Mineralium Deposita

, Volume 49, Issue 6, pp 751–775 | Cite as

Sulfur sources of sedimentary “buckshot” pyrite in the Auriferous Conglomerates of the Mesoarchean Witwatersrand and Ventersdorp Supergroups, Kaapvaal Craton, South Africa

  • B. M. Guy
  • S. Ono
  • J. Gutzmer
  • Y. Lin
  • N. J. Beukes


Large rounded pyrite grains (>1 mm), commonly referred to as “buckshot” pyrite grains, are a characteristic feature of the auriferous conglomerates (reefs) in the Witwatersrand and Ventersdorp supergroups, Kaapvaal Craton, South Africa. Detailed petrographic analyses of the reefs indicated that the vast majority of the buckshot pyrite grains are of reworked sedimentary origin, i.e., that the pyrite grains originally formed in the sedimentary environment during sedimentation and diagenesis. Forty-one of these reworked sedimentary pyrite grains from the Main, Vaal, Basal, Kalkoenkrans, Beatrix, and Ventersdorp Contact reefs were analyzed for their multiple sulfur isotope compositions (δ34S, Δ33S, and Δ36S) to determine the source of the pyrite sulfur. In addition, five epigenetic pyrite samples (pyrite formed after sedimentation and lithification) from the Middelvlei and the Ventersdorp Contact reefs were measured for comparison. The δ34S, Δ33S, and Δ36S values of all 41 reworked sedimentary pyrite grains indicate clear signatures of mass-dependent and mass-independent fractionation and range from −6.8 to +13.8 ‰, −1.7 to +1.7 ‰, and −3.9 to +0.9 ‰, respectively. In contrast, the five epigenetic pyrite samples display a very limited range of δ34S, Δ33S, and Δ36S values (+0.7 to +4.0 ‰, −0.3 to +0.0 ‰. and −0.3 to +0.1 ‰, respectively). Despite the clear signatures of mass-independent sulfur isotope fractionation, very few data points plot along the primary Archean photochemical array suggesting a weak photolytic control over the data set. Instead, other factors command a greater degree of influence such as pyrite paragenesis, the prevailing depositional environment, and non-photolytic sulfur sources. In relation to pyrite paragenesis, reworked syngenetic sedimentary pyrite grains (pyrite originally precipitated along the sediment-water interface) are characterized by negative δ34S and Δ33S values, suggesting open system conditions with respect to sulfate supply and the presence of microbial sulfate reducers. On the contrary, most reworked diagenetic sedimentary pyrite grains (pyrite originally precipitated below the sediment-water interface) show positive δ34S and negative Δ33S values, suggesting closed system conditions. Negligible Δ33S anomalies from epigenetic pyrite suggest that the sulfur was sourced from a mass-dependent or isotopically homogenous metamorphic/hydrothermal fluid. Contrasting sulfur isotope compositions were also observed from different depositional environments, namely fluvial conglomerates and marine-modified fluvial conglomerates. The bulk of the pyrite grains from fluvial conglomerates are characterized by a wide range of δ34S values (−6.2 to +4.8 ‰) and small Δ33S values (±0.3 ‰). This signature likely represents a crustal sulfate reservoir derived from either volcanic degassing or from weathering of sulfide minerals in the hinterland. Reworked sedimentary pyrite grains from marine-modified fluvial conglomerates share similar isotope compositions, but also produce a positive Δ33S/δ34S array that overlaps with the composition of Archean barite, suggesting the introduction of marine sulfur. These results demonstrate the presence of multiple sources of sulfur, which include atmospheric, crustal, and marine reservoirs. The prevalence of the mass-dependent crustal sulfur isotope signature in fluvial conglomerates suggests that sulfate concentrations were probably much higher in terrestrial settings in comparison to marine environments, which were sulfate-deficient. However, the optimum conditions for forming terrestrial sedimentary pyrite were probably not during fluvial progradation but rather during the early phases of flooding of low angle unconformities, i.e., during retrogradational fluvial deposition, coupled in some cases with marine transgressions, immediately following inflection points of maximum rate of relative sea level fall.


Pyrite Sulfur Isotope Sedimentary Pyrite Diagenetic Pyrite Pyrite Nodule 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



This work is supported by a research grant to NJB by the National Research Foundation, Pretoria (GUN 2053184) and a NASA Exobiology grant, NNX07AU12G to SO. Danie Thompson and Dawie Strydom of Taung Gold, Louis Cloete of AngloGold Ashanti, and particularly Hans Brouwer of Gold Fields (now Sibanye Gold) are gratefully acknowledged for providing access to drill-core and underground mine samples. This manuscript benefited greatly from discussions with Donna Falconer, Eva Stueeken, and Breana Hashman. The editors, Bernd Lehmann and Hartwig Frimmel, and two anonymous reviewers are thanked for their constructive comments on earlier versions of the manuscript.

