Investigation of Organic Matters and their Roles in Deposition and Phosphate Mineralization in the Kuh-e-Sefid Deposit, Ramhormoz

Document Type : Research Article

Authors

Shahid Chamran University of Ahvaz

Abstract

Introduction
It has been recently stated that phosphorite deposits are in fact marine biogenic materials, due to bacterial activity producing bio-apatite. In addition, Phosphorites contain 15–20 wt.% P2O5 (Tzifas et al., 2014). In this deposit, phosphate mineralization has occurred as phosphorite lenses with Eocene age within the Pabdeh Formation, with thickness up to 1.5 meters and width of 15 meters and its hosted rock is black shale. According to the presence of indices of fossils such as Globorotalia, Hantkenina, its age can be attributed to the middle Eocene. The Pabdeh formation is a very rich organic matter in addition to the presence of phosphate (Damiri, 2011). The formation due to planktonic foraminifera rich in organic matter is like the hydrocarbon source rock (Daneshian et al., 2012). In marine basins where upwelling and productivity are limited, phosphates may develop outside of microbial cells and also within bacterial cellular structures, formed by slow bacterial assimilation of phosphorus from assaying organic matter in areas of restricted sedimentation (O’Brine et al., 1981). It is therefore suggested that the upwelling currents did that in the recycling of phosphorus from dead organisms such as fishes and other marine vertebrates. The aim of this study is investigation of organic matter’s species and their roles in deposition and phosphate mineralization in the Kuh-e-Sefid phosphate deposit using XRD, FTIR and Rock-Eval pyrolysis.

Materials and methods
In field observations, 12 samples were selected and they were taken from units of phosphate and shale host rock in the Kuh-e-Sefid phosphate ore deposit. Ten cross sections were studied by conventional microscopic methods. Rock-Eval analysis was used in order to determine the organic carbon in the geology Department of the Shahid Chamran University of Ahvaz. The Phosphorite samples were determined by XRD at the Kansaran Binaloud Company in the Science and Technology campus in Tehran. FTIR analyses were carried out on the phosphorite samples in the chemistry department of the Shahid Chamran University of Ahvaz.

Results
Organic matter appears to be essential for phosphogenesis in two ways: 1) as an energy supply for redox change and 2) as a source of phosphate. Similarly, bacteria are important on two levels: 1) they provide a mechanism for the release of phosphorus from phospholipids and other high-energy phosphorus compounds by organic phosphate cracking and organic carbon oxidation, 2) they are capable of concentrating and precipitating phosphate (Jarvis, 1992).The sedimentary organic matter is first decomposed exclusively by aerobic bacteria. When O2 is completely utilized, further decomposition occurs via sulfate reduction until the oxidants are exhausted, then phosphorus and carbon are released from organic matter during decomposition (Ingall and Cappellen, 1990). Field observation and microscopic studies indicate that phosphate-bearing layers mainly consist of shale, marl, limestone with textures varying from wackestone to packestone forms. Also, phosphate components such as plettal, ooid, intraclast, fish skeletal fragments and microfossils are present. In additions to phosphate and biogenic component, nonphosphate minerals such as glauconite, calcite, pyrite, iron oxide and quartz, are present in different forms and sizes. The results of XRD analysis show the mineral phosphate (fluorapatite) besides calcite as one of the nonphosphate components in the Kuh-e-Sefid ore deposit as the main constituents, while the minerals montmorillonite and quartz are minor constituents. FTIR studies reveal qualitative information about the bonding pattern and nature of the components of the organic matters. Thus, phosphogenesis in marine phosphate deposits resulting in the destruction of areas around the continents that contain different components of phosphate and non-phosphate, and the resulting destruction of organic materials as well. Therefore, according to data from the Rock Evil, samples of the deposit represent more continental carbon. In general, it can be shown that, most of the phosphate mineralization in this deposit is mainly of a continental origin, and it is partly as a result of decomposition and oxidation of organic matter by bacteria and microorganisms that occurs.

