Geochemical

Journal,

Vol.

14,

pp. 303

to

315,

1980

303

Lead

isotopic and

feature

of the Besshi-type on the ore lead

deposits

its bearing
KAzuo

evolution

SATO' and University

Higashi 1980;

AKIRA SASAKI' of Tokyo, Bunkyo-ku,

Ibaraki 25,

Earthquake

Research Institute,
Survey

Tokyo
305,2

113'

and Geological

of Japan,

1-1-3, Yatabe, December

Japan

(Received October 23,

Accepted

1980)

Additional lead isotope measurements have been made on pyrite samples from the Mesozoic and Paleozoic Besshi-type deposits and on a galena sample from the Proterozoic stratiform mineralization in the Flin Flon area, Canada. The supplemented data for the Besshi-type mineralization confirm, on the one hand, the previous observation that leads in this type of deposit are isotopically variable and are con sistently deficient in 707Pb relative to the major lead (conformable) ore system, and reveal, on the other hand, that, in some cases, a small but significant isotopic variation exists even within a single deposit. The isotopic pattern of these deposits, which is similar to that of the ocean-ridge basalts, is in striking contrast with a uniform isotopic composition and its conformity with the evolutionary pattern of the major lead orebodies found in one of the Mesozoic deposits examined, and thus reinforces the previous view that the lead in most Besshi-type deposits may have been derived mainly from the mantle. The 2O'Ph deficiency relative to the major lead ore system and other two remarkable features common to most Besshi-type deposits, close association with mafic magmatism and generally Pb-impoverished nature, are also recognized in the Flin Flon area. Similar examples of stratiform deposits seem to exist in other areas. The Besshi-type and other 10'Pb deficient deposits appear to indicate the presence of a mantle-derived ore-lead system. The mineralization of such deposits seems to occur most commonly in Archean to early Proterozoic and late Paleozoic to Mesozoic terrains, but might occur also in other simatic environments, whereas the large Pb-rich orebodies presumably of crustal origin may only be found in Proterozoic to Phanerozoic sialic environments. The current concept of global tectonic history appears to be generally consistent with the view of two major evolutionary systems of stratiform ore leads.

INTRODUCTION

Previous works on the lead isotopic com position of stratiform sulfide deposits from Japan (SATOand SASAKI,1973, 1976) indicated the presence of two distinct types of common lead in these ores. The isotope ratios obtained for the Cenozoic polymetallic kuroko-type min eralization show only a small variation, being generally close to the modem point of the growth curves of major lead ("conformable") orebodies (see for the growth curves STACEY and KRAMERS, 1975; CUMMING and RICHARDS, 1975).
On the contrary, the lead isotope data from pre-Cenozoic bedded cupriferous iron sulfide (Besshi-type or kieslager) deposits are found to be quite variable, showing a pattern clearly dif

ferent from the major lead ore system but more or less similar to the isotopic pattern of basaltic rocks of the present-day ocean ridges. It was suggested that the isotopic feature might in dicate a mantle origin of lead in this group of deposits unlike the major lead orebodies for which the crustal origin had widely been ac cepted (SATO and SASAKI,1978). The purpose of the present work is to confirm this pre liminary view on the Besshi-type ore lead with additional data from a more extensive area and to discuss its possible geochemical implication in the systematics of ore-lead isotopic evolution.
Figure 1 illustrates locations of the deposits examined in this paper. Most of them are in the regionally metamorphosed Permo-Carbonif erous sedimentary pile (the Sambagawa meta

304

K. SATOand A. SASAKI
logical Survey of Japan, study (ITOH, 1976).
As will be discussed some shield the stratiform regions Besshi-type ore show ores.

morphic terrain) in the Outer Zone of Southwest Japan but some are in weakly or non-meta morphosed Paleozoic to Mesozoic terrains else where. As to the geological setting and further details of the Besshi-type ore deposits in Japan, the reader is referred to the previous paper (SAro and SASAKI, 1976) and the references cited therein. Like the previous work (SAro and SASAKI, 1976), the specimens were obtained from pyrite separates prepared by S. ITOH,Geo

for his minor element

below, existing features this data similar for to a

leads isotopic In

from

Precambrian connection,

galena Canada

specimen from was isotopically

the Flin Flon mine, examined for reference.

