Mineral.

Deposita 26, 83-88 (1991)

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neralium slta

9 Springer-Verlag 1991

Ni-Mo-PGE-Au-rich ores in Chinese black shales and speculations on possible analogues in the United States
R.M. Coveney, Jr 1 and C. Nansheng 2

1 Department of Geosciences, University of Missouri-Kansas City, Kansas City, Missouri 64110-2499, United States 2 Institute of Geochemistry, Academia Sinica, Guiyang, Guizhou Province, People's Republic of China Received: March 1990/Accepted: December 1990 To our knowledge the Zunyi deposits are the only mines in the world where Mo is the primary product recovered from shale. The Zunyi Mo mines annually yield ,~ 1000 tonnes of ore averaging ,-~4 wt.% Mo and containing up to 4% Ni, 2% Zn, 0.7 ppm Au, 50 ppm Ag, 0.3 ppm Pt, 0.4 ppm Pd, and 30 ppb Ir (Chen et al. 1982, Fan 1983, Fan et al. 1984, Chen 1988, Chen and Coveney 1989). Peak values are near 7.7% Mo, 2700 ppm Se and 2.5% As. Precious metals are not extracted from the ores, but mine tailings are stockpiled for eventual recovery. The sulfide ore (Fig. 2) consists mainly of a mixture of nodular pyrite, nodular phosphorite and pellets of solid organic matter (so-called stone coal), quartz and shale. Relatively coarse ( ~ 1 mm-diameter) nodular textures grade to coatings of sulfides on tiny (1-10 micrometer) spherules of organic matter (Fan 1983). Ore minerals include jordisite, pyrite, vaesite, gersdorffite, polydymite and millerite (Fan 1983). Some massive sulfide samples are very dense but others are suprisingly light because of abundant organic matter and large amounts of pores. Preliminary SEM/EDAX studies of several sulfide nodules consisting chiefly of pyrite indicate that the porous rims of nodules contain much more Ni (Fig. 3) than the interiors. The exterior portions of some nodules contain more Se and As than the interior portions. Some are rimmed with a relatively late Mo-rich phase, probably jordisite. Mo may even be present in the rim of the nodule shown in Fig. 3 because small amounts of Mo ( < ,-~1%) are obscured by interference between the K-alpha peak of S and the L-alpha peak for Mo and because of the relatively high excitation potential for Mo K-alpha. Sulfur isotope values (6 34S) for four samples drilled from pyrite nodules from Zunyi average -9.98 per mil relative to the Canon Diablo Troilite standard (range of values=-7.3 to -11.2). Analysis of one rim of porous (and possibly corroded) pyrite from Zunyi yields a 6 34S value of + 3.7 per mil, appreciably heavier than the interior of the nodule which measures -10.2 per mil (Fig. 3). Siliceous venting tubes and chert beds found in the underlying (late Sinian) Doushantuo Formation of north

Abstract. Molybdenum-rich black shales from the Cam-

brian of south China contain sulfide beds with > 2 wt. % Mo, > 2 wt.% Ni and 200-700 mg/T each for Au, Pt and Pd. Similar deposits occur in Canada. In the U.S. Midwest, Paleozoic black shales contain an extensive Mo anomaly and sporadic enrichments for Pt group elements, suggesting the presence of Ni-Mo-PGE-Au sulfide deposits like those being mined in China.

Chen et al. (1982) reported enriched values for Ni, Mo, V, Cu, U, Ba and Ag from lower Cambrian black shales in ten provinces in south China, including Yunnan, Guizhou, Hunan, Jiangxi and Zhejiang (Fig. 1). Black illitic Cambrian shales from these occurrences average 350ppm Mo and 150 ppm Ni (Fan 1983). Moreover, values exceeding 4 wt. % V20 5 have been reported from carbonaceous and phosphatic Cambrian black shales of south China (Zhang 1983). All together, the metal-rich shales define an extensive Mo anomaly extending for hundreds of thousands of square kilometers (Chen et al. 1982). The Cambrian black shales contain thin sulfide lenses and beds with ore-grade enrichments of Mo and Ni and lesser values of PGE and Au. Sulfide lenses are mined for Mo in Guizhou and similar deposits were once mined for Mo and Ni in Hunan. Analogous deposits are known from at least one other location, the Selwyn Basin of Canada. They may occur elsewhere, for example in the Paleozoic of the central United States (Chen and Coveney 1989).
Zunyi, Guizhou

Discovered in 1979 and mined since 1985, the Zunyi Mo deposits are located near Songlin, close to Zunyi (Tsunyi) in the province of Guizhou. Ore occurs as thin (5-15 cm) sulfide lenses and beds in nearly fiat-lying black shales of the lower Cambrian Niutitang Formation a few meters above its contact with the Proterozoic Z (Sinian) Doushantuo Formation.

