Abstract
South African basalt-hosted chalcedonies provided an ideal case study, to (a) achieve information about the origin of mineral-forming fluids, the process of chalcedony formation and weathering alteration and (b) to verify if the geochemical and micro-textural characterization of chalcedony allowed multiple provenances to be distinguished. For the first time, Drakensberg chalcedonies from the Karoo Jurassic basalts and Windsorton chalcedonies from the alluvial environment of the Vaal River (traversing the Allanridge basaltic–andesitic lavas) were investigated by optical microscopy, laser ablation inductively coupled plasma mass spectroscopy and isotope ratio mass spectrometry (16O, 18O). The results showed that the compositional differences observed in Drakensberg and Windsorton chalcedonies could not be explained by changes in host rocks composition. The tholeiitic basaltic–andesitic lavas of the Allanridge Formation (Pniel Group, comparison term for Windsorton samples) and the tholeiitic basaltic–andesitic lavas of the Golden Gate Unit (Drakensberg Group, comparison term for Drakensberg specimens) proved to be very similar, also in terms of alteration degree. Conversely, both geochemical and oxygen isotope compositions clearly supported a relatively low temperature, hydrothermal origin for all the investigated chalcedonies, further indicating that differences mostly occurred during their formation (fluid circulation). Moreover, several characteristics suggested deposition in non-equilibrium conditions, although oxidizing conditions were most likely. Weathering processes were effective in the alluvial environment only, leading to a wider compositional heterogeneity of Windsorton chalcedonies with respect to Drakensberg samples. Lastly, a correlation between color and chromophores (Fe and Mn) amounts was lacking while a correlation between the geochemical composition and the texture was clearly observed in several specimens.
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References
Bau M, Koschinsky A (2009) Oxidative scavenging of cerium on hydrous Fe oxide: evidence from the distribution of rare earth elements and yttrium between Fe ox-ides and Mn oxides in hydrogenetic ferromanganese crusts. Geochem J 43:37–47. https://www.terrapub.co.jp/journals/GJ/pdf/4301/43010037.pdf
Bau M, Koschinsky A, Dulski P, Heinz JR (1996) Comparison of the partitioning behaviors of yttrium, rare earth elements, and titanium between hydrogenetic marine ferromanganese crusts and seawater. Geochim Cosmochim Acta 60:1709–1725. https://doi.org/10.1016/0016-7037(96)00063-4
Beer M (1992) Achate und andere Mineralien aus den nordost-böhmischen Melaphyren. Mineralien-Welt 4:47–51 (ISSN:0939-6640)
Blankenburg H-J, Pilot J, Werner CD (1982) Erste Ergebnisse der Sauerstoffisotopenuntersuchungen an Vulkanitachaten und ihre genetische Interpretation. Chem Erde 41:213–217
Blankenburg H-J (1988) Achat. Deutscher Verlag für Grundstoffindustrie, Leipzig
Braun J-J, Pagel M, Muller J-P, Bilong P, Michard A, Guillet B (1990) Cerium anomalies in lateritic profiles. Geochim Cosmochim Acta 54:781–795. https://doi.org/10.1016/0016-7037(90)90373-S
Brown RW, Summerfield MA, Gleadow AJW (2002) Denudational history along a transect across the Drakensberg Escarpment of southern Africa derived from apatite fission track thermochronology. J Geophys Res 107(B12):1–18. https://doi.org/10.1029/2001jb000744
