Rare earth element geochemistry of the Upper Permian limestone: the Kanigorgeh mining district, NW Iran

The limestone of the Ruteh Formation of Upper Permian age in the Kanigorgeh district (northeast of Bukan, NW Iran) contains several layers and lenses of bauxitic ores. Mineralogical data show that this limestone consists of calcite and quartz as major and plagioclase, kaolinite, and hematite as minor mineral phases. Geochemical analyses reveal that the proportions of ?REEs (La-Lu) in this limestone vary from 35.28 to 160.78 ppm. The values of Eu and Ce anomalies (normalized to PAAS) of the limestone have ranges of 1.11-1.68 and 0.89-1.16, respectively. The high values of ?REEs; low values of Y/Ho; strong and positive correlations between ?REEs and elements such as Si, Al, Ti, V, Co, Ni, Rb, Cu, and Nb; and negative correlations between CaO and ?REEs suggest that the observed variations in values of ?REEs in the limestone were controlled principally by the quantity of detrital materials. Geochemical data also illustrate that the observed positive Eu anomalies in the limestone may be due to the presence of plagioclase and also a function of diagenetic processes. Furthermore, the variations in Ce anomalies may be due to the detrital input. The distribution of REEs (normalized to chondrite) illustrates different patterns in both rocks (the limestone and the bauxitic ores) in light of differentiation degree of LREEs from HREEs and values of conservative indexes such as Eu anomaly. Considering these pronounced discrepancies, it appears that the limestone, despite having relatively high concentration of ?REEs, did not play a significant role in supplying lanthanides for the bauxitic ores.

Rare earth element geochemistry of the Upper Permian limestone: the Kanigorgeh mining district, NW Iran

The limestone of the Ruteh Formation of Upper Permian age in the Kanigorgeh district (northeast of Bukan, NW Iran) contains several layers and lenses of bauxitic ores. Mineralogical data show that this limestone consists of calcite and quartz as major and plagioclase, kaolinite, and hematite as minor mineral phases. Geochemical analyses reveal that the proportions of ?REEs (La-Lu) in this limestone vary from 35.28 to 160.78 ppm. The values of Eu and Ce anomalies (normalized to PAAS) of the limestone have ranges of 1.11-1.68 and 0.89-1.16, respectively. The high values of ?REEs; low values of Y/Ho; strong and positive correlations between ?REEs and elements such as Si, Al, Ti, V, Co, Ni, Rb, Cu, and Nb; and negative correlations between CaO and ?REEs suggest that the observed variations in values of ?REEs in the limestone were controlled principally by the quantity of detrital materials. Geochemical data also illustrate that the observed positive Eu anomalies in the limestone may be due to the presence of plagioclase and also a function of diagenetic processes. Furthermore, the variations in Ce anomalies may be due to the detrital input. The distribution of REEs (normalized to chondrite) illustrates different patterns in both rocks (the limestone and the bauxitic ores) in light of differentiation degree of LREEs from HREEs and values of conservative indexes such as Eu anomaly. Considering these pronounced discrepancies, it appears that the limestone, despite having relatively high concentration of ?REEs, did not play a significant role in supplying lanthanides for the bauxitic ores.