Supplementary material

126_2014_518_Fig10_ESM.jpg (5 mb)
Fig. S1

Variations in pyrite texture in black shale (Transvaal Supergroup). a Radiating pyrite spheroids (DIA-5). Note framboid core (DIA-1). b Putative atoll structures (DIA-1). c Spheroidal pyrite nodules (DIA-5). Compare with Fig. 3n. d Bladed, radiating pyrite (DIA-5). e Banded pyrite (DIA-5). f Fine-grained radiating pyrite (DIA-5). g, h Pyrite concretion (DIA-5). Note differential pyritization. i, j Euhedral pyrite crystals (DIA-6). Note zoning in j and compare zoning with Fig. 4g. (JPEG 4.99 MB)


  1. Agangi A, Hofmann A, Wohlgemuth-Ueberwasser CC (2013) Pyrite zoning as a record of mineralization in the Ventersdorp Contact Reef, Witwatersrand Basin, South Africa. Econ Geol 108:1243–1272Google Scholar
  2. Armstrong RA, Compston W, Retief EA, Williams LS, Welke HJ (1991) Zircon ion microprobe studies bearing on the age and evolution of the Witwatersrand basin. Precambrian Res 53:243–266Google Scholar
  3. Bailey AC, Law JDM, Cadle AB, Phillips GN (1990) The Zandfontein Quartzite Formation, a marine deposit in the Central Rand Group, Witwatersrand Supergroup. S Afr J Geol 93:135–146Google Scholar
  4. Bao H, Rumble D, Lowe DR (2007) The five stable isotope compositions of Fig Tree barites: implications on sulfur cycle in ca 3.2 Ga oceans. Geochim Cosmochim Acta 71:4868–4879Google Scholar
  5. Barnicoat AC, Henderson IHC, Knipe RJ, Yardley BWD, Napier RW, Fox NPC, Kenyon AK, Muntingh DJ, Strydom D, Winkler KS, Lawrence SR, Cornford C (1997) Hydrothermal gold mineralization in the Witwatersrand basin. Nature 386:820–824Google Scholar
  6. Barton ES, Hallbauer DK (1996) Trace-element and U-Pb isotope compositions of pyrite types in the Proterozoic Black Reef, Transvaal Sequence, South Africa: implications on genesis and age. Chem Geol 133:173–199Google Scholar
  7. Bekker A, Holland HD, Wang PL, Rumble D, Stein HJ, Hannah JL, Coetzee LL, Beukes NJ (2004) Dating the rise of atmospheric oxygen. Nature 427:117–120Google Scholar
  8. Beukes NJ (1995) Stratigraphy and basin analysis of the West Rand Group with special reference to prospective areas for placer gold deposits. (Unpubl. Report), Rand Afrikaans University (University of Johannesburg), 117pGoogle Scholar
  9. Beukes NJ, Cairncross B (1991) A lithostratigraphic–sedimentological reference profile for the late Mozaan Group, Pongola Sequence: application to sequence stratigraphy and correlation with the Witwatersrand Supergroup. S Afr J Geol 94:44–69Google Scholar
  10. Beukes NJ, Nelson JP (1995) Sea-level fluctuation and basin subsidence controls on the setting of auriferous paleoplacers in the Archean Witwatersrand Supergroup: a genetic and sequence stratigraphic approach. Extended Abstract, South African Geocongress, pp 860–863Google Scholar
  11. Binder B, Keppler H (2011) The oxidation state of sulfur in magmatic fluids. Earth Planet Sci Lett 301:190–198Google Scholar
  12. Bubela B, Cloud P (1983) Sulfide mineralization of microbial cells. J Aust Geol Geophys 8:355–357Google Scholar
  13. Canfield DE, Raiswell R, Westrich JT, Reaves CM, Berner RA (1986) The use of chromium reduction in the analysis of reduced inorganic sulfur in sediments and shales. Chem Geol 54:149–155Google Scholar
  14. Carstens H (1985) Early diagenetic cone-in-cone structures in pyrite concretions. J Sediment Res 55:105–108Google Scholar
  15. Carstens H (1986) Displacive growth of authigenic pyrite. J Sediment Res 56:252–257Google Scholar
  16. Catuneanu O (2001) Flexural partitioning in the Late Archaean Witwatersrand foreland system, South Africa. Sediment Geol 141–142:95–112Google Scholar
  17. Catuneanu O, Biddulph MN (2001) Sequence stratigraphy of the Vaal Reef facies associations in the Witwatersrand foredeep, South Africa. Sediment Geol 141–142:113–130Google Scholar
  18. Chaussidon M, Albarède F, Sheppard SMF (1989) Sulphur isotope variations in the mantle from ion microprobe analyses of micro-sulphide inclusions. Earth Planet Sci Lett 92:144–156Google Scholar
  19. Cloete LM (2009) Characterization of a recently discovered zone of intense hydrothermal alteration, deformation and unusual Au mineralization at Anglogold Ashanti’s Kopanang gold mine. MSc Thesis (Unpubl.), University of Johannesburg, South Africa, 91pGoogle Scholar
  20. Coward MP, Spencer RM, Spencer CE (1995) Development of the Witwatersrand Basin, South Africa. In: Coward MP, Ries AC (eds) Early Precambrian Processes, vol 95, Geol Soc Lond Spec Publ., pp 243–269Google Scholar