Brown K, Marean CW, Herries AIR, Jacobs Z, Tribolo C, Braun D, Roberts DL, Meyer MC, Bernatchez J (2009) Fire as an engineering tool of early modern Humans. Science 325:859–862. https://doi.org/10.1126/science.1175028
Cairncross B (2004) Field guide to rocks and minerals of Southern Africa. Struik New Holland Publishing, Cape Town, p 297
Cairncross B, Dixon R (1995) Minerals of South Africa. Geological Society of South Africa, Publisher (ISBN No.0-620-19324-7)
Cairncross B, du Plessis H (2018) Stilbite and associated minerals from the Butha-Buthe district, Lesotho, southern Africa. Rocks Miner 93:306–317. https://doi.org/10.1080/00357529.2018.1454104
Clark R (2002) Fairburn Agate: gem of South Dakota. Silverwind Agates, Publ, Appleton
Cornell DH, Meintjies PG, van der Westhuizen WA, Frei D (2017) Microbeam U-Pb Zircon dating of the Makwassie Formation and underlying units in the Ventersdorp Supergroup of South Africa. S Afr J Geol 120:525–540. https://doi.org/10.25131/gssajg.120.4.525
Cross BL (1996) The agates of Northern Mexico. Burgess International Group, Edina
Crow C, Condie KC (1988) Geochemistry and origin of late Archean volcanics from the ventersdorp supergroup, South Africa. Precambrian Res 42:19–37. https://doi.org/10.1016/0301-9268(88)90008-3
Duarte LC, Hartmann LA, Ronchi LH, Berner Z, Theye T, Massonne HJ (2011) Stable isotope and mineralogical investigation of the genesis of amethyst geodes in the Los Catalanes gemological district, Uruguay, southernmost Paraná volcanic province. Miner Depos 46:239–255. https://doi.org/10.1007/s00126-010-0323-6
Duncan AR, Marsh JS (2006) The Karoo Igneous Province. In: Johnson MR, Anhaeusser CR, Thomas RJ (eds) The geology of South Africa. Geological Society of South Africa, Pretoria, pp 501–520
Duncan AR, Erlank AJ, Marsh JS (1984) Regional geochemistry of the Karoo igneous province. Spec Publ Geol Soc S Afr 13:355–388 (ISBN 0 7988 2123 X)
Dunlevey JN, Ramluckan VR, Mitchell AA (1993) Secondary mineral zonation in the Drakensberg Basalt Formation, South Africa. S Afr J Geol 96:215–20. https://hdl.handle.net/10520/AJA10120750_488
Fallick AE, Jocelyn J, Donnelly T, Guy M, Behan C (1985) Origin of agates in volcanic rocks from Scotland. Nature 313:672–674. https://doi.org/10.1038/313672a0
Fallick AE, Jocelyn J, Hamilton PJ (1987) Oxygen and hydrogen stable isotope systematics in Brazilian agates. In: Rodriguez-Clemente R, Taedy Y (eds) Geochemistry and mineral formation in the Earth surface. Centre Nationale de la Recherche Scientifique, Paris, pp 99–117 (ISBN 84 00 06683 9)
Frondel C (1962) The system of mineralogy. Silica minerals, vol III. Wiley, New York
Frondel C (1978) Characters of quartz fibers. Am Miner 63:17–27
Gliozzo E (2019) Variations on the silica theme: classification and provenance from Pliny to current supplies. In: Artioli G, Oberti R (eds) EMU notes in mineralogy, the contribution of mineralogy to Cultural Heritage, vol. 20, chapter 2. The Mineralogical Society, Twickenham, UK, pp 59–131
Gliozzo E, Grassi N, Bonanni P, Meneghini C, Tomei MA (2011) Gemstones from Vigna Barberini at the Palatine Hill (Rome, Italy). Archaeometry 53(3):469–489
Gliozzo E, Mattingly DJ, Cole F, Artioli G (2014) In the footsteps of Pliny: tracing the sources of Garamantian carnelian from Fazzan, south-west Libya. J Archaeol Sci 52:218–241