84

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Fig. 1. Locations of Ni-Mo deposits in Cambrian black shales, south China. Ni-Mo sulfide bed occurrences include Dezhe (De), Zhejin (Zh), Zunyi (Zu), Dayong (Da), Cili (Ci), Duchang (Du) and

Lizhe (Li). Locations of major suture zones, flysch terrane, and ophiolites (irregular black) generalized from Hsu et al. (1988). Karst areas generalized from various sources

The province of Guizhou (including the immediate area of the Zunyi Mo mine) contains some of the finest known examples of tower karst topography. Extending throughout the provinces of Yunnan, Guizhou, Guangxi and Hunan, the spectacular karst region of south China is a product of deep modern weathering which, as discussed below, may have influenced development of the ores. Other locations in South China Metal-rich Cambrian black shales occur in nine other provinces in south China besides Guizhou (Chen et al. 1982). About 300-400 km northeast of Zunyi (Fig. 1), Cambrian shales near Dayong and Cili, Hunan, contain similar nodular Ni-Mo sulfide beds (Fig. 2) with enriched values for Ni, Mo, Au and P G E (Fan 1983). Sulfide beds near D a y o n g were formerly mined for Ni and Mo. Other N i - M o deposits occur in Cambrian shales near Dezhe, Yunnan (Chen et al. 1982), at Duchang, Jiangxi (Fan 1983), and in m e t a m o r p h o s e d lower Cambrian beds near Lizhe, Zhejiang (Chen and Yang 1987). All known occurrences of the N i - M o sulfide beds are found close to the Precambrian-Cambrian boundary. The areal distribution

Fig. 2. Ore Slabs from Zunyi and Dayong. Similar nodular textures are shown by the Ni-Mo sulfides in samples collected 350 km apart

Guizhou (Chen 1988) suggest a hydrothermal source of metals in some cases. Quartz crystals from the vent tubes contains fluid inclusions with homogenization temperatures between 158 and 172~

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Fig. 3. SEM views of pyrite nodule in Ni-Mo ore bed from Early Cambrian black shale, Zunyi, Guizhou. Elemental analyses by energy dispersive X-ray spectrometry (EDAX); S-isotype analyses by mass spectrometric techniques (Krueger Enterprises) on samples drilled from nodule with a 1 mm microdrill. The late (Ni-rich) pyrite rim contains relatively heavy sulfur (634S = + 3.7 per mil, contrasting with -10.2 per mil for pyrite in the interior of the nodule of some of the highest grade occurrences of Ni-Mo sulfide ore forms a linear belt, possibly controlled by basement fractures, which extends ENE from Yunnan through Guizhou, Hunan, and Jianxi to Zhejiang (Fig. 1). Despite many similarities, there are differences among the deposits. For example, at some deposits, Fan (1983) notes the presence of sphalerite, pentlandite, tennantite and violarite as well as the ore minerals listed above for Zunyi. Tuffs are associated with the mineralized horizons at some locations. Origins of the ores Judging from surface exposures, few of the Ni-Mo deposits can have the genetic connections with the marie or ultramafic source/host rocks characteristic of conventional (igneous-affiliated) P G E deposits. Small late Paleozoic or Mesozoic ophiolite melanges containing peridotites, gabbros and spilites (Hsu etal. 1988) occur sparsely near the zone of Ni-Mo ore shale occurrences. Yet only the Duchang occurrence has ophiolites nearby (Fig. 1). On the basis of elevated Ir values Fan (1983) and Fan etal. (1984) have suggested extraterrestrial source for
some

