Characterisation of six supergene ferromanganese ore samples revealed that P was hosted by several different Fe and Mn oxides. Goethite had the highest (up to >1% or higher) and highest mean (up to 0.32%) P contents, then cryptomelane-hollandite (mean up to 0.12% P) and nsutite-pyrolusite (mean up to 0.14% P). When present in the same sample, nsutite had a higher mean P content than pyrolusite. Phosphate minerals were not detected in the samples. P deportment was variable with deposit, deposit type and within individual mineral grains. EPMA showed that P content is elevated in cryptomelane with higher Mn/(Fe + Al + Si) ratios and in todorokite with lower Mn/(Fe + Al + Si) ratios. The results show that higher phosphorus supergene ferromanganese ores with considerable cryptomelane and nsutite contents are likely to have multi-phase Fe-P and Mn-P deportment. The propensity for very fine-scale intergrowths of goethite and Mn oxides ± aluminosilicates in some ore types means that reliable characterisation of P deportment is critical in informing potential P-reduction pathways for ferroalloy feedstocks. P was most probably incorporated into Mn oxides via near-surface adsorption via complexation with cations such as Ca or Mg in todorokite, but the presence of structural P cannot be precluded in cryptomelane and nsutite.
BloomTAFosnachtDRHaezebrouckDM. The influence of phosphorus on the properties of sheet steel products and methods used to control steel phosphorus levels in steel product manufacturing. Iron and Steelmaker.1990; 17: 35–41.
2.
BasuS. Studies on dephosphorisation during steelmaking. Unpublished Doctoral Thesis, Royal Institute of Technology, Stockholm, Sweden, 73 p.2007.
3.
WellsMARamanaidouER. Occurrence and mineralogical association of phosphorus in Australian bedded iron ore deposits. Proceedings, Iron Ore 2017, Perth, Australia, 11–13 July, 331–336, 2011.
4.
DashevskiiVYAleksandrovAALeontievLI. The problem of phosphorus in the production of manganese ferroalloys. Steel in Translation2020; 50: 707–712.
5.
SparrowGJLuLLovelRR,et al.Chemical separation of iron ore. In: LuL (ed.) Iron ore: mineralogy, processing and environmental sustainability, 2nd ed. Cambridge, Cambridgeshire, UK: Woodhead Publishing, 2021, pp. 397–420.
6.
DashevskiiVYKashinVLLyakishevNP, et al.Dephosphorization of manganese ferroalloys with CaO & MnO based slag-forming mixtures. The Proceedings of INFACON1998; 8: 300–301.
7.
GasikMIGladkikhVA. The investigation of phosphorus chemical bond in the manganese-ore materials. The Fourteenth International Ferroalloys Congress May 31–June 4, 2015, Kiev, Ukraine – Energy efficiency and environmental friendliness are the future of the global ferroalloy industry, pp.470–478. 2015.
8.
DashevskiiVYAleksandrovAAZhdanovbAV, et al.Improved manganese extraction in the production of manganese ferroalloys. Steel Translation2017; 47: 557–560.
9.
OlsenSETangstadMLindstadT. Production of manganese ferroalloys. Trondheim: Tapir Academic Press, 2007.
10.
HanPZhangGChuS. Reducing dephosphorization of silicomanganese ferroalloys by CaO-based slag. Metall Res Technol2017; 114: 605–610.
11.
ShinDJGaoXUedaS, et al. Selective reduction of phosphorus from manganese ore to produce ferromanganese alloy with low phosphorus content. J Sustain Metall2019; 5: 362–377.
12.
MorrisRC. A pilot study of phosphorus distribution in parts of the Brockman Iron Formation, Hamersley Group, Western Australia. Annual Report of the Western Australian Department of Mines1973: 75–81.
13.
DukinoRDEnglandBMKneeshawM. Phosphorus distribution in BIF-derived iron ores of Hamersley Province, Western Australia. Transact Instit Min Metall B: Applied Earth Sci2000; 109: 168–176.
14.
CloutJMF. Iron formation-hosted iron ores in the Hamersley province of Western Australia. . Transact Instit Min Metall B: Applied Earth Sci2006; 115: 115–125.
15.