Götze J, Nasdala L, Kleeberg R, Wenzel M (1998) Occurrence and distribution of “moganite” in agate/chalcedony: a combined micro-Raman, Rietveld, and cathodoluminescence study. Contrib Minerol Petrol 133:96–105. https://doi.org/10.1007/s004100050440
Götze J, Tichomirowa M, Fuchs H, Pilot J, Sharp ZD (2001) Geochemistry of agates: a trace element and stable isotope study. Chem Geol 175:523–541. https://doi.org/10.1016/S0009-2541(00)00356-9
Götze J, Möckel R, Kempe U, Kapitonov I, Vennemann T (2009) Characteristics and origin of agates in sedimentary rocks from the Dryhead area, Montana, USA. Mineral Mag 73:673–690. https://doi.org/10.1180/minmag.2009.073.4.673
Götze J, Nasdala L, Kempe U, Libowitzky E, Rericha A, Vennemann T (2012) The origin of black colouration in onyx agate from Mali. Mineral Mag 76:115–127. https://doi.org/10.1180/minmag.2012.076.1.115
Götze J, Gaft M, Möckel R (2015) Uranium and uranyl luminescence in agate/chalcedony. Mineral Mag 79:983–993. https://doi.org/10.1180/minmag.2015.079.4.08
Götze J, Möckel R, Vennemann T, Müller A (2016) Origin and geochemistry of agates in Permian volcanic rocks of the Sub-Erzgebirge basin, Saxony (Germany). Chem Geol 428:77–91. https://doi.org/10.1016/j.chemgeo.2016.02.023
Haake R, Holzhey G (1989) Achate in kugelformigen Rhyoliten des Rotliegenden im sachsisch-thuringischem Raum. Chem Erde 49:173–183
Harris C (1988) Oxygen isotope geochemistry of a quartz-agate geode from north-western Namibia. Commun Geol Surv S W Africa/Namibia 4: 49–51 http://www.mme.gov.na/files/publications/866_Harris_O%20isotopes%20of%20quartz-agate%20geodes.pdf
Harris C (1989) Oxygen-isotope zonation of agates from Karoo volcanics of the Skeleton Coast, Namibia. Am Mineral 74:476–481
Heaney OJ (1993) A proposed mechanism for the growth of chalcedony. Contrib Mineral Petrol 115:66–74. https://doi.org/10.1007/BF00712979
Heaney PJ, Davis AM (1995) Observation and origin of self-organized textures in agates. Science 269:1562–1565. https://doi.org/10.1126/science.269.5230.1562
Holzhey G (2001) Contribution to petrochemical-mineralogical characterization of alteration processes within the marginal facies of rhyolitic volcanic of lower Permian Age, Thuringian Forest, Germany. Chem Erde 61:149–186
Jourdan F, Féraud G, Bertramd H, Watkeys MK, Renne PR (2007) Distinct brief major events in the Karoo large igneous province clarified by new 40Ar/39Ar ages on the Lesotho basalts. Lithos 98:195–209. https://doi.org/10.1016/j.lithos.2007.03.002
Keyser N (1998) The geology and geochemistry of the Ventersdorp Supergroup in the area between Vryburg, Ottosdal and Mafikeng. Geol Surv S Afr Bull 122:117
Landmesser M (1995) “Mobility by metastability”: silica transport and accumulation at low temperatures. Chem Erde 55:149–176
Landmesser M (1998) “Mobility by metastability” in sedimentary and agate petrology: applications. Chem Erde 58:1–22
Ledevin M (2013) Les cherts Archéens de la ceinture de roches vertes de Barberton (3.5–3.2 Ga), Afrique du Sud. Processus de formation et utilisation comme proxys paleo-environnementaux. Phd Thesis in Earth Sciences. Université de Grenoble, France https://pdfs.semanticscholar.org/ba20/9cd4ccaef739c0a7a442446565adca80d2c5.pdf
Liu TG, Miah MRU, Schmitt R (1988) Cerium: a chemical tracer of paleo-oceanic redox conditions. Geochim Cosmochim Acta 52:1361–1371. https://doi.org/10.1016/0016-7037(88)90207-4
Lock BE, Reid DR, Broderick TJ (1974) Stratigraphy of the Karroo volcanic rocks in the Barkly East District. S Afr J Geol 77:117–29. https://hdl.handle.net/10520/AJA10120750_343