constituents of the ores. Whether or not a bolide is involved, the characteristic nodular textures of the sulfide beds implies a syngenetic origin (Fan 1983, Chen et al. 1982). It seems more likely that submarine springs or some other terrestrial source provided supplied metals to the shales, perhaps during sedimentation. The linear distribution of known ores may reflect migration of mineralizing fluids through deep fractures from deep-crustal or mantle sources. Another possibility is expulsion of fluids during orogenic events reflected by thick flysch or slate terrane (Hsu et al. 1988) located south of the main oregrade occurrences. However there may also have been an epigenetic component of mineralization. Our preliminary data indicate that late pyrite contains more Ni, Se and M o than early pyrite. It also contains distinctly heavier sulfur than the interiors of nodules. The second stage may, of course, merely represent the last events of syngenesis, but we do not think that this is the case because of the sharp differences between early and late pyrite (Fig. 3). The ages and cause(s) of the inferred second stage of mineralization are unknown but the geologic setting of south China suggests at least two possibilities.

86 The second stage may have been caused by an epigenetic hydrothermal event. For example, suturing of tectonic plates during the Mesozoic (Hsu et al. 1988) may have induced migration of hydrothermal fluids through the adjacent terrane. Diagenetic fluids and basinal brines responsible for M V T Pb-Zn mineralization are capable of mobilizing P G E (Macdonald 1987, Lechler and Hsu 1989 a) and M o (Erickson et al. 1981, 1987, Coveney and Glascock, 1989). A second possibility is suggested by the unusually widespread and well-developed Quaternary karst of south China. Disnar (1981) and others have shown that Mo and Se are readily fixed by organic matter at ambient temperatures and acid p H conditions although they are quite mobile at high p H values. Possibly M o and Se were mobilized at low temperatures by high p H solutions equilibrated with carbonate beds and were then precipitated wherever the pregnant solutions infiltrated sulfide beds. This mechanism would readily explain the juxtaposition of well-developed karst with beds that are exceptionally enriched in Mo. Finally it should be noted that the mineralization m a y be related to a n c i e n t weathering. U n c o n f o r m i t y U deposits, associated with the early-middle Proterozoic stratigraphic boundary, carry enriched values for Ni, Mo, Au and P G E (Hulbert et al. 1988). Grauch (1989) and Grauch and Mosier (1987) note that such deposits originate by complex processes that probably involve deep weathering, m e t a m o r p h i s m and migration of basinal brines although the relative importance of each factor remains unassessed. Such deposits have m a n y features in c o m m o n with the N i - M o - P G E - A u deposits of China (e.g., an identical suite of metals associated with a major stratigraphic unconformity). Investigations in progress in our laboratories should clarify whether or not these resemblances have genetic significance. Unconventional sedimentary PGE occurrences in Canada O f all known deposits N i - M o sulfide beds in black shales of the Selwyn basin (Canadian Yukon) most closely resemble those of China. Like the Chinese deposits, those in Canada have bed thicknesses of ~ 5 - 1 5 cm, contain abundant vaesite, appreciable values for Ni, Mo, P G E and Au and spatial association with a major unconformity at the edge of a sedimentary basin. These beds contain as much as 5.8% Ni, 1% Zn and 800 mg/t P G E (L.J. Hulbert, personal communication 1988; Parry 1989, R.C. Carne personal communication 1990). Differences include somewhat lower values for M o ( < 0.4% Mo) and Devonian host strata. The Chinese and Canadian deposits were both discovered a little more than a decade ago, and it is entirely possible that similar deposits have been overlooked elsewhere. Enriched P G E values are known from other sedimentary occurrences (Table 1), such as the Kupferschiefer of Poland (Kucha 1982), Mn-mineralized pipes in limestones in N e v a d a (Lechler and Hsu 1989 b) and the Carboniferous of the U.S. Midwest (Chyi 1982). P G E values in excess of 100 ppb (mg/t) are c o m m o n in such occurrences (Table 1). Table 1. Peak values for Au, PGE and Ni in non-placer sedimentary deposits compared with conventional (igneous-hosted) PGE ores ppb (mg/T) Au
Black shales

wt% Ni Pt Pd Ir 20 0.7 1.0 0.4 5.1 5.8 0.2 0.04

Poland ~ 3 000 000 340 000 1 600 000 China 2 700 300 380 Yukon Canada 3 86 540 210 Oklahoma USA 4 19 150 Nevada USA 5 30 10 Indiana USA 6 4 <20 <20 Indiana USA 7 63 16
Other sediments