  21. Crowe SA, Døssing LN, Beukes NJ, Bau M, Kruger SJ, Frei R, Canfield DE (2013) Atmospheric oxygenation three billion years ago. Nature 501:535–538Google Scholar
  22. de Wit MJ, Armstrong RA, Kamo SL, Erlank AJ (1993) Gold-bearing sediments in the Pietersburg Greenstone Belt: age equivalents of the Witwatersrand Supergroup sediments, South Africa. Econ Geol 88:1242–1252Google Scholar
  23. de Wit MJ, Furnes H, Robins B (2011) Geology and tectonostratigraphy of the Onverwacht Suite, Barberton Greenstone Belt, South Africa. Precambrian Res 186:1–27Google Scholar
  24. Dimroth E (1979) Significance of diagenesis for the origin of Witwatersrand-type uraniferous conglomerates. Philos Trans R Soc Lond A291:277–287Google Scholar
  25. Domagal-Goldman SD, Kasting JF, Johnston DT, Farquhar J (2008) Organic haze, glaciations and multiple sulfur isotopes in the Mid-Archean Era. Earth Planet Sci Lett 269:29–40Google Scholar
  26. England BM, Ostwald J (1993) Framboid-derived structures in some Tasman fold belt base-metal sulphide deposits, New South Wales, Australia. Ore Geol Rev 7:381–412Google Scholar
  27. England GL, Rasmussen B, Krapez B, Groves DI (2002) Paleoenvironmental significance of rounded pyrite in siliciclastic sequences of the Late Archaean Witwatersrand Basin: oxygen-deficient atmosphere or hydrothermal evolution? Sedimentology 49:1133–1156Google Scholar
  28. Eriksson PG, Condie KC, Tirsgaard H, Mueller WU, Altermann W, Miall AD, Aspler LB, Catuneanu O, Chiarenzelli JR (1998) Precambrian clastic sedimentation systems. Sediment Geol 120:5–53Google Scholar
  29. Falconer DM (2003) Sediment-hosted gold and sulphide mineralization, Belle Brook, Southland, New Zealand. MSc Thesis (Unpubl.), University of Otago, New Zealand, 373pGoogle Scholar
  30. Falconer DM, Craw D, Youngson JH, Faure K (2006) Gold and sulphide minerals in Tertiary quartz pebble conglomerate gold placers, Southland, New Zealand. Ore Geol Rev 28:525–545Google Scholar
  31. Farquhar J, Bao H, Thiemans M (2000) Atmospheric influence of Earth’s earliest sulfur cycle. Science 289:756–758Google Scholar
  32. Farquhar J, Peters M, Johnston DT, Strauss H, Masterson A, Wiechert U, Kaufman AJ (2007) Isotopic evidence for Mesoarchaean anoxia and changing atmospheric sulphur chemistry. Nature 449:706–709Google Scholar
  33. Farquhar J, Cliff J, Zerkle AL, Kamyshny A, Poulton SW, Claire M, Adams D, Harms B (2013) Pathways for Neoarchean pyrite formation constrained by mass-independent sulfur isotopes. Proc Natl Acad Sci U S A. doi: 10.1073/pnas.1218851110 Google Scholar
  34. Feather CE, Koen GM (1975) The mineralogy of the Witwatersrand Reefs. Miner Sci Eng 7:189–224Google Scholar
  35. Ferry JM (1981) Petrology of graphitic sulfide-rich schists from south-central Maine: an example of desulfidation during prograde regional metamorphism. Am Mineral 66:908–930Google Scholar
  36. Fleet ME (1998) Detrital pyrite in Witwatersrand gold reefs: X-ray diffraction evidence and implications for atmospheric evolution. Terra Nova 10:302–306Google Scholar
  37. Frimmel HE (1997) Chlorite thermometry in the Witwatersrand basin: constraints on the Paleoproterozoic geotherm in the Kaapvaal Craton, South Africa. J Geol 105:601–615Google Scholar
  38. Frimmel HE (2005) Archaean atmospheric evolution: evidence from the Witwatersrand Gold Fields, South Africa. Earth-Sci Rev 70:1–46Google Scholar
  39. Frimmel HE (2008) Earth’s continental crustal gold endowment. Earth Planet Sci Lett 267:45–55Google Scholar
  40. Frimmel HE, Groves DI, Kirk J, Ruiz J, Chesley J, Minter WEL (2005) The formation and preservation of the Witwatersrand Gold Fields, the World's largest gold province. In: Hedenquist JW, Thompson JFH, Goldfarb RJ, Richards JP (eds) Economic Geology 100th Anniversary Volume. Society of Economic Geologists, Littleton, pp 769–797Google Scholar
  41. Frizzo P, Rampazzo G, Molinaroli E (1991) Authigenic iron sulphides in recent sediments of the Venice Lagoon (Northern Italy). Eur J Mineral 3:603–612Google Scholar
  42. Gaillard F, Scaillet B, Arndt NT (2011) Atmospheric oxygenation caused by a change in volcanic degassing pressure. Nature 478:229–232Google Scholar
  43. Genis J (1990) The sedimentology and depositional environment of the Beatrix Reef, Witwatersrand Supergroup. MSc Thesis (Unpubl.), University of the Witwatersrand, Johannesburg, South AfricaGoogle Scholar