Luttinen AV (2018) Bilateral geochemical asymmetry in the Karoo large igneous province. Sci Rep. https://doi.org/10.1038/s41598-018-23661-3
Marsh JS, Eales HV (1984) The chemistry and petrogenesis of igneous rocks of the Karoo central area, Southern Africa. Geol Soc S Afr Spec Publ 13:27–67
Marsh JS, Hooper PR, Rehacek J, Duncan RA, Duncan AR (1997) Stratigraphy and age of Karoo basalts of Lesotho and implications for correlation within the Karoo igneous province. In: Mahoney JJ, Coffin MF (eds) Large igneous province: continental: oceanic and planetary flood volcanism, geophysical monograph series. American Geophysical Union, Washington, pp 247–272
Matsuhisa Y, Goldsmith JR, Clayton RN (1979) Oxygen isotopic fractionation in the system quartz-albite-anorthite-water. Geochim Cosmochim Acta 43:1131–1140. https://doi.org/10.1016/0016-7037(79)90099-1
McCarthy TS (1983) Evidence for the former existence of a major southerly flowing river in Griualand West. S Afr J Geol 86:37–49. https://hdl.handle.net/10520/AJA10120750_376
McCrank GFD, Misiura JD, Brown PA (1981). Plutonic rocks in Ontario. Geological Survey of Canada Paper 80–23, 171 pp. https://doi.org/10.4095/109543
McDonough WF, Sun SS (1995) The composition of the Earth. Chem Geol 67:1050–1056. https://doi.org/10.1016/0009-2541(94)00140-4
Merino E, Wang Y, Deloule E (1995) Genesis of agates in flood basalts: twisting of chalcedony fibers and trace-element geo-chemistry. Am J Sci 295:1156–1176. https://doi.org/10.2475/ajs.295.9.1156
Mitchell AA, Ramluckan VR, Dunlevey JN, Eglington BM (1996) The basalt stratigraphy of the Sani Pass, Kwazulu/Natal Drakensberg. S Afr J Geol 99:251–262. https://hdl.handle.net/10520/EJC-93477327e
Möckel R, Götze J (2007) Achate aus sächsischen Vulkaniten des Erzgebirgischen Beckens. Veröff. Mus. f. Naturk. Chemnitz 30:25–60. http://mineralienkabinett.org/2007_moeckel_goetze.pdf
Möckel R, Götze J, Sergeev SA, Kapitonov IN, Adamskaya EV, Goltsin NA, Vennemann T (2009) Trace-element analysis by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS): a case study for agates from Nowy Kościoł, Poland. SibFU 2:123–138
Mountain ED (1953) Agate pebbles on the south-eastern coast of the Union. S Afr J Geol 56:177–182. https://hdl.handle.net/10520/AJA10120750_2186
Mourre V, Villa P, Henshilwood CS (2010) Early use of pressure flaking on lithic artifacts at Blombos cave, South Africa. Science 330:659–662. https://doi.org/10.1126/science.1195550
Moxon JT (1996) Agate: microstructure and possible origin. Terra, Doncaster
Moxon JT (2017) A re-examination of water in agate and its bearing on the agate genesis enigma. Mineral Mag 81:1223–1244. https://doi.org/10.1180/minmag.2017.081.002
Moxon T, Reed SJB (2006) Agate and chalcedony from igneous and sedimentary hosts aged 13 to 3480 Ma: a cathodoluminescence study. Mineral Mag 70:485–498. https://doi.org/10.1180/0026461067050347
Moxon T, Nelson DR, Zhang M (2006) Agate recrystallization: evidence from samples found in Archaean and Proterozoic host rocks, Western Australia. Aust J Earth Sci 53:235–248. https://doi.org/10.1080/08120090500499255
Moxon T, Reed SJB, Zhang M (2007) Metamorphic effects on agate found near the Shap granite, Cumbria, England: as demonstrated by petrography, X-ray diffraction and spectroscopic methods. Mineral Mag 71:461–476. https://doi.org/10.1180/minmag.2007.071.4.461