0 \S NDK
0

Kp~D~

12

C
a F 4 w x I

~PQpN E5" OF SoV~N ,0 \O \N0\N

C

0 Z

j~~)

to-E \NNEP
;v

a
r

D
B

6 m

-17
-(ersO

~ `soJ~Yo~y \12the
~PPpN 5 myo9a doNE

01

00 0
0 500 km

Fig. 1. A map showingthe locations of Besshi-type depositss examinedand two major tectonic units in the South west Japan. 1, Okuki; 2, Chihara; 3, Shirataki; 4, Sazare; S, Shingu; 6, limori; 7, Oi; 8, Kune; 9, Yanahara; 10, Tsuchikura;11, Gojo; 12, Taro; 13, Shimokawa.

Lead

isotopic

feature

305

ANALYTICAL PROCEDURE

Lead extraction and purification procedures for pyrite samples are the same as previously described (SATO and SASAKI,1976). Prior to decomposition with HNO,-HC1, samples were treated with warm, dilute HCI for several hours. Some of the samples were found to release sub stantial fraction of lead during this treatment. When sufficient amount of lead was recovered, isotopic analysis was made on the HC1-soluble fraction. The galena sample from the Flin Flon mine was treated in the same manner as de scribed in CUMMING et al. (1979). Lead isotope ratios were measured with the surface emission single Re-filament ionization technique on a Micromass-30 mass spectrometer using on-line data processing system. The details are the same as in CUMMING et al. (1979). Reproducibility of the measurement determined from fourty four replicate analyses of the National Bureau of Standards sample SRM-981 in the entire experimental period (over seven months) is 0.15% for 206Pb/R04Pb,0.18% for 20'Pb/209Pb , and 0.27% for 20WPb/204Pb, respec tively, in 2a.
RESULTS

and 3. Lead isotope data available for deep-sea sediments (REYNOLDS and DASCH,1971; CHURCH, 1976; MEIJER, 1976) and for basaltic rocks from the present-day ocean ridges (CHURCH and TATSUMOTO, 1975; TATSUMOTO, 1978) are also plotted for comparison. Meteoritic isochron in Fig. 2 is of a slope corresponding to an age of 4.57b.y. (TATSUMOTO et at, 1973; see also STACEY and KRAMERS,1975; CUMMINGand RICHARDS, 1975). The growth curve for major lead ore system proposed by CUMMING and RICHARDS (1975) is indicated in both of Figs.2 and 3. As seen from Figs. 2 and 3, both the Mesozoic and the Paleozoic stratiform deposits in Japan show considerable isotopic variation. In Fig. 2, they plot below the ore-lead growth curve with the exception of Taro mine (open squares), delineating a narrow band with a gentle slope to the right of the meteoritic isochron. In Fig. 3, the data plot mostly to the lower right of the growth curve. In this case, deposits with higher 206Pb/209Pbratios appear to deviate more significantly from the growth curve, mak ing again an exception of Taro mine.
The data of Flin Flon lead obtained in this study are compared with those by SLAWSON and RUSSELL (1973) in Table 2.

Lead isotope data for the pre-Cenozoic stratiform sulfide deposits from Japan are listed in Table 1, which includes some of the previous results by SATOand SASAKI (1976, 1978). The data for the Paleozoic Shingu and Kune mines in the Outer Zone of Southwest Japan were first obtained in this study. Those for the Mesozoic Taro and the Paleozoic Sazare and Okuki mines were supplemented by one or more samples. The values previously reported for two Paleozoic samples (Okuki No. 1414 and Oi No. 5) and one Mesozoic sample (Shimokawa No. 1810) (SATO and SASAKI,1978) were replaced by the new data, though no significant difference ap peared to exist. Thus, the data presented here for Shimokawa and Oi mines are all based on the new measurements.
The data in Table 1 are plotted in Figs. 2

LEAD ISOTOPIC FEATURE OF THE BESSHI-TYPE DEPOSITS IN JAPAN

Paleozoic deposits The preliminary isotopic investigation by SATO and SASAKI(1976) in dicated that leads from the Paleozoic terrain are isotopically variable in each of the two major tectonic units in the Southwest Japan. The lead in the Outer Zone of Southwest Japan appeared to be particularly variable in 206Pb/ 2O4Pbratio . It was suggested that the isotopic variability, though not so evident in the principal deposits occurring in the Shikoku Island, may generally be present along the whole extension of the Outer Zone. The lead isotope data now available for a more extensive area confirm the wide range of 2D6Pb/204Pbratio in the Outer Zone and reveal a significant variation within

306

K.