  44. Gibson RL, Wallmach T (1995) Low pressure-high temperature metamorphism in the Vredefort Dome, South Africa–anticlockwise pressure-temperature path followed by rapid decompression. Geol J 30:121–135Google Scholar
  45. Grassineau NV, Nisbet EG, Bickle MJ, Fowler CMR, Lowry D, Mattey DP, Abell P, Martin A (2001) Antiquity of the biological sulphur cycle: evidence from sulphur and carbon isotopes in 2700 million year old rocks of the Belingwe belt, Zimbabwe. Proc R Soc Lond Ser B Biol Sci B268:113–119Google Scholar
  46. Grassineau NV, Nisbet EG, Fowler CMR, Bickle MJ, Lowry D, Chapman HJ, Mattey DP, Abell P, Yong J, Martin A (2002) Stable isotopes in the Archaean Belingwe belt, Zimbabwe: evidence for a diverse microbial mat ecology. In: Fowler CMR, Ebinger CJ, Hawkesworth CJ (eds) The Early Earth: Physical, Chemical and Biological Development. Geological Society, London, Special Publication 199, pp 309–328Google Scholar
  47. Guo Q, Strauss H, Schröder S, Gutzmer J, Wing BA, Baker MA, Kaufman AJ, Kim ST, Farquhar J (2009) Reconstructing earth’s surface oxidation across the Archean-Proterozoic transition. Geology 37:399–402Google Scholar
  48. Gutzmer J, Nhleko N, Beukes NJ, Pickard A, Barley ME (1999) Geochemistry and ion microprobe (SHRIMP) age of a quartz porphyry sill in the Mozaan Group: geochronological implication for the Pongola and the Witwatersrand Supergroups. S Afr J Geol 102:139–146Google Scholar
  49. Guy BM (2012) Pyrite in the Mesoarchean Witwatersrand Supergroup, South Africa. PhD Thesis (Unpubl.), University of Johannesburg, South Africa, 492pGoogle Scholar
  50. Guy BM, Beukes NJ, Gutzmer J (2010) Paleoenvironmental controls on the texture and chemical composition of pyrite from non-conglomeratic sedimentary rocks of the Mesoarchean Witwatersrand Supergroup, South Africa. S Afr J Geol 113:195–228Google Scholar
  51. Guy BM, Ono S, Gutzmer J, Kaufman AJ, Lin Y, Fogel ML, Beukes NJ (2012) A multiple sulfur and organic carbon isotope record from non-conglomeratic sedimentary rocks of the Mesoarchean Witwatersrand Supergroup, South Africa. Precambrian Res 216–219:208–231Google Scholar
  52. Habicht KS, Gade M, Thamdrup B, Berg P, Canfield DE (2002) Calibration of sulfate levels in the Archean ocean. Science 298:2372–2374Google Scholar
  53. Hallbauer DK (1986) The mineralogy and geochemistry of Witwatersrand pyrite, gold, uranium and carbonaceous matter. In: Anhaeusser CR, Maske S (eds) Mineral Deposits of Southern Africa. Geological Society of South Africa, Johannesburg, pp 731–752Google Scholar
  54. Hallbauer DK, von Gehlen K (1983) The Witwatersrand pyrites and metamorphism. Mineral Mag 47:473–479Google Scholar
  55. Hartzer FJ (2000) Geology of Transvaal inliers in the Bushveld complex. Counc Geosci 88:222pGoogle Scholar
  56. Hattori K, Campbell FA, Krouse HR (1983) Sulphur isotope abundances in Aphebian clastic rocks; implications for the coeval atmosphere. Nature 302:323–326Google Scholar
  57. Hessler AM, Lowe DR (2006) Weathering and sediment generation in the Archean: an integrated study of the evolution of siliciclastic sedimentary rocks of the 3.2 Ga Moodies Group, Barberton Greenstone Belt, South Africa. Precambrian Res 151:185–210Google Scholar
  58. Hirdes W (1979) The Proterozoic gold-uranium Kimberley Reef placers in the Evander and East Rand Goldfields Witwatersrand, South Africa: different facies and their source area aspects. PhD Thesis (Unpubl.), University of Heidelberg, Germany, 199pGoogle Scholar
  59. Hirdes W, Saager R (1983) The Proterozoic Kimberley Reef placer in the Evander Goldfields, Witwatersrand, South Africa. Monograph Series on Mineral Deposits 20, Gebrudewr Borntraeger, 101pGoogle Scholar
  60. Hoefs J, Nielsen H, Schidlowski M (1968) Sulfur isotope abundances in pyrite from the Witwatersrand Conglomerates. Econ Geol 63:975–977Google Scholar
  61. Hofmann A, Bekker A, Rouxel O, Rumble D, Master S (2009) Multiple sulphur and iron isotope composition of detrital pyrite in Archaean sedimentary rocks: a new tool for provenance analysis. Earth Planet Sci Lett 286:436–445Google Scholar
  62. Hutchinson RW, Viljoen RP (1987) Re-evaluation of gold source in Witwatersrand ores. S Afr J Geol 91:157–173Google Scholar
  63. Jamieson JW, Wing BA, Farquhar J, Hannington MD (2012) Neoarchaean seawater sulphate concentrations from sulphur isotopes in massive sulphide ore. Nat Geosci 6:61–64Google Scholar
  64. Johnston DT (2011) Multiple sulfur isotopes and the evolution of Earth’s surface sulfur cycle. Earth-Sci Rev 106:161–183Google Scholar