Discussion
- Since shales rich in organic matter are capable of transferring sedimentary phosphorus as organic materials, it can be concluded that the deposits shale as the phosphate deposits host were the main factors of phosphorus transmission and the most mineralization occurs in parts that are rich in organic matter.
- Rock-Eval results showed that more samples contain continental carbon and this suggests that phosphate mineralization is of continental origin in this deposit and it is partly achieved by biodegradation of organic matter by microorganisms.
- FTIR, XRD studies have proved the frequency of fluorapatite minerals with calcite and organic materials that are most probably associated with phosphate mineralization in the deposit.
- FTIR studies reveal mineral-organic bounds such as OH, Carboxylic OH, Carboxylic acid C=O, C≡C Alkaline, group CH2, C=C aromatic, CH Aliphatic and aromatic stretching associated with identified mineralization.

Acknowledgements
Many thanks are due to the office of vice-chancellor of Chamran University of Ahvaz for valuable information concerning the field work and sampling.

References
Damiri, K., 2011. Geology, Geochemistry and Genesis of the Phosphate Ocurences in the Pabdeh Formation, southwestern Iran. M.Sc. Thesis, Shahid chamran University, Ahvaz, Iran, 146 pp. (in Persian with English abstract)
Daneshian, J., Norouzi, N., Baghbani, D. and Aghanabati, A., 2012. Biostratigraphy of Oligocene and lower Miocene sediments (Pabdeh, Asmari, Gachsaran and Mishan formations) on the basis of Foraminifera in Southwest Jahrum, interior Fars. Scientific Quarterly Journal, Geosciences, 21)83(:157-166. (in Persian with English abstract)
Ingall, E.D. and Cappellen, P.V., 1990. Relation between sedimentation rate and burial of organic phosphorus and organic carbon in marine sediments. Geochimica et Cosmochimica Ada, 54(2): 373-386.
Jarvis, I., 1992. Sedimentology, geochemistry and origin of phosphate chalks. The upper cretaceous deposits of NW Europe. Sedimentology, 39(1):55-97.
O’Brine, G.W., Harris, J.R., Milnes, A.R. and Veeh, H.H., 1981.Bacterial origin of East Australian continental margin phosphorites. Nature, 294: 442-444.
Tzifas, I.Tr., Goldelitsas, A., Magganas, A., Anderoulakaki, E., Eleftheriond, G., Mertzimckis, T.J. and Perraki, M., 2014. Uranium-bearing phosphatized limestone of new Greece. Journal of Geochemical Exploration, 143: 62-37.