SATO and A. SASAKI

Table

1.

Isotopic

composition

of lead in the Besshi-type

...Pb/'04Pb
-Paleozoic deposits

deposits from Japan

"Pb/209Pb
Reference

Locality

and sample

307Pb/20'4Pb

Outer

Zone

1. Okuki

Southwest Japan mine, Ehime

Pyrite Pyrite Pyrite Pyrite

No. No. No. No.

1201 1308 (R) 1414 (R) 1901

Ehime

17.983 18.166 18.152 17.939 18.842 18.786 18.825 18.769 19.321 19.378 17.900 18.268 18.306 17.465 17.491 17.820 17.941

15.459 15.488 15.450 15.422 15.59 15.51 15.54 15.54 15.629 15.637 15.496 15.44 15.45

37.76 37.933 37.790 37.600 38.56 38.32 38.39 38.44 38.733 38.775 37.815 37.82 37.93 37.245 37.262 37.524 37.689

(3) (1) (1) (1) (2) (2) (2) (2) (1) (1) (1) (2) (2) (1) (1) (1) (1)

2. Chihara mine, Pyrite

3. Shirataki mine, Kochi Pyrite No. 3009 Pyrite No. 6038 4. Sazare mine, Ehime Pyrite No. 3095 (R) Pyrite No. 3099 (R) Pyrite No. 3099 (L) 5. Shingu mine, Ehime Pyrite No. 3020 (R) 6. limori mine, Wakayama Pyrite No. 66 (L) Pyrite No. 89 (L) 7. Oi mine, Shizuoka Pyrite No. 5 (R) Pyrite No. 21 (L) 8. Kune mine, Shizuoka Pyrite No. 9 (R) Pyrite No. 9 (L) Inner Zone of Southwest Japan
9. Yanahara mine, Okayama

15.391 15.394
15.435 15.459

Pyrite No. Y-8 (L) Pyrite No. Y-194 (R) 10. Tsuchikura mine, Shiga Pyrite No. 27 (R) Pyrite No. 60 (R)

17.987 17.965 18.050 17.862 -Mesozoic deposits

15.48 15.50 15.50 15.42

37.76 37.86 37.53 37.44

(2) (2) (2) (2)

11. Gojo mine, Wakayama Pyrite (L) 12. Taro mine, Iwate Galena No. 511 Galena No. 71-T-38 Galena concentrate (av. of 3) 13. Shimokawa mine, Hokkaido Iron sulfide ore No. 1535 (L) Iron sulfide ore No. 1606 (L) Iron sulfide ore No. 1810 (R) Iron sulfide ore No. 1810 (L)

18.249 18.70 18.712 18.704 18.129 18.075 18.266 18.299

15.42 15.64 15.621 15.611 15.509 15.492 15.514 15.539

37.77 38.68 38.669 38.601 38.064 37.991 38.184 38.262

(2) (2) (4) (1) (1) (1) (1) (1)

Numbers given to deposits are those on Fig. 1. (L) and (R) denote HG-soluble and residual fractions, respectively (see text). Reference: (1) This work, (2) SATO and SASAKi, 1976, (3) SATo and SASAKI, 1978, (4) DoE and ZARTMAN,1979. each of the Okuki and Sazare mines, Shikoku Island. Some of the Outer Zone leads are more enriched in 206Pb than expected from any of the existing models for the major lead ore sys tem. Among others, two samples of the Sazare

mine have the highest 2O6Pb/204Pb ratio and, in Fig. 2, plot far to the right of the modem point of CUNNING-RICHARDS' growth curve. They are still more enriched in 206Pb than the oceanic sediment leads.