  65. Kamber BS, Whitehouse MJ (2007) Micro-scale sulphur isotope evidence for sulphur cycling in the late Archean shallow ocean. Geobiology 5:5–17Google Scholar
  66. Kaufman AJ, Johnston DT, Farquhar J, Masterson AL, Lyons TW, Bates S, Anbar AD, Arnold GL, Garvin J, Buick R (2007) Late archean biospheric oxygenation and atmospheric evolution. Science 317:1900–1903Google Scholar
  67. Ketzer JM, Holz M, Morad S, Al-Aasm IA (2003) Sequence stratigraphic distribution of diagenetic alterations in coal-bearing paralic sandstones: evidence from the Rio Bonito Formation (early Permian) southern Brazil. Sedimentology 50:855–877Google Scholar
  68. Kirk J, Ruiz J, Chesley J, Titley S, Walshe J (2001) A detrital model for the origin of gold and sulfides in the Witwatersrand basin based on Re-Os isotopes. Geochim Cosmochim Acta 65:2149–2159Google Scholar
  69. Koglin N, Frimmel HE, Minter WEL, Brätz H (2010) Trace-element characteristics of different pyrite types in Mesoarchaean to Palaeoproterozoic placer deposits. Mineral Deposita 45:259–280Google Scholar
  70. Köppel VH, Saager R (1974) Lead isotope evidence on the detrital origin of Witwatersrand pyrites and its bearing on the provenance of the Witwatersrand gold. Econ Geol 69:318–331Google Scholar
  71. Kositcin N, Krapez B (2004) SHRIMP U-Pb detrital zircon geochronology of the Late Archaean Witwatersrand Basin of South Africa: relation between zircon provenance age spectra and basin evolution. Precambrian Res 129:141–168Google Scholar
  72. Kositcin N, McNaughton NJ, Griffin BJ, Fletcher IR, Groves DI, Rasmussen B (2003) Textural and geochemical discrimination between xenotime of different origin in the Archaean Witwatersrand Basin, South Africa. Geochim Cosmochim Acta 67:709–731Google Scholar
  73. Krapez B (1985) The Ventersdorp Contact Placer: a gold-pyrite placer of stream and debris-flow origins from the Archaean Witwatersrand Basin of South Africa. Sedimentology 32:223–234Google Scholar
  74. Kröner A, Jaeckel P, Brandl G (2000) Single zircon ages for felsic to intermediate rocks from the Pietersburg and Giyani greenstone belts and bordering granitoid orthogneisses, northern Kaapvaal Craton, South Africa. J Afr Earth Sci 30:773–793Google Scholar
  75. Kump LR, Barley ME (2007) Increased subaerial volcanism and the rise of atmospheric oxygen 2.5 billion years ago. Nature 448:1033–1036Google Scholar
  76. Large RR, Danyushevsky LV, Hollit C, Maslennikov VV, Meffre S, Gilbert S, Bull SW, Scott R, Emsbo P, Thomas H, Singh B, Foster J (2009) Gold and trace element zonation in pyrite using a laser imaging technique: implications for the timing of gold in orogenic and Carlin-style sediment-hosted deposits. Econ Geol 104:635–668Google Scholar
  77. Large RR, Meffre S, Burnett R, Guy B, Bull S, Gilbert S, Goemann K, Danyushevsky LV (2013) Evidence for an intra-basinal source and multiple concentration processes in the formation of the Carbon Leader Reef, Witwatersrand Supergroup, South Africa. Econ Geol 108:1–28Google Scholar
  78. Large RR, Halpin JA, Danyushevsky LV, Maslennikov VV, Bull SW, Long JA, Gregory DD, Lounejeva E, Lyons TW, Sack PJ, McGoldrick PJ, Calver CR (2014) Trace element content of sedimentary pyrite as a new proxy for deep-time ocean–atmosphere evolution. Earth Planet Sci Lett 389:209–220Google Scholar
  79. Law JDM, Phillips GN (2005) Hydrothermal replacement model for Witwatersrand gold. In: Hedenquist JW, Thompson JFH, Goldfarb RJ, Richards JP (eds) Economic Geology 100th Anniversary Volume. Society of Economic Geologists, Littleton, pp 799–811Google Scholar
  80. Lefticariu L, Pratt LA, LaVerne JA, Schimmelmann A (2010) Anoxic pyrite oxidation by water radiolysis products—a potential source of biosustaining energy. Earth Planet Sci Lett 292:57–67Google Scholar
  81. Lott DA, Coveney RM, Murowchick JB, Grauch RI (1999) Sedimentary exhalative nickel-molybdenum ores in South China. Econ Geol 94:1051–1066Google Scholar
  82. McCarthy TS (1992) Syn-sedimentary deformation in the Witwatersrand basin. In: A short course reviewing recent developments in the understanding of the Witwatersrand basin v 1. Economic Geology Research Unit, University of the Witwatersrand, pp 85–94Google Scholar
  83. McLean PJ, Fleet ME (1989) Detrital pyrite in the Witwatersrand gold fields of South Africa: evidence from truncated growth banding. Econ Geol 84:2008–2011Google Scholar