Kentucky 8 Australia 9 Canada 10

Conventional ores 11

2 5 36 000 260 120 120

200 620 12 000 4 800 4 200 340

1 330 14 000 3 000 14 800 360

200 530 10

0.18 0.24 1.30

Bushveld RSA Stillwater USA Sudbury Canada

1 Permian Kupferschiefer (Kucha, 1982) 2 Cambrian sulfide bed (Fan, 1983) 3 Devonian sulfide bed (Parry, 1989) 4 Mississippian (Orth et al., (1988) 5 Devonian (Lechler and Hsu, 1989b) 6 Pennsylvanian (Coveney and Glascoek, 1989) 7 Devonian-Mississip. (Lechler and Hsu, 1989b) 8 Pennsylvanian, Number 9 Coal (Chyi, 1982) 9 Proterozoic, Coronation Hill (Grauch, 1989) 10 Proterozoic, Athabasca (Grauch, 1989) 11 Average values, from Hulbert et al. (1988)

Carboniferous beds of the Central United States In the central United States, anomalous values for P G E are known from Devonian-Mississippian black shales of Indiana (Lechler and Hsu 1989b), Mississippian black shales of O k l a h o m a (Orth et al. 1988), and Pennsylvanian (Upper Carboniferous) coals of Kentucky (Chyi 1982) (Fig. 4). Black marine shales from the Devonian-Mississippian boundary and in the Pennsylvanian are markedly enriched in heavy metals. Like the Chinese black shales they routinely contain values between tens and thousands of parts per million Mo (Shaffer et al. 1981, Coveney and Martin | 983, Coveney et al. 1987, Coveney and Glascock 1989). For example, the Pennsylvanian Mecca Quarry, Excello, Logan Quarry and Holland shales of Indiana contain a v e r a g e values > 1000 p p m in Indiana. Some of these same beds can be traced to Illinois, Iowa, Kentucky and Missouri where they typically contain hundreds of p p m Mo. Concentrations gradually diminish to tens of p p m Mo in Kansas and O k l a h o m a (Coveney et al. 1987, Coveney and Glascock 1989). Other Pennsylvanian black shales contain hundreds of p p m M o in Kansas and Missouri (Coveney and Glascock 1989). U.S. shales contain enriched values for Mo comparable in magnitude and areal extent (Fig. 4) to those of the Chinese black shales (Fig. 1).

87

Fig. 4. Locations of PGE enrichments in Carboniferous beds, central United States. Distribution of Pennsylvanian coals and shales is approximated by extent of Mecca Quarry Shale and equivalent beds (modif. from Wanless and Wright, 1978). Coals in Kentucky (1) contain up to 210 ppb Pt (Chyi, 1982). Heavy stippling shows original distribution of Chattanooga Shale and equivalents (from Conant and Swanson, 1961; Nuelle, 1988; Amsden, 1988) which contain PGE enrichments in Oklahoma (2, from Orth et al., 1988) and Indiana (3, from Lechler and Hsu, 1989b). The Midwest contains extensive karst and major Pb-Zn deposits (MVT) formed by basinal brines that may have been derived from the Illinois, Anadarko and Arkoma basins (e.g., Leach and Rowan, 1986). Basement features (e.g., Humboldt fault, the Reelfoot rift, and the midcontinent geophysical anomlay) are from Bickford et al. (1986)

the Central North American rift system (Midcontinent geophysical anomaly) has been suggested by Berendsen (1989). At present it is impossible to say whether or not NiMo-PGE-Au deposits similar to those of China exist in the central United States, where many of the most critical areas associated with major basement structures are buried. Nevertheless the question is sufficiently important that we will briefly summarize the evidence. There are important similarities between the central United States and southern China. Most notably both areas contain broad expanses of metalliferous Paleozoic black shales with very enriched values for Mo (> 100 to 2000 ppm). Both have broad regions of karst and both border sedimentary basins. Known PGE anomalies in the Carboniferous beds of the central United States are of the same order of magnitude as the values in the Ni-Mo beds in China. These anomalies are located in the vicinity of major basement structures that could have acted as feeder zones. On the other hand, the Chinese deposits are located in a tectonically active area rather than a craton. At least some are associated with tuff beds suggesting the possibility of a critical genetic role for igneous activity which can probably be ruled out in the central United States. If this is the case, other places in the United States such as Nevada, where Lechler and Hsu (1989 a, b) report significant PGE values associated with sediments, would clearly be more suitable areas than the Midwest for prospecting.