Lead

isotopic

feature

307

Leads of the lowest 206Pb/"Pb ratio are found in two samples from the Oi mine, central Japan. In Fig. 2, they lie just on the 4.57b.y. meteoritic isochron and are thus distinctly less radiogenic than any of the major lead ores of Paleozoic age which are all known to plot to the right of the meteoritic isochron (e.g. CUMMING and RICHARDS, 1975). The other samples from the Outer Zone fall between the above two extremes. Another isotopic feature of the Paleozoic ore leads indicated by the previous investiga tion was their consistent deficiency in 207Pb relative to the major lead ore system. The data now available clearly confirm this observation. In addition, except for the Mesozoic Taro mine, all the pre-Cenozoic ores form a linear array in the 2o'Ph/2o4pb vs. aoopb/2MPb plot (Fig. 2) which is almost indistinguishable from that of the ocean ridge basalt leads. Also in Fig. 3, they plot generally close to the data for ridge basalts rather than the data for major lead ores.
Mesozoic examined deposits are known Three Mesozoic deposits

in age (I{ANEHIRA and TATSUMI,1970). The time difference in mineralization is small, if any, but these deposits are isotopically different from one another. The leads from Taro mine (open squares) are relatively radiogenic and plot close to the ore-lead growth curve in both of Figs. 2 and 3, while the leads from Shimokawa and Gojo mines (solid squares) form a less radiogenic group, falling significantly below the growth curve in the 407Pb/ZMPb_ 206pb/204Pb diagram (Fig. 2). The latter group is close to some of the Paleozoic leads. In the 2o8Pb/2OMPb306Pb/ 209Pb diagram , however, the Shimokawa leads all lie on the growth curve (Fig. 3).
Further Mesozoic between The small in the sites mill tion. deposit deposits data the inspection terrain from the reveals Shimokawa isotopic two concentrate the same to be unique uniformity of the another and the data from Taro mine from from isotopic of among the leads. show whereas, different the the all mine Taro the composi a distinction

Shimokawa galenas

but significant Taro and mine, a galena isotopic

variation,

have essentially This appears examined.

to be Jurassic

or Cretaceous

aesshi-type 0 16 Outer Zone Inner Zone

deposits

Ocean-ridge Deep-sea

basalts sediments

)Paleozoic Mesozoic
7
/

a a

0
15.5 a a

o e

00

ore-lead

growl

ei SW
rioi ", i

15
i

fee ti7
17 18 206Pb/ 20'Ph 19

Fig. 2. 20'PbP04Pb vs 306Pb/204Pb plot for the Besshi-type deposits, deep-seasediments(REYNOLDS and DASCH, 1971; CHURCH, 1976; MEIIER, 1976) and basaltic rocks from the present-day ocean ridges (CHURCH and TArsuMOTO,1975; TATSUMOTO, 1978). Ore-leadgrowth curve of CUMMING and RICHARDS (1975) and mete oritic isochron of 4.57b.y. (STACEY and KRAMER S, 1975; CUMMING and RICHARDS, 1975) are shown.

308

K. SATO

and A. SASAKI

a remarkable isotopic uniformity within a single deposit (OSTIC et al., 1967) also attract con ORE LEADS siderable attention. While the significance of It is well known that certain large orebodies these striking isotopic features is still not very of stratiform or conformable type (major lead clear at present, it seems generally agreed that orebodies) show a systematic isotopic pattern the lead of such deposits comes from crustal that can be approximated by a single evolu environment (ARMSTRONG,1968; RICHARDS, tionary system (CUMMING and RICHARDS,1975; 1971). The data for major lead ores of various STACEY and KRAMERS, 1975). Many examples of ages may then be interpreted to represent a
POSSIBLE ORIGINS OF THE BESSHI-TYPE

39 O O

Besshi-type Outer Inner Zone Zone

deposits
car.

}Paleozoic
Dasalts sediments

}Mesozoic
Ocean-ridge Deep-sea

80 ~8

800

L a 0 N

38

r.

j
zob 0e 37 17

18

19

206Pb/ 204Pb Fik. 3. 208Pb/209Pb vs. 106Pb/204Pb plot for the Besshi-type deposits,deep-seasediments(REYNOLDS and DASCH 1971; CHURCH, 1976; MEIJER, 1976) and basaltic rocks from the present-day ocean ridges (CHURCH and TATSUMOTO, 1975; TATSUMOTO, 1978). Ore-lead growth curve is from CUMMLYG and RICHARDS (1975).