Keywords


Abed, A.M. and Sadaqah, R.M., 2012.Enrichment of uranium in the uppermost Al-Hisa Phosphorite Formation, Eshi‐ diyya basin, southern Jordan. Journal of African Earth Sciences, 77:31-40.
Awadalla, G.S., 2010. Geochemistry and microprobe investigations of Abu Tartur REE-bearing phosphorite, Western Desert, Egypt. Journal of African Earth Sciences, 57(5): 431-443.
Benalioulhaj, S. and Trichet, J., 1990. Comparative study by infrared spectroscopy of the organic matter of phosphate-rich (Oulad Abdoun basin) and black shale (Timahdit basin) series (Morocco). Organic Geochemistry, 16(4-6): 649-660.
Birch, G.F., 1979. Phosphatic rocks on the western margin of South Africa. Journal of Sedimentary Research, 49(1): 93–110.
Boggs, S., 2009. Petrology of Sedimentary Rocks. Cambridge University Press, New York, 600 pp.
Calderon, F.J., Maysoon, M.M., Vigil, M.F., David, C.N., Joseph, G.B. and Reeves, J.B., 2011.Diffuse-reflectance mid-infrared spectral properties of soils under alternative crop rotations in a semi-arid climate. Communications in Soil Science and Plant Analysis, 42(17): 2143–2159.
Cohen, P.A., Schopf, J.W., Butterfield, N.J., Kudryavtsev, A.B. and Macdonald, F.A., 2011. Phosphate biomineralization in mid-Neoproterozoic protists. Geology, 39(6): 539–542.
Cooke, N.E., Fuller, O.M. and Gaikwad, R.P., 1986. FT-i.r. spectroscopic analysis of coals and coal extracts. Fuel, 65(9): 1254-1260.
Damiri, K., 2011. Geology, Geochemistry and Genesis of the Phosphate Ocurences in the Pabdeh Formation, southwestern Iran. M.Sc. Thesis, Shahid chamran University, Ahvaz, Iran, 146 pp. (in Persian with English abstract)
Daneshian, J., Norouzi, N., Baghbani, D. and Aghanabati, A., 2012. Biostratigraphy of Oligocene and lower Miocene sediments (Pabdeh, Asmari, Gachsaran and Mishan formations) on the basis of Foraminifera in Southwest Jahrum, interior Fars. Scientific Quarterly Journal, Geosciences, 21)83(:157-166. (in Persian with English abstract)
Ellerbrock, R.H. and Gerke, H.H., 2004. Characterizing organic matter of soil aggregate coatings and biopores by Fourier transform infrared spectroscopy. European Journal of Soil Science, 55(2): 219–228.
Fazio, A.M., Scasso, R.A., Castro, L.N. and Carey, S., 2007. Geochemistry of rare earthelements in early- diagenetic Miocene phosphatic concretions of Patagonia, Argentina: Phosphogenetic implications. deep-Sea Research II, 54(11-13): 1414-1432.
Gezici, O., Demir, I., Demircan, A., Unlu, N. and Karaarslan, M., 2012. Subtractive-FTIR spectroscopy to characterize organic matter in lignite samples from different depths. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 96: 63–69.
Glenn, C.R., Follmi, K.B., Riggs, S.R., Baturin, G.N., Grimm, K.A., Trappe, J., Abed, A.M., Olivier, C.G., Garrison, R.E., Ilyin, A.V., Jehl, C., Rohrlich, V., Sadaqah, R.M.Y., Schidlowski, M., Sheldon, R.E. and Siegmund, H., 1994. Phosphorus and phosphorites: Sedimentology and environments of formation. Eclogae geologicae, Helvetiae. 87(3) : 747-788.
Guido, A., Mastandrea, A., Demasi, F., Tosti, F. and Russo, F., 2012. Organic matter remains in the laminated microfabrics of the Kess-Kess mounds (Hamar Laghdad, Lower Devonian, Morocco). Sedimentary Geology, 263–264: 194–201.
Hiatt, E.E., Pufahl, P.K. and Edwards, C.T., 2015.Sedimentary phosphate and associated fossil bacteria in a Paleoproterozoic tidal flat in the 1.85 Ga Michigamme Formation, Michigan, USA. Sedimentary Geology, 319: 24–39.
Ingall, E.D. and Cappellen, P.V., 1990. Relation between sedimentation rate and burial of organic phosphorus and organic carbon in marine sediments. Geochimica et Cosmochimica Ada, 54(2): 373-386.
Jarvis, I., 1980 .Geochemistry of phosphatic chalks and hardgrounds from the Santonian to early Campanian (Cretaceous) of northern France. Journal of the GeologicalSociety, 137(6):705–721.
Jarvis, I., 1992. Sedimentology, geochemistry and origin of phosphate chalks. The upper cretaceous deposits of NW Europe. Sedimentology, 39(1):55-97.
Kamaee, L., 2009. Quaternary Geology. Geosciences and Mining Monthly, 3(30): 16-18. (in Persian)
