g r a p h i c u n i f o r m i t y .

ACKNOWLEDGEMENT

T h e a u t h o r s are grateful to Mrs. A.L. G r a n t for t y p i n g of t h e m a n u s c r i p t , to

Mrs. M. K a d a r for d r a u g h t i n g , to Mr. G. Small for p h o t o g r a p h y , a n d to Mrs.
M . H . G o v e t t for editorial assistance.

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