Fig. 2. Lead
Location

isotope data for galenas from

206Pb/206Pb
15.359 15.315 15.387 15.709 15.745

Flin Flon
201pb/21pb
15.147 15.106 15.116 15.256 15.22R

area,

Canada 208Pb/204Pb
34.937 34.846 34.940 35.176 35.297 Reference

Flin Flon mine, footwal zone, main ore bed, 10th level Flin Flon mine, 2210 level, 78 stops Chisel Lake mine, 650 level, 821 scope Snake Lake, surface showing Film Flon mine, 3rd sub above 1120 level, Q stope

(1) (2) (2) (2) (2)

Reference.'

(1) This work, (2) SLAwsov and RUSSELL,

1973.

N 0

Lead

isotopic

feature

309

certain crust.

evolutionary

system

of lead in the earth's

SATO and SASAKI (1976) suggested that leads from most of the pre-Cenozoic stratiform sulfide deposits in Japan come from an evolu tionary system of some other class than that of the major lead ores. The linear trend in 20'Pb/ 104Ph 206Pb/204Pb diagram obtained for the Besshi-type ores (Fig. 2) seems to be of some significance with respect to their origin, par ticularly the source of lead in the Outer Zone of Southwest Japan. The isotopic development of leads showing such a linear trend can usually be approximated by the evolution in a group of closed systems with the same initial isotopic composition but differing U/Pb ratios.
Alternatively, the isotopic pattern may be regarded as a mixing line of two isotopically distinct leads. We observe the least radiogenic leads in the samples from Oi near the north eastern end of the Outer Zone and the most radiogenic leads in the Sazare mine far to the southwest (see Fig. 1). If the large spread of data for the Outer Zone leads represents various proportions of mixing of these two groups of lead, the process may have occurred along the axis of mineralization belt extending over a distance as long as 500km. This seems rather unrealistic.

The deficiency in 20'Pb observed in most of the Besshi-type deposits indicates that their source region remained depleted in uranium compared to the major lead ore system in the early stage of its development, say for the first 2 billion years of the earth's history (RUSSELL, 1972). Then, the exceeding variability in 206Pb/ 2o6Pb ratio and the nearly linear relationship of the 2o6Pb/204Pband 20'Pb/204Pb ratios observed for the Outer Zone leads may be interpreted to be indicative of varying degrees of U enrich ment of the source region at some time signi ficantly later than the formation of stable crust. The U enrichment only in the later third of earth's history causes no significant increase in the "'Pb/204Pb ratios.
The only U-Th-Pb system of this kind is known to exist is the oceanic mantle. that The

prime isotopic pattern of the present-day oceanic mantle is generally thought to be represented by the lead in basaltic rocks from the ocean floor, particularly from ocean ridges (ARMSTRONG and COOPER, 1971). In fact, the data from ridge basalts plotted in Figs. 2 and 3 appear to show a pattern favorable to the mantle derivation of the Outer Zone leads. This is consistent with the view that the magmatism in the Outer Zone has a prime feature of eruption of mafic rocks which may have occurred along a local rift zone on the ocean floor(SuGISAKiand TANAKA, 197 1). Fractional change in the 20'Pb/104Pb ratio of the source region expected for the late Paleozoic to present time interval (-300m.y.) is much smaller than that in the 2o6Pb/2o6Pbratio, and, therefore, the corresponding change in the slope of the linear array in 2D'Pb/i04Pb vs. 206Pb/209Pb plot would be insignificant. The existence of highly 206Pb enriched leads in the Outer Zone may come into question, because 206Pb/200Pb ratios exceeding 19 have been found only in some of the oceanic island lavas (OVERSBY and GAST, 1970; OVERSBY et al., 1971). This .06Pb enrichment may possibly be due to some later modification. Admixture of lead from continental crust to the mantle-derived lead would result in a shift of the isotope ratios consistently toward higher values. The crustal lead data are known to plot generally on or above the ore-lead growth curve in both the 27pb/2o4pb 2o6Pb/2o6Pband 208Pb/2o6Pb _ 2o6Pb/ 2o6Pb diagrams (DOE and ZARTMAN , 1979). If it is supposed that the 106Pbenrichment in some of the Paleozoic Outer Zone ores is the effect of contamination by the crustal lead, the upward shift of their 20'Pb/204Pb and 2DBPb/204Pb ratios is more likely to be conspicuous than the ores with lower 206Pb/204Pbratios. No such trend is seen in both Figs. 2 and 3. Instead, in Fig. 3, the most 206Pb enriched leads of the Sazare mine appear to deviate rather in the opposite direction, being farther from the field of con tinental crust lead. The higher 106Pb/309Pb ratios concerned might have resulted from the incorporation of radiogenic component generated solely by the