Conclusions

Black shales may have ore grade enrichments in the vicinity of the Reelfoot Rift where Chyi (1982) reports enhanced values for Pt in Pennsylvanian coals. Lechler and Hsu (1989b) find lesser but still appreciable values for PGE in equivalents of the Devonian-Mississippian Chattanooga Shale (up to 63 ppb Pt in Indiana). Ore-grade enrichments may also be associated with the Humboldt fault of Kansas or elsewhere near faults bounding the Midcontinent geophysical anomaly. Orth et al. (1988) have reported whole-rock values as large as 160 ppb for Pt in beds near the Devonian-Mississippian boundary near Ada, Oklahoma, for example. The basement near this location is intensely faulted and structurally complex as it lies on an extension of the Humboldt fault (Fig. 4). Distal to this major basement structure, in eastern Kansas and western Missouri, what may be minor expulsion vents are found in limestones next to the metal-rich Pennsylvanian shales. These take the form of Pb-Zn mineralized pipes such as the one at the Jumbo mine (Blasch and Coveney 1988) and minor structures such as mineralized animal burrows or root casts containing ferroan dolomite with or without calcite, barite, petroleum or sphalerite (Ragan 1987). Because of poor exposure, it is unclear whether or not major hydrothermal venting and mineralization occurred near major basement structures such as the Humboldt fault, though the possibility exists. The likelihood that PGE ores or unconformity-related U deposits may be associated with

The Ni-Mo-PGE-Au sulfide beds of south China probably originated as exhalites from submarine springs during the Cambrian. Some metals of economic interest may have been added later by circulating basinal brines or by modern supergene events related to deep karst weathering. A genetic role for deep ancient weathering, analogous to unconformity U deposits, is also conceivable. Extraterrestrial sources for PGE are an interesting possibility, but probably need not be invoked without additional evidence. Discovered only recently, the Ni-Mo-Pt-Au deposits of China and Canada may be only the first indications of a globally significant source for Ni, Mo and PGE. Similar deposits may well exist in Poland or elsewhere in association with metalliferous black shales. Although evidence is inconclusive concerning the existence of Ni-Mo-PGE-Au sulfide beds in the Paleozoic of the U.S. Midwest, there are sufficient similarities in the settings - major Mo anomalies, possible feeder fractures in the basement, extensive karst - to justify exploration. Acknowledgements. We appreciate the support of the National Science Foundations of the United States (Grant EAR89-17322) and the People's Republic of China. Travel and seed grants from the School of Graduate Faculties and Research, the Center for International Affairs, and the College of Arts and Sciences at the University of Missouri-Kansas City were essential. Discussions with Zhang Aiyun, R.C. Carne, Fan Delian, G.A. Desborough, E.D.