Lamontagnea, J., Dumasb, P., Mouilletb, V. and Kister, J., 2001. Comparison by Fourier transform infrared (FTIR) spectroscopy of different ageing techniques: application to road bitumens. Fuel, 80(4): 483–488.
Landais, P., 1996. Organic geochemistry of sedimentary uranium ore deposits. Ore Geology Review, 11(1-3): 33–51.
Liou, S.C., Chen, S.Y., Lee, H.Y. and Bow, J.C., 2004.Structural characterization of nano-sized calcium deficient apatite powders. Biomaterials, 25(2): 189-196.
Mukherjee, S. and Srivastava, S.K., 2006. Minerals Transformations in NortheasternRegion Coals of India on Heat Treatment. Energy and Fuels, 20(3): 1089-1096.
Namadmalian, A., Okhovat, Z. and Moemenzade, M., 1998. Phosphate in iran. Geological Survey Of Iran, Tehran, 189 pp.
‌O’Brine, G.W., Harris, J.R., Milnes, A.R. and Veeh, H.H., 1981.Bacterial origin of East Australian continental margin phosphorites. Nature, 294: 442-444.
Ogihara, S., 1999. Geochemical characteristics of phosphorite and carbonate nodules from the Miocene Funakawa Formation, western margin of the Yokote Basin, northeast Japan. Sedimentary Geology, 125(1-2): 69–82.
Parrish, J.T. and Curtis, R.L., 1982. Atmospheric circulation, upwelling, and organic-rich rocks in the Mesozoic and Cenozoic eras. Palaeogeography, Palaeoclimatology, Palaeoecology, 40(1-3): 31-66.
Pavia, D.L., Lampman, G.M. and Kriz, G.S. (translated by Movassagh, B), 2002.Introduction to spectroscopy. Elmifanni Publication, Tehran, 652 pp.
Porter, K.G. and Robbins, E.J., 1981. Zooplankton fecal pellets link fossil fuel and phosphate deposits. Science, 212(4497): 931–933.
Rao, V.P. and Lamboy, M., 1996.Genesis of apatite in the phosphatized limestones of the western continental shelf of India. Marine Geology, 136(1-2): 41–53.
Schmitt, J. and Flemming, H.C., 1998. FTIR-spectroscopy in microbial and material analysis. International Biodeterioration and Biodegradation, 41(1): l-11.
Schuffert, J.D., Jahnke, R.A., Kastner, M., Leather, J., Sturz, A. and Wing, M.R., 1994. Rates of formation of modern phosphorite off western Mexico. Geochimica et Cosmochimica Acta, 58(22): 5001–5010.
Scopelliti, G., Bellanca, A., Neri, R. and Sabatino, N., 2010. Phosphogenesis in the Bonarelli Level from northwestern Sicily, Italy: petrographic evidence of microbial mediation and Ree behavior. Cretaceous Research, 31(2): 237-248.
Sheldon, R.P., 1987. Association of phosphatic and siliceous marine sedimentary deposits. In: J.R. Hein (Editor), Siliceous Sedimentary Rock-hosted Ores and Petroleum. Van Norstrand Reinhold Company, New York, pp. 58–80.
Slansky, M. (translated by Malekghasemi, F. and Simmonds, V.M.), 2003. Geology of sedimentary phosphates. Forough Azadie Publication, Tabriz, 240 pp.
Soudry, D., Ehrlich, S., Yoffe, O. and Nathan, Y., 2002. Uranium oxidation state and relatedvariations in geochemistry of phosphorites from the Negev (southern Israel).Chemical Geology, 189(3–4): 213–230.
Stamatakis, M.G., 2004. Phosphate deposits of Neogene age in Greece. Mineralogy, geochemistry and genetic implications. Chemie der Erde Geochemistry, 64(4): 329-357.
Stamatakis, M.G. and Koukouzas, N.K., 2001. The occurrence of phosphate minerals related with lacustrine clayey diatomite deposits, Thessaly, Central Greece. Sedimentary Geology, 139(1): 33–47.
Tribovillard, N., Re´court, Ph. and Trentesaux, A., 2010. Bacterial calcification as a possible trigger for francolite precipitation under sulfidic conditions. Comptes Rendus Geoscience, 342(1): 27–35.
Tzifas, I.Tr., Goldelitsas, A., Magganas, A., Anderoulakaki, E., Eleftheriond, G., Mertzimckis, T.J. and Perraki, M., 2014. Uranium-bearing phosphatized limestone of new Greece. Journal of Geochemical Exploration, 143: 62-37.
Veeh, H.H., Burnett, W.C. and Soutar, A., 1973. Contemporary phosphorites on the continental margin of Peru. Science, 181(4102): 844–845.
Whitney, D.L. and Evans, B.W., 2010. Abbreviations for names of rock-forming minerals. American Mineralogist, 95(1): 185-187.
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