310

K. SATO and

A. SASAKI

decay of uranium in some post-mineralization environment. This would cause a considerable increase in 206Pb/108Pbratio without any signi ficant increase in 207Pb/209Pband 208Pb/204Pb ratios. There is indication of admixed radiogenic component in some of the samples examined. Three samples were analyzed for their respective acid-soluble and residual fractions (see Table 1). For each of the three, Sazare No. 3099 and Kune No. 9 from the Paleozoic terrain and Shi mokawa No. 1810 from the Mesozoic terrain, it appears that the acid-soluble lead is slightly more enriched in 206Pb than the insoluble lead. The quantities are clearly too small to account for all of the observed 106Pb enrichment. The isotopic pattern of the Outer Zone Besshi-type ore leads is, therefore, still interpreted to have mainly originated in the mantle. The isotopic pattern of the Inner Zone deposits seems to show no essential distinction from that of the Outer Zone deposits. From the limited data presently available for the Inner Zone, one may assume a significant contribu tion of the mantle lead in general, though there remains possibility of contamination from other sources of lead (SATO and SASAKI,1976). As to the Mesozoic deposits, the difference in isotopic pattern observed between the Taro and Shimokawa mines seems to correlate with the type of associated magmatism. In the Taro mine, the mineralization is closely associated with the activity of felsic volcanic rocks (TATSUMI et al., 1970), while in the Shimokawa mine the magmatism is abyssal basaltic (KOSAKA, 1975) like in the Outer Zone mineralization. The isotopic variability and 2O7Pb deficient character of the Shimokawa leads may originate from their evolution in an environment similar to that of the Paleozoic Outer Zone leads. As noted already, the 2O8Pb/204Pbratios of the Shimokawa leads deviate from the general trend of the Paleozoic leads. It is unclear at present whether this shift corresponds to the evolution of the source system for the time interval from late Paleozoic to late Mesozoic or reflects some diversity of its Th/U ratio.
The uniformity of the isotopic composition

observed in the Taro leads seems to be con sistent with its closeness to the major lead ore system. In both of the 207Pb/206Pb vs. 106Pb/ 209Pband 208Pb/204Pb vs . 206Pb/204Pb plots, the data for Taro leads fall in the middle of the cluster of deep-sea sediment data which define a spectrum of the present-day crustal leads, but still lie in a range expected from the general trend of the data for major lead ores, i.e. sys tematic increase in radiogenic character with time. In this connection, it may be significant that the Taro mine is a Pb-Zn mineralization similar to the major lead orebodies, whereas the other Besshi-type deposits are generally Pb im poverished with little, if any, galena. This dif ference may also agree with the differing origins of lead in the two types of deposits, mantle and crust. RE-EXAMINATION OF
ORE-LEAD ISOTOPE SYSTEMATICS It has already been recognized that lead

isotope data for some "major lead orebodies" slightly deviate from the systematic pattern established for the majority of data to form a subgroup which is characterized by the defi ciency in .07Pb relative to any of the average growth curves proposed (RICHARDS, 1968; OVERSBY, 1974). Our data of the Besshi-type deposits may show that, in some stratiform ore leads, there is an evolutionary environment clearly distinct from the major lead ore system. It may be justified to re-examine the data for "major lead orebodies" from thi s point of view. An inspection of the data covering various geologic ages (COOPER et al., 1969; STACEY et al., 1969; SLAWSON and RUSSELL,1973; CUMMING and GuDJURGIS, 1973; RICHARDS, 1975) indicates that the small deficiency in 207Pb is mostly an attribute of the mineralization in the Archean to early Proterozoic terrains. An application of a simple single-stage model to these deposits yields relatively low p values compared with those for later mineralizations, indicating an increase in U/Pb ratio of the source region at some Archean to early Proterozoic time (2.6