  84. Minter WEL (1972) Sedimentology of the Vaal Reef in the Klerksdorp area. PhD Thesis (Unpubl.), University of the Witwatersrand, South Africa, 112pGoogle Scholar
  85. Minter WEL, Feather CE, Glatthar CW (1988) Sedimentological and mineralogical aspects of the newly discovered Witwatersrand placer deposit that reflect Proterozoic Weathering, Welkom Gold Field, South Africa. Econ Geol 83:481–491Google Scholar
  86. Morse JW, Luther GW III (1999) Chemical influences on trace metal-sulfide interactions in anoxic sediments. Geochim Cosmochim Acta 63:3373–3378Google Scholar
  87. Myers RE, McCarthy TS, Stanistreet IG (1990) A tectono-sedimentary reconstruction of the development and evolution of the Witwatersrand basin with particular emphasis on the Central Rand Group. S Afr J Geol 93:180–201Google Scholar
  88. Myers RE, Zhou T, Phillips GN (1993) Sulphidation in the Witwatersrand Goldfields: evidence from the Middelvlei Reef. Mineral Mag 57:395–405Google Scholar
  89. Ohfuji H, Rickard D (2005) Experimental syntheses of framboids—a review. Earth-Sci Rev 71:147–170Google Scholar
  90. Ohmoto H, Goldhaber MB (1997) Sulfur and carbon isotopes. In: Barnes HL (ed) Geochemistry of Hydrothermal Ore Deposits. John Wiley and Sons, New York, pp 571–611Google Scholar
  91. Ono S, Eigenbrode JL, Pavlov AA, Kharecha P, Rumble D, Kasting JF, Freeman KH (2003) New insights into Archean sulfur cycle from mass-independent sulfur isotope records from the Hamersley Basin, Australia. Earth Planet Sci Lett 213:15–30Google Scholar
  92. Ono S, Wing B, Johnston DT, Farquhar J, Rumble D (2006) Mass-dependent fractionation of quadruple sulfur isotope system as a new tracer of sulfur biogeochemical cycles. Geochim Cosmochim Acta 70:2238–2252Google Scholar
  93. Ono S, Beukes NJ, Rumble D (2009a) Origin of two distinct multiple-sulfur isotope compositions of pyrite in the 2.5 Ga Klein Naute Formation, Griqualand West Basin, South Africa. Precambrian Res 169:48–57Google Scholar
  94. Ono S, Kaufman AJ, Farquhar J, Sumner DY, Beukes NJ (2009b) Lithofacies control on multiple-sulfur isotope records and the Neoarchean sulfur cycles. Precambrian Res 169:58–67Google Scholar
  95. Ono S, Whitehill AR, Lyons JR (2013) Contribution of isotopologue self-shielding to sulfur mass-independent fraction during sulfur dioxide photolysis. J Geophys Res-Atmos 118:1–11Google Scholar
  96. Palmer JA (1986) Paleoweathering in the Witwatersrand and Ventersdorp Supergroups. MSc Thesis (Unpubl.), University of the Witwatersrand, South Africa, 166pGoogle Scholar
  97. Partridge MA, Golding SD, Baublys KA, Young E (2008) Pyrite paragenesis and multiple sulfur isotope distribution in late Archean and early Paleoproterozoic Hamersley Basin sediments. Earth Planet Sci Lett 272:41–49Google Scholar
  98. Philippot P, Van Zuilen M, Lepot K, Thomazo C, Farquhar J, Van Kranendonk MJ (2007) Early Archaean microorganisms preferred elemental sulphur, not sulfate. Science 317:1534–1537Google Scholar
  99. Philippot P, Van Zuilen M, Rollion-Bard C (2012) Variations in atmospheric sulphur chemistry on early Earth linked to volcanic activity. Nat Geosci 5:668–674Google Scholar
  100. Phillips GN, Dong G (1994) Chert-plus-pyrite-pebbles in the Witwatersrand goldfields. Int Geol Rev 36:65–71Google Scholar
  101. Phillips GN, Law JDM (2000) Witwatersrand gold fields: geology, genesis and exploration. Soc Econ Geologists (SEG) Rev 13:439–500Google Scholar
  102. Phillips GN, Myers RE (1989) Witwatersrand gold fields: part II. An origin for Witwatersrand gold during metamorphism and associated alteration. Econ Geol Monogr 6:598–608Google Scholar
  103. Phillips GN, Powell R (2011) Origin of Witwatersrand gold: a metamorphic devolatilization-hydrothermal replacement model. Appl Earth Sci 120:112–129Google Scholar
  104. Phillips GN, Myers RE, Palmer JA (1987) Problems with the placer model for Witwatersrand gold. Geology 15:1027–1030Google Scholar
  105. Poujol M, Robb LJ, Anhaeusser CR, Gericke B (2003) A review of the geochronological constraints on the evolution of the Kaapvaal Craton, South Africa. Precambrian Res 127:181–213Google Scholar
  106. Ramdohr P (1958) New observations on the ores of the Witwatersrand in South Africa and their genetic significance. Transactions of the Geological Society of South Africa 61:1–50, AnnexureGoogle Scholar
  107. Rantzsch U, Gauert CDK, Van der Westhuizen WA, Duhamel I, Cuney M, Beukes GJ (2011) Mineral chemical study of U-bearing minerals from the Dominion Reefs, South Africa. Mineral Deposita 46:187–196Google Scholar