Moxon T, Petrone CM, Reed SJB (2013) Characterization and genesis of horizontal banding in Brazilian agate: an X-ray diffraction, thermogravimetric and electron microprobe study. Mineral Mag 77:227–248. https://doi.org/10.1180/minmag.2013.077.3.02
Partridge TC, Brink ABA (1967) Gravels and terraces of the lower Vaal basin. S Afr Geogr J 49:21–38. https://doi.org/10.1080/03736245.1967.10559417
Pemberton J (1978) The geochemistry and petrology of Karroo basalts of the Barkly east area, north eastern Cape. Thesis presented for the degree of Master of Science at Rhodes University, Grahamstown
Porraz G, Texier P-J, Archer W, Piboule M, Rigaud J-P, Tribolo C (2013) Technological successions in the Middle Stone Age sequence of Diepkloof Rock Shelter, Western Cape, South Africa. J Archaeol Sci 40:3376–3400. https://doi.org/10.1016/j.jas.2013.02.012
Potgieter CD, Snyman CP, Förtsch EB (1982) Epigenetic laumontite in the Jurassic Clarens and Drakensberg Formations of the Karoo Sequence. S Afr J Geol 85:203–210. https://hdl.handle.net/10520/AJA10120750_1085
Prinsloo LC, van der Merwe EM, Wadley L (2018) The thermal behaviour of silica varieties used for tool making in the Stone Age. J Therm Anal Calorim 131:1135–1145. https://doi.org/10.1007/s10973-017-6602-z
Ramluckan VR (1992). The petrology and geochemistry of the Karoo Sequence basaltic rocks in the Natal Drakensberg at Sani Pass. M.Sc. thesis (unpublished, University of Durban-Westville (now KwaZuluNatal), Durban, South Africa
Rhodes RC, Krohn DH (1972) Tectonic control over regional geochemical variation in the Karroo basaltic Province of Southern Africa. S Afr J Geol 75:11–21. https://hdl.handle.net/10520/AJA10120750_2744
Rudnick RL, Gao S (2003) the composition of the continental crust. In: Holland HG, Turekian KK (eds) Treatise on geochemistry, vol 3. The crust. Elsevier, Oxford, pp 1–64
Saunders JA (1990) Oxygen-isotope zonation of agates from Karoo volcanics of the Skeleton Coast, Namibia: discussion. Am Mineral 75:1205–1206. http://www.minsocam.org/ammin/AM75/AM75_1205.pdf
Schmitt-Riegraf C (1996) Magmenentwicklung und spät-bis post-magmatische Alterationsprozesse permischer Vulkanite im Nordwesten der Nahe-Mulde. Münster Forsch Geol Paläont 80:1–251
Shields G, Stille P (2001) Diagenetic constraints on the use of cerium anomalies as palaeoseawater redox proxies: an isotopic and REE study of Cambrian phosphorites. Chem Geol 175:29–48. https://doi.org/10.1016/S0009-2541(00)00362-4
Strauch G, Nitzsche H-M, Holzhey G (1994) Isotopenuntersuchungen an Rhyolithen und Achatbildungen. Neues Jb Miner Abh 165:103–104
Sumner PD, Hall KJ, van Rooy JL, Meiklejohn KI (2009) Rock weathering on the eastern mountains of southern Africa: review and insights from case studies. J Afr Earth Sci 55:236–244. https://doi.org/10.1016/j.jafrearsci.2009.04.010
Tiepolo M, Bottazzi P, Palenzona M, Vannucci R (2003) A laser probe coupled with ICP-double focusing sector-field mass spectrometer for in situ analysis of geological samples and U-Pb dating of zircon. Can Mineral 41:259–272. https://doi.org/10.2113/gscanmin.41.2.259
van Achterbergh E, Ryan CG, Jackson SE, Griffin WL (2001) Data reduction software for LA-ICP-MS. In: Sylvester P (ed) Laser-ablation-ICPMS in the earth sciences: principles and applications, vol 29. Mineralogical Association of Canada, Ottawa, Ont., Canada, pp 239–243
Van der Westhuizen WA, de Bruiyn H, Meintjies PG (2006) The Ventersdorp Supergroup. In: Johnson MR, Anhaeusser CR, Thomas RJ (eds) The geology of South Africa. Council for Geoscience, Johannesburg, pp 187–208