Lead

isotopic

feature

311

1.6b.y. ago) (OVERSBY, 1974). There has been an understanding that a stable continental crust came into existence in this period (e.g. ENGEL et aL, 1974). Higher p values for strati form deposits in Proterozoic to Phanerozoic terrains of continental regions seem to agree with their assumed crustal origin. Because of their low apparent p values, the data of such Archean deposits as Barberton, South Africa and Manitouwadge, Canada have been liable to be excluded to obtain a better fit of a growth curve to the majority of data (OsTlc et al., 1967; STACEY et al., 1969; COOPER et al., 1969; STACEY and KRAMERS, 1975; CUMMING and RICHARDS, 1975). The Archean deposits have another significant isotopic feature that their geologic ages are fairly close to the values expected from the simple single-stage model (OYERSRY, 1974), whereas considerable deviations from the model are commonly ob served for younger deposits (Osric et al., 1967; RICHARDS, 1971; STACEY and KRAMERS,1975). This primitive isotopic pattern of the Archean

stratiform deposits also attracts our attention and reminds us that these deposits occur pre dominantly in the greenstone belts and seem to be relatively Pb impoverished as compared with the "high-p-type" stratiform deposits in Pro terozoic to Phanerozoic terrains. Another example of this type of Archean deposits may be seen in the Noranda area, Canada. In this area, ore-lead data (CUMMING and GUDJURGIS, 1973) show the consistently 207Pb deficient pat tern, and their least radiogenic value yields a model age that would be close to the mineraliza tion age. These features as well as the isotopic pattern distinct from most of the younger major lead ores are favorable to the mantle origin of lead.
Judging association that Flon, same two Proterozoic class from with stratiform may deposits their mafic Pb poor deposits be nature and close early Flin the and magmatism, we consider and into Pb poor

of possibly Finland deposits.

ages, Outokumpu, as the Archean

Canada,

incorporated

The Outo

kumpu-type

are extremely

16

M CL O N a a

e.unl-type

In

0
f

Min

Flop

13.T1

14
r

13

12

11

12

13

14

15

16

17

18

19

206Pb/ 204Pb

Fig. 4. 207Pb/204Pb 206Pb/109Pb diagram showingtwo types of stratiform ore leads and ore-leadgrowth curve of GUMMING and RICHARDS (1975). Open circles, major lead orebodiesof presumedcrustal origin (COOPER et al, 1969; STACEY et al., 1969; RICHARDS, 1975) and Taro mine, Japan (this work). Solid circles, Besshi-type and other possibly mantle-derived deposits. Data source: (1) COOPER et al., 1969; (2) STACEY et aL, 1969; (3) SLAWSON and RUSSELL, 1973; (4) CUNNING and GUDJURGIS, 1973; (5) DOE and ZARTMAN 1979;(6) AHO, 1979; (7) this work

312

K. SATO and

A. SASAKI

have a lithologic feature similar to that of the Besshi-type deposits (0. Kouvo, priv. communi cation, September, 1978). The data for the Flin Flon area in Table 2 and the data available for Outokumpu lead (AHO, 1979) indicate that these two Proterozoic mineralizations are both significantly 20'Pb deficient compared with other major lead ores of similar ages. As has been pointed out by SLAWSON and RUSSELL (1973), the lead from the Flin Flon area appears to show, to some extent, an isotopic variability, though it is unclear whether this variability is of the same origin as in the Besshi-type deposits. In addition to the Archean to Proterozoic deposits, there exist a few examples of strati form deposits which have already been suggested to be of mantle origin (DoE and ZARTMAN, 1979). Among others, the stratiform massive sulfide deposit at Troodos, Cyprus is known to be a Pb impoverished mineralization possibly associated with the late Cretaceous submarine mafic magmatism. However, lead isotope data of this deposit, barely falling within the limits of oceanic mantle values (DoE and ZARTMAN, 1979), do not appear to be so distinct from the

major lead ore system as compared with the clear distinction established by the Besshi-type ore leads. In this respect, it may be intriguing that the Troodos ophiolite complex, in which the Cyprus mineralization occurs, is suggested by MIYASHIRO (1973) to be the products of an island-arc magmatism.
Compared to the Cyprus, Paleozoic to early Mesozoic deposits at Shasta, U.S.A. and Buchans, Canada look more clearly different from the major lead ores of similar ages in that they are significantly deficient in 20'Pb relative to any of the ore-lead growth curves. These deposits have also been suggested to be of mantle origin (DoE and ZARTMAN, 1979). In Figs. 4 and 5 are plotted lead isotope data available for these possibly mantle-derived de posits together with the data for the other major lead orebodies. It is clear in Fig. 4 that the leads of presumed mantle derivation tend to deviate slightly but consistently from the general evolu tionary pattern of the major lead ores, suggest ing the presence of their own evolutionary sys tem. The 209Pb deficient pattern shows that the system was relatively less enriched in U perhaps