  108. Reimer TO, Mossman DJ (1990) Sulphidation of Witwatersrand black sands: from enigma to myth. Geology 18:426–429Google Scholar
  109. Reimold WU, Przybylowicz WJ, Gibson RL (2004) Quantitative major and trace elemental mapping by PIXE of concretionary pyrite from the Witwatersrand Basin, South Africa. X-Ray Spectrom 33:189–203Google Scholar
  110. Reinhard CT, Raiswell R, Scott C, Anbar AD, Lyons TW (2009) A late Archean sulfidic sea stimulated by early oxidative weathering of the continents. Science 326:713–716Google Scholar
  111. Robb LJ, Davis D, Kamo SL, Meyer FM (1992) Ages of altered granites adjoining the Witwatersrand basin with implications for the origin of gold and uranium. Nature 357:677–680Google Scholar
  112. Roerdink DL, Mason PRD, Farquhar J, Reimer T (2012) Multiple sulfur isotopes in Paleoarchean barites identify an important role for microbial sulfate reduction in the early marine environment. Earth Planet Sci Lett 331–332:177–186Google Scholar
  113. Ruppert LF, Hower JC, Eble CF (2005) Arsenic-bearing pyrite and marcasite in the Fire Clay coal bed, middle Pennsylvanian Breathitt Formation, eastern Kentucky. Int J Coal Geol 63:27–35Google Scholar
  114. Saager R (1970) Structures in pyrite from the Basal Reef in the Orange Free State goldfield. Trans Geol Soc South Africa 73:29–46Google Scholar
  115. Saager R, Muff R (1986) The auriferous placer at Mount Robert, Pietersburg Greenstone Belt. In: Anhaeusser CR, Maske S (eds) Mineral Deposits of Southern Africa. Geological Society of South Africa, Johannesburg, pp 213–220Google Scholar
  116. Saager R, Stupp HD, Utter T, Matthey HO (1986) Geological and mineralogical notes on placer occurrences in some conglomerates of the Pongola sequence. In: Anhaeusser CR, Maske S (eds) Mineral Deposits of Southern Africa. Geological Society of South Africa, Johannesburg, pp 473–487Google Scholar
  117. SACS (South African Committee for Stratigraphy) (2006) A revised stratigraphic framework for the Witwatersrand Supergroup. Counc Geosci Lithostratigraphic Ser 42:1–7Google Scholar
  118. Schidlowski M (1965) Probable life forms from the Precambrian of the Witwatersrand System (South Africa). Nature 205:895–896Google Scholar
  119. Schieber J (2002) Sedimentary pyrite: a window into the microbial past. Geology 30:531–534Google Scholar
  120. Schieber J, Riciputi L (2005) Pyrite-marcasite coated grains in the Ordovician Winnipeg Formation Canada: an intertwined record of surface conditions, stratigraphic condensation, geochemical “reworking”, and microbial activity. J Sediment Res 75:905–918Google Scholar
  121. Schmitz MD, Bowring SA, de Wit MJ, Gartz V (2004) Subduction and terrane collision stabilize the western Kaapvaal craton tectosphere 2.9 billion years ago. Earth Planet Sci Lett 222:363–376Google Scholar
  122. Schneiderhan E, Zimmerman U, Gutzmer J, Mezger K, Armstrong R (2011) Sedimentary Provenance of the Neoarchean Ventersdorp Supergroup, South Africa: shedding light on the evolution of the Kaapvaal Craton during the Neoarchean. J Geol 119:575–596Google Scholar
  123. Scholz F, Neumann T (2007) Trace element diagenesis in pyrite-rich sediments of the Achterwasser lagoon, SW Baltic Sea. Mar Chem 107:516–532Google Scholar
  124. Scott RJ, Meffre S, Woodhead J, Gilbert SE, Berry RF, Emsbo P (2009) Development of framboidal pyrite during diagenesis, low-grade regional metamorphism, and hydrothermal alteration. Econ Geol 104:1143–1168Google Scholar
  125. Selles-Martinez J (1996) Concretion morphology, classification and genesis. Earth-Sci Rev 41:177–210Google Scholar
  126. Smithies RH, van Kranendonk MJ, Champion DC (2007) The Mesoarchean emergence of modern subduction. Gondwana Res 11:50–68Google Scholar
  127. Staude S, Wagner T, Markl G (2007) Mineralogy, mineral compositions and fluid evolution at the Wenzel Hydrothermal Deposit, Southern Germany: implications for the formation of the Kongsberg-type silver deposits. Can Mineral 45:1147–1176Google Scholar
  128. Strauss H, Beukes NJ (1991) A geochemical study of carbon and sulfur in sedimentary rocks from the Witwatersrand and Ventersdorp Supergroups and its bearing on the depositional environment. (Unpubl. Progress Report), Rand Afrikaans University (University of Johannesburg), 37pGoogle Scholar
  129. Stueeken EE, Catling DC, Buick R (2012) Contributions to late Archaean sulphur cycling by life on land. Nat Geosci 5:722–725Google Scholar