Venneman TW, Morlok A, von Engelhardt W, Kyser K (2001) Stable isotope composition of impact glasses from the Nördlinger Ries impact crater, Germany. Geochim Cosmochim Acta 65:1325–1336. https://doi.org/10.1016/S0016-7037(00)00600-1
Wadley L, de la Peña P, Prinsloo LC (2017) Responses of South African agate and chalcedony when heated experimentally, and the broader implications for heated archaeological minerals. J Field Archaeol 42:364–377. https://doi.org/10.1080/00934690.2017.1337438
Wang Y, Merino E (1990) Self-organizational origin of agates: banding, fiber twisting, composition, and dynamic crystallization model. Geochim Cosmochim Acta 54:1627–1638. https://doi.org/10.1016/0016-7037(90)90396-3
Wang Y, Merino E (1995) Origin of fibrosity and banding in agates from flood basalts. Am J Sci 295:49–77. https://doi.org/10.2475/ajs.295.1.49
Wedepohl KH (1978) Handbook of Geochemistry. Springer, Berlin
Wilson MGC, McKenna N, Lynn MD (2007) The occurrence of diamonds in South Africa. Council for Geoscience, Pretoria, p 105
Wood SA (1990) The aqueous geochemistry of the rare-earth elements and yttrium. 2. Theoretical predictions of speciation in hydrothermal solutions to 350 °C at saturation water vapor pressure. Chem Geol 88:99–125. https://doi.org/10.1016/0009-2541(90)90106-H
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The authors are indebted to the two anonymous reviewers for providing insightful comments which improved the quality of our manuscript. One of us (BC) acknowledges that this research was partly funded by the NRF (National Research Foundation) and CIMERA (the DST-NRF Centre of Excellence for Integrated Mineral and Energy Resource Analysis). Any opinions, findings and conclusions or recommendations expressed are those of the author, and therefore, the NRF and CIMERA do not accept liability in regard thereto.
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531_2019_1737_MOESM1_ESM.tif
Supplementary material 1 Binary plots showing the geochemical variation of SiO2 wt% contents with respect to significant minor elements in Drakensberg (A–F) and Windsorton (G–L) samples. In Windsorton binary diagrams (G–L), black full circles indicate Windsorton samples while grey full circles in the background represent the Drakensberg Group samples. The outlier sample Win6 has been omitted (TIFF 51340 kb)
531_2019_1737_MOESM2_ESM.tif
Supplementary material 2 Geochemical profiles on samples Win10, 11 and 12. Macro (scanner) images have been provided per each sample. Along Fe and Mn profiles, B = Brown; W = white; O = orange; G = grey; Bk = blackish (TIFF 64761 kb)
531_2019_1737_MOESM3_ESM.tif
Supplementary material 3 Geochemical profiles on samples Win13, 14 and 15. Macro (scanner) images have been provided per each sample. Along Fe and Mn profiles, O = orange; B = Brown; G = grey; Bk = blackish (TIFF 64761 kb)
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Gliozzo, E., Cairncross, B. & Vennemann, T. A geochemical and micro-textural comparison of basalt-hosted chalcedony from the Jurassic Drakensberg and Neoarchean Ventersdorp Supergroup (Vaal River alluvial gravels), South Africa. Int J Earth Sci (Geol Rundsch) 108, 1857–1877 (2019). https://doi.org/10.1007/s00531-019-01737-3
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DOI: https://doi.org/10.1007/s00531-019-01737-3