40

38

a a

36

34

5
e

32
I

11

12

13

14

15

16

17

18

19

206Pb/114Pb

Fig. S. 208Pb/109Pb 20bPb/204Pb diagram showing two types of stratiform ore leads and ore-leadgrowth curve of CUMMING and RICHARDS (1975). Legendsare the same as in ft . 4. See also Fig. 4 for data sourceof the mantle-typedeposits.

Lead

isotopic

feature

313

for the first half to two third of the earth's history. A later U enrichment may have oo cuffed to a greater or lesser extent in this parent system, but the relative .0'Pb deficiency is thought to have mostly been preserved even in Paleozoic mineralizations. RUSSELL (1972) sug

presumably of crustal origin occur in Proterozoic to Phanerozoic terrains of continental regions where prevail sialic materials with relatively high U/Pb ratios. This continental regime appears to agree well with the Pb-rich nature of these de posits. The major lead ores of this class may gested that `oceanic materials now enclosed in only be expected in such environments since continental rocks' might be identified by means the Proterozoic, while the mineralization of the of their lead isotope characteristics. Such a class of possible mantle derivation might occur reasoning seems to be substantiated by the de in terrains of some oceanic regime other than the above two major simatic environments in posits discussed here. Figure 5 does not seem to define a distinct the Archean to early Proterozoic and the late pattern except that the data from Besshi-type Paleozoic to Mesozoic. From the viewpoint of global tectonics, and other possibly mantle-derived Phanerozoic deposits plot significantly to the lower right of ENGEL et al. (1974) divided chemical evolution CUMMING-RICHARDS' growth curve. The positions of the earth's crust into three major stages: of the Besshi-type and other Phanerozoic ore (1) the Archean, (2) the Proterozoic-Paleozoic leads in Fig. 5 implies a lowering in Th/U ratio and (3) the Mesozoic-Cenozoic. In terms of of their source region relative to the system significant geological episodes, these three may represented by the growth curve. The effect be specified respectively by (I) greenstone belt of lowering in Th/U ratio may have become magmatism, (2) growth of continental crust and significant to be relfected in lead isotopic pat (3) continental rifting followed by the rise of tern only late in the earth's history. Only a mantle material. With small modification al small difference may be expected between Th/U lowed for the suggested time intervals, this ratios of the two parent systems, crust and threefold division of global tectonic history ap mantle, because of the close geochemical co pears to be generally consistent with the occur herence between Th and U. rence of the two classes of stratiform ore leads discussed here.
POSSIBLE BEARING OF STRATIFORM ORE LEADS ON THE EARTH CRUST EVOLUTION

As is evident

from the above examples,

the

mineralization of possibly mantle-derived strati form ores belongs mostly to either of two major tectonic regimes. One is the type of large-scale continental rifting and ocean-floor spreading during the late Paleozoic to Mesozoic time which may have brought abundant mantle material to the surface. The other is the type called green stone belt characteristic of Archean to early Proterozoic terrains. The predominance of mafic materials apparently common to the two tectonic environments seems to correlate with the isotopic and chemical characteristics ob served in the mineralization in such environ ments.
On the other hand, many large orebodies

Acknowledgments-New lead isotope data for this study were obtained in Department of Physics, University of Alberta, Edmonton where one of us (A.S.) was a visiting scientist from 1978 to 1979. We are particularly grateful to GEORGE CUMMINGfor his kind arrangement in this respect. Technical assistance by DRAGANKRSTICwas invaluable. S. ITOH,Geological Survey of Japan, kindly supplied most of the samples of Japanese Besshi-type ores. The galena specimen from Flin Flon was made available through the courtesy of R. M. FARQUHARand S. D. SCOTT, University of Toronto. OLAVI KOUVO, Geological Survey of Finland, provided helpful informa tion about Outokumpu deposits.
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