___

  • Abedini A, Calagari AA (2013a). Rare earth elements geochemistry of Sheikh-Marut laterite deposit, NW Mahabad, West- Azarbaidjan province, Iran. Acta Geol Sin-Engl 87: 176–185.
  • Abedini A, Calagari AA (2013b). Geochemical characteristics of bauxites: the Permian Shahindezh horizon, NW Iran. N J Geol Palaont Abh 270: 301–324.
  • Abedini A, Calagari AA (2013c). Geochemical characteristics of Kanigorgeh ferruginous bauxite horizon, West-Azarbaidjan province, NW Iran. Period Mineral 82: 1–23.
  • Abedini A, Calagari AA (2014). REE geochemical characteristics of titanium-rich bauxites: the Permian Kanigorgeh horizon, NW Iran. Turkish J Earth Sci 23: 513–532.
  • Aghanabati A (2004). Geology of Iran. Tehran, Iran: Geological Survey of Iran (in Persian).
  • Armstrong-Altrin JS, Verma SP, Madhavaraju J, Lee YI, Ramasamy S (2003). Geochemistry of Late Miocene Kudankulam Limestones, South India. Int Geol Rev 45: 16–26.
  • Bau M (1996). Controls on fractionation of isovalent trace elements in magmatic and aqueous systems: Evidence from Y/Ho, Zr/ Hf and lanthanide tetrad effect. Contrib Mineral Petr 123: 323–333.
  • Bau M, Koschinsky A, Dulski P, Hein JR (1996). Comparison of the partitioning behaviours of yttrium, rare earth elements, and titanium between hydrogenetic marine ferromanganese crusts and seawater. Geochim Cosmochim Ac 60: 1709–1725.
  • Bellanca A, Masetti D, Neri R (1997). Rare earth elements in limestone/marlstone couplets from the Albian-Cenomanian Cismon section (Venetian region, northern Italy): assessing REE sensitivity to environmental changes. Chem Geol 141: 141–152.
  • Brand U, Veizer J (1980). Chemical diagenesis of a multi component carbonate system: trace elements. J Sediment Petr 50: 1219– 1236.
  • Byrne RH, Liu X, Schijf J (1996). The influence of phosphate coprecipitation on rare earth element distributions in natural waters. Geochim Cosmochim Ac 60: 3341–3346.
  • Calagari AA, Abedini A (2007). Geochemical investigations on Permo–Triassic bauxite deposit at Kanisheeteh, east of Bukan, Iran. J Geochem Explor 94: 1–18.
  • Calagari AA, Kangrani F, Abedini A (2010). Geochemistry of minor, trace and rare earth elements in Biglar Permo-Triassic bauxite deposit, northwest of Abgarm, Ghazvin Province, Iran. J Sci Islamic Repub Iran 21: 225–236.
  • Calagari AA, Kangrani F, Abedini A (2015). Geochemical characteristics of a laterite: the Jurassic Zan deposit, Iran. Acta Geodyn Geomater 12: 67–77.
  • De Baar HJW, German CG, Elderfield H, Van-Gaans P (1988). Rare earth elements distributions in anoxic waters of the Cariaco Trench. Geochim Cosmochim Ac 52: 1203–1219.
  • Derry LA, Jacobsen SB (1990). The chemical evolution of Precambrian seawater: evidence from REEs in banded iron formations. Geochim Cosmochim Ac 54: 2965–2977.
  • Elderfield H (1988). The oceanic chemistry of the rare earth elements. Philos T Roy Soc A 325: 105–126.
  • Elderfield H, Greaves MJ (1982). The rare earth elements in seawater. Nature 296: 214–219.
  • Elderfield H, Upstill-Goddard R, Sholkovitz ER (1990). The rare earth elements in rivers, estuaries, and coastal seas and their significance to the composition of ocean waters. Geochim Cosmochim Ac 54: 971–991.
  • German CR, Elderfield H (1990). Application of Ce anomaly as a paleo-redox indicator: the ground rules. Paleoceanography 5: 823–833.
  • Greaves MJ, Elderfield H, Sholkovitz ER (1999). Aeolian sources of rare earth elements to the Western Pacific Ocean. Mar Chem 68: 31–38.
  • Hanilçi N (2013). Geological and geochemical evolution of the Bolkardağı bauxite deposits, Karaman-Turkey: transformation from shale to bauxite. J Geochem Explor 133: 118–137.
  • Kamineni DC, Efthekhar-Nezad J (1977). Mineralogy of the Permian laterite of Northwestern Iran. Tscher Miner Petrog 24: 195–204.
  • Karadağ M, Kupeli S, Aryk F, Ayhan A, Zedef V, Doyen A (2009). Rare earth element (REE) geochemistry and genetic implications of the Mortaş bauxite deposit (Seydişehir/Konya–Southern Turkey). Chemie Erde-Geochem 69: 143–159.
  • Liu YG, Miah MRU, Schmitt RA (1988). Cerium: a chemical tracer for paleooceanic redox conditions. Geochimica Cosmochim Ac 52: 1361–1371.
  • Liu X, Wang Q, Deng J, Zhang Q, Sun S, Meng J (2010). Mineralogical and geochemical investigations of the Dajia Salento-type bauxite deposits, western Guangxi, China. J Geochem Explor 105: 137–152.
  • Madhavaraju J, González-León CM (2012). Depositional conditions and source of rare earth elements in carbonate strata of the Aptian-Albian Mural Formation, Pitaycachi section, northeastern Sonora, Mexico. Revista Mexicana de Ciencias Geológicas 29: 478–491.
  • Madhavaraju J, González-León CM, Lee YI, Armstrong-Altrin, JS, Reyes-Campero LM (2010). Geochemistry of the Mural Formation (Aptian-Albian) of the Bisbee Group, Northern Sonora, Mexico. Cretaceous Res 31: 400–414.