88 Goebel, R.I. Grauch, J.B. Maynard, J.B. Murowchick, B.E. Nesbitt and D.F. Sangster have been invaluable. We particularly wish to thank L.J. Hulbert for calling attention to the Selwyn Basin. Professors D.P. Hopkins and J.B. Murowchick provided helpful comments on the m s . Some analyses were supplied by M.D. Glascock (University of Missouri Research Reactor). Sulfur isotope analyses were performed by Krueger Enterprises. Scott Robinson of the UMKC School of Dentistry coordinated SEM studies. This paper is a contribution to International Geological Correlations Programme Project Number 254, "Metalliferous Black Shales and Related Ore Deposits". Jan Pasava and Richard I. Grauch organized the IGC session at which these results were first reported (Chen and Coveney 1989). Disnar, J.-R.: Etude exp6rimental de la fixation de m6taux par un mat6riau sbdimentaire actual d'origine algaire - lI. Fixation 'in vitro' de UO~ +, Cu 2+, Ni 2+, Pb 2+, Co 2 , Mn 2+, ainsi que VOW, MoO4 , et GeO~-. Geochim. Cosmochim. Acta 45: 363z379 (1981) Erickson, R.L., Mosier E.L., Odland, S.K., Erickson, M.S.: A favorable belt for possible mineral discovery in subsurface Cambrian rocks in southern Missouri. Econ. Geol. 76:921-933 (1981) Erickson, R.L., Erickson, M.S., Chazin, B., Bacter, J.W., Masters, J.M., Eidel, J.J. (1987) Subsurface geochemical investigation in western and southern Illinois. A pilot study. Illinois Geol. Surv. Mineral Notes 98: (1987) Fan Delian: Polyelements in the Lower Cambrian black shale series in southern China. In: The Significance of Trace Metals in Solving Petrogenetic Problems and Controversies, Augustithis, S.S. ed., Theophrastus Publications S.A., Athens, 447-474 (1983) Fan Delian, Yang Ruiying, Huang Zhongxiang: The Lower Cambrian black shale series and iridium anomaly in south China. In: Academia Sinica, Developments in Geoscience, Contributions to the 27th IGC, Moscow, 215-224 (1984) Grauch, R.I.: Early-Middle Proterozoic unconformities: Sources for platinum group and precious metals. In: Schindler, K.S., ed., Report of the Fifth Annual McKelvey Forum, USGS Circ. 1035:26 (1989) Grauch, R.I., Mosier, D.L.: Descriptive model of unconformity U-Au. In: Cox, D.P., and Singer, D.A. eds., Mineral Deposit Models USGS Bull. 1693:248-250 (1987) Hsu, K.J., Sun Shu, Chen Haihong, Pen Haipo, Sengor, A.M.C.: Mesozoic overthrusts in south China. Geology 16:418-421 (1988) Hulbert, L.J., Duke, J.M., Eckstrand, O.R., Lydon, J.W., Scoates, R.F.J.: Geological environments of the platinum group elements. Geol. Surv. Canada Open File 1440:148 p. (1988) Kucha, H.: Platinum group metals in the Zechstein copper deposits, Poland. Econ. Geol. 77:1578-1591 (1982) Leach, D.L., Rowan, E.L.: Genetic link between Ouachita foldbelt tectonism and the Mississippi Valley-type lead-zinc deposits of the Ozarks. Geology 14:931-935 (1986) Lechler, P.J., Hsu, L.C.: Possible controls on the distribution of hydrothermal platinum group minerals in western North America. Geol. Soc. Amer. Abstr. with Programs 21:A131 (1989a) Lechler, P.J., Hsu, L.C.: Review of hydrothermal platinum-group metal deposits. Soc. Min. Engin. Preprint 89-55:7 (1989 b) Mcdonald, A.J.: The platinum group element deposits: Classification and genesis. Geoscience Canada 14:155-166 (1987) Nuelle, L.M.: Distribution of radionuclides in Missouri geologic terranes: A summary of available data and the need for more data. In: Marikos, M.A., Hansman, R.H., eds., Missouri Dept. Natur. Res. Spec. PuN. 4:75-90 (1988) Orth, C.J., Quintana, L.R., Gilmore, J.S., Barrick, J.E., Haywa, J.N., Spesshardt, S.A.: Pt-group anomalies in the lower Mississippian of southern Oklahoma. Geology 16:627-630 Parry, D.: The petrographic analysis of the host rock and vaesite bearing horizon on the Nick property, Yukon Territory, undergraduate thesis, University of Alberta, Edmonton, 22 p. (1989) Ragan, V.M.: Geothermometry and organic matter-mineral link for the mineralization at the Prescott Zinc deposit and adjacent country rock of Linn County, Kansas. M.S. Thesis: Univ. of Missouri, Kansas City (1987) Shaffer, N.R., Leininger, R.K., Ripley, E.M., Gilstrap, M.S.: Heavy metals in organic-rich New Albany Shale of Indiana. Geol. Soc. Amer. Programs with Abstracts 13:551 (1981) Wanless, H.R., Wright, C.R.: Paleoenvironmentalmaps of Pennsylvanian rocks, Illinois basin and northern midcontinent region: Geol. Soc. Amer. Map MC-23:31 (1978) Zhang Aiyun: The geochemistry of vanadium in the marine black rock sequence of Yangjiabao. Proc. XI Internat. Congr. Carbonifer. Stratigr. Geol., Madrid, 2:31-42 (1983)

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