  130. Tankard AJ, Jackson MPA, Eriksson KA, Hobday DK, Hunter DR, Minter WEL (1982) Crustal evolution of Southern Africa, 3.8 Billion Years of Earth History. Springer-Verlag, New York, 523pGoogle Scholar
  131. Taylor KG, Macquaker JHS (2000) Early diagenetic pyrite morphology in a mudstone-dominated succession: the Lower Jurassic Cleveland Ironstone Formation, eastern England. Sediment Geol 131:77–86Google Scholar
  132. Thomas HV, Large RR, Bull SW, Maslennikov V, Berry RF, Fraser R, Froud S, Moye R (2011) Pyrite and pyrrhotite textures and composition in sediments, laminated quartz veins, and reefs at Bendigo Gold Mine Australia: insights for ore genesis. Econ Geol 106:1–31Google Scholar
  133. Tucker RF (1980) The sedimentology and mineralogy of the Composite Reef on Cooke Section, Randfontein Estates Gold Mine, Witwatersrand, South Africa. MSc Thesis (Unpubl.), University of the Witwatersrand, South Africa, 355pGoogle Scholar
  134. Turchyn AV, Tipper ET, Galy A, Lo JK, Bickle MJ (2013) Isotope evidence for secondary sulfide precipitation along the Marsyandi River, Nepal, Himalayas. Earth Planet Sci Lett 374:36–46Google Scholar
  135. Tweedie KAM (1968) The stratigraphy and sedimentary structures of the Kimberley Shales in the Evander gold field, Eastern Transvaal, South Africa. Trans Geol Soc South Africa 71:235–256Google Scholar
  136. Ueno Y, Ono S, Rumble D, Maruyama S (2008) Quadruple sulfur isotope analysis of ca 3.5Ga Dresser Formation: new evidence for microbial sulfate reduction in the Early Archean. Geochim Cosmochim Acta 72:5675–5691Google Scholar
  137. Utter T (1978) Morphology and geochemistry of different pyrite types from the Upper Witwatersrand System of the Klerksdorp goldfield, South Africa. Geol Rundsch 67:774–804Google Scholar
  138. Verrezen J (1987) Sedimentology of the Vaal Reef paleoplacer in the western portion of Vaal Reefs Mine. MSc thesis (Unpubl.), Rand Afrikaans University (University of Johannesburg), South Africa, 194pGoogle Scholar
  139. Wacey D, Saunders M, Brasier MD, Kilburn MR (2011) Earliest microbially mediated pyrite oxidation in 3.4 billion-year-old sediments. Earth Planet Sci Lett 301:393–402Google Scholar
  140. Wagner T, Boyce AJ (2006) Pyrite metamorphism in the Devonian Hunsrück Slate of Germany: insights from laser microprobe sulfur isotope analysis and thermodynamic modeling. Am J Sci 306:525–552Google Scholar
  141. Watchorn MB (1981) The stratigraphy and sedimentology of the West Rand basin in the Western Transvaal. PhD Thesis (Unpubl.), University of the Witwatersrand, South Africa, 154pGoogle Scholar
  142. Watchorn MB, O’Brien MF (1991) The significance of marine modification in some Witwatersrand placers—an example from the Lower Witwatersrand, West Rand Group. S Afr J Geol 94:333–339Google Scholar
  143. Wiese RG, Fyfe WS (1986) Occurrence of iron sulfides in Ohio coals. Int J Coal Geol 6:251–276Google Scholar
  144. Wilkin RT, Barnes HL, Brantley SL (1996) The size distribution of framboidal pyrite in modern sediments: an indicator of redox conditions. Geochim Cosmochim Acta 60:3897–3912Google Scholar
  145. Wilkin RT, Arthur MA, Dean WE (1997) History of water-column anoxia in the Black Sea indicated by pyrite framboid size distributions. Earth Planet Sci Lett 148:517–525Google Scholar
  146. Woodland BG (1975) Pyritic cone-in-cone concretions Fieldiana. Geology 33:125–139Google Scholar
  147. Zhao B (1998) A mineralogical and geochemical study of alteration associated with the Ventersdorp Contact Reef in the Witwatersrand Basin. PhD Thesis (Unpubl.), University of the Witwatersrand, South Africa, 297pGoogle Scholar
  148. Zhou T, Phillips GN, Dong G, Myers RE (1995) Pyrrhotite in the Witwatersrand gold fields, South Africa. Econ Geol 90:2361–2369Google Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

  • B. M. Guy
    • 1
    • 4
  • S. Ono
    • 2
  • J. Gutzmer
    • 1
    • 3
  • Y. Lin
    • 2
    • 5
  • N. J. Beukes
    • 1
  1. 1.Department of GeologyUniversity of JohannesburgJohannesburgSouth Africa
  2. 2.Department of Earth, Atmospheric, and Planetary SciencesMassachusetts Institute of TechnologyCambridgeUSA
  3. 3.Helmholtz-Institute Freiberg for Resource TechnologyFreibergGermany
  4. 4.Mineral ServicesSGS South AfricaJohannesburgSouth Africa
  5. 5.School of Earth and Space SciencesUniversity of Science and Technology of ChinaHefeiPeople’s Republic of China

Personalised recommendations