  • Madhavaraju J, Lee Y (2009). Geochemistry of the Dalmiapuram Formation of the Uttatur Group (Early Cretaceous), Cauvery basin, southeastern India: implications on provenance and paleo-redox conditions. Revista Mexicana de Ciencias Geológicas 26: 380–394.
  • Madhavaraju J, Ramasamy S (1999). Rare earth elements in limestones of Kallankurichchi Formation of Ariyalur Group, Tiruchirapalli Cretaceous, Tamil Nadu. J Geol Soc India 54: 291–301.
  • Mameli P, Mongelli G, Oggiano G, Dinelli E (2007). Geological, geochemical and mineralogical features of some bauxite deposits from Nurra (western Sardinia, Italy): insights on conditions of formation and parental affinity. Int J Earth Sci 96: 887–902.
  • Masuzawa, T, Koyama M (1989). Settling particles with positive Ce anomalies from the Japan Sea. Geophys Res Lett 16: 503–506.
  • McLennan SM (1989). Rare earth elements in sedimentary rocks: Influence of provenance and sedimentary processes. In: Lipin BR, McKay GA, editors. Geochemistry and Mineralogy of Rare Earth Elements. Chantilly, VA, USA: Mineralogical Society of America, pp. 169–200.
  • Mongelli G (1997). Ce-anomalies in the textural components of Upper Cretaceous karst bauxites from the Apulian carbonate platform (southern Italy). Chem Geol 140: 69–79.
  • Mongelli G, Boni M, Buccione R, Sinisi R (2014). Geochemistry of the Apulian karst bauxites (southern Italy): chemical fractionation and parental affinities. Ore Geol Rev 63: 9–21.
  • Murphy K, Dymond J (1984). Rare earth element fluxes and geochemical budget in the eastern equatorial Pacific. Nature 307: 444–447.
  • Murray RW, Ten Brink MRB, Brumsack HJ, Gerlach DC, Russ GP 3rd (1991a). Rare earth elements in Japan Sea sediments and diagenetic behaviour of Ce/Ce*: results from ODP Leg 127. Geochim Cosmochim Ac 55: 2453–2466.
  • Murray RW, Ten Brink MRB, Gerlach DC, Russ GP 3rd, Jones DL (1991b). Rare earth, major and trace elements in chert from the Franciscan complex and Monterey Group, California: assessing REE sources to fine grained marine sediments. Geochim Cosmochim Ac 55: 1875–1895.
  • Nagarajan R, Madhavaraju J, Armstrong-Altrin JS, Nagendra R (2011). Geochemistry of Neoproterozoic limestones of the Shahabad Formation, Bhima Basin, Karnataka, southern India. Geosci J 15: 9–25.
  • Nagendra R, Nagarajan R, Bakkiaraj D, Armstrong-Altrin JS (2011). Depositional and post-depositional setting of Maastrichtian limestone, Ariyalur Group, Cauvery Basin, South India: a geochemical appraisal. Carbonates Evaporites 26: 127–147.
  • Nath BN, Roelandts I, Sudhakar M, Plueger WL (1992). Rare earth element patterns of the Central Indian Basin sediments related to their lithology. Geophys Res Lett 19: 1197–1200.
  • Nothdurft LD, Webb GE, Kamber BS (2004). Rare earth element geochemistry of Late Devonian reefal carbonates, Canning Basin, Western Australia: confirmation of a seawater REE proxy in ancient limestone. Geochim Cosmochim Ac 68: 263– 283.
  • Nozaki Y, Zhang J, Amakawa H (1997). The fractionation between Y and Ho in the marine environment. Earth Planet Sci Lett 148: 329–340.
  • Piepgras DJ, Jacobsen SB (1992). The behaviour of rare earth elements in seawater: precise determination of variations in the North Pacific water column. Geochim Cosmochim Ac 56: 1851–1862.
  • Piper DZ (1974). Rare earth elements in the sedimentary cycle: a summary. Chem Geol 14: 285–304.
  • Rollinson HU (1993). Using Geochemical Data: Evaluation, Presentation, Interpretation. London, UK: Longman Scientific and Technical.
  • Sholkovitz ER (1992). Chemical evolution of rare earth elements: fractionation between colloidal and solution phases of filtered river water. Earth Planet Sci Lett 114: 77–84.
  • Siby K, Nath BN, Ramaswamy V, Naman D, Gnaneshwar R, Kamesh Raju KA, Selvaraj K, Chen CTA (2008). Possible, detrital, diagenetic and hydrothermal sources for Holocene sediments of the Andaman back arc basin. Mar Geol 247: 178–193.
  • Song C, Herong G, Linhua S (2014). Geochemical characteristics of REE in the Late Neo-Proterozoic limestone from northern Anhui Province, China. Chin J Geochem 33: 187–193.
  • Taylor Y, McLennan SM (1985). The Continental Crust: Its Composition and Evolution. 1st ed. Oxford, UK: Blackwell.
  • Toyoda D, Nakamura Y, Masuda A (1990). Rare earth elements of Pacific pelagic sediments. Geochim Cosmochim Ac 54: 1093– 1103.
  • Turekian KK, Wedepohl KH (1961). Distribution of elements in some major units of earth’s crust. Geol Soc Am Bull 72: 175– 192.
  • Veizer J (1983). Trace elements and isotopes in sedimentary carbonates. In: Reeder RJ, editor. Carbonates: Mineralogy and Chemistry, Vol. 11. Chantilly, VA, USA: Mineralogical Society of America, pp. 265–299.