ManuelJRCloutJMF. Goethite classification, distribution and properties with reference to Australian iron deposits. Proceedings, Iron Ore 2017, Perth, Australia, 24–26 July, 567–574. 2017.
16.
PowncebyMIHapugodaSManuelJ, et al.Characterisation of phosphorus and other impurities in goethite-rich iron ores – possible P incorporation mechanisms. Min Eng2019; 143: 106022.
17.
SpierCALevettARosièreCA. Geochemistry of canga (ferricrete) and evolution of the weathering profile developed on itabirite and iron ore in the Quadrilátero Ferrífero, Minas Gerais, Brazil. Miner Deposita2019; 54: 983–1010.
18.
OstwaldJEnglandBM. Phosphorus in Iron Duke ore. BHP Research and New Technology, Central Research Laboratories, Unpublished Report CRL/TM/20/89. (Cited in Dukino et al., 2000). 1989.
19.
AcharyaBCRaoDSSahooRK,et al.Phosphorus in the siliceous manganese ores of Nishikhal, Orissa. Indian J Geol1994a; 66: 15–23.
20.
AcharyaBCRaoDSSahooRK. Mineralogy and genesis of Kutinga manganese deposit, South Orissa, India. Journal of Mineralogy. Petrol Econ Geol1994b; 89: 317–328.
21.
AcharyaBCRaoDSSahooRK. Mineralogy, chemistry and genesis of Nishikhal manganese ores of South Orissa, India. Mineral Deposita1997; 32: 79–93.
22.
RaoGVMohapatraBKTripathyAK. Enrichment of the manganese content by wet high intensity magnetic separation from Chikla manganese ore, India. Magnetic Electrical Separat1998; 9: 69–82.
23.
AcharyaBCNayakBK. Mineral chemistry of manganese ores associated with Precambrian Eastern Ghats complex of Andhra Pradesh-Orissa, India. J Mineral Petrol Econ Geol1998; 93: 214–231.
24.
Da CostaGMHerzogLR. Association between phosphorus and iron oxides in manganese ores. Am Mineral2011; 96: 68–73.
25.
TaylorBNKuyattCE. Guidelines for evaluating and expressing the uncertainty of NIST measurement results. Natl. Inst. Stds. Tech. Technical Note 1297 (Washington DC: U.S. Govt. Print. Off.) 20 pp.1994.
26.
CoelhoAA. TOPAS And TOPAS-Academic: an optimization program integrating computer algebra and crystallographic objects written in C++. J Appl Crystallog2018; 51: 210–218.
27.
TaylorJCClappRA. New Features and Advanced Applications of Siroquant: A Personal Computer XRD Full Profile Quantitative Analysis Software Package. Advances in X-Ray Analysis, Volume 35,Issue A: First Pacific-International Congress on X-ray Analytical Methods (PICXAM). Fortieth Annual Conference on Applications of X-ray Analysis, August 7–16, 1991, 49–55. 1991.
28.
PostJEVon DreeleRBBuseckPR. Symmetry and cation displacements in hollandites: structure refinements of hollandite, cryptomelane and priderite. Acta Crystallograp B1982; 38: 1056–1065.
29.
VicatJFanchonEStrobelP,et al.The structure of K1.33Mn8O16 and cation ordering in hollandite-type structures. Acta Crystallograp Sec B Struct Sci1986; 42: 162–167.
30.
MiuraHBanerjeeHHariyaY, et al.Hollandite and cryptomelane in the manganese oxide deposits of the Sausar Group, India. Mineral J1987; 13: 424–433.
31.
KudoHMiuraHHariyaY. Tetragonal-monoclinic transformation of cryptomelane at high temperature. Mineral J1990; 15: 50–63.
32.
LiJ-WVasconcelosPMZhangW, et al.Timing and duration of supergene mineralization at the Xinrong manganese deposit, western Guangdong Province, South China: cryptomelane 40Ar/39Ar dating. Mineral Deposita2007; 42: 361–383.
33.
MorrisRC. Genesis of iron ore in banded iron-formation by supergene and supergene-metamorphic processes – a conceptual model. Handbook of strata-bound and stratiform ore deposits. K. H. Wolf. Amsterdam, Elsevier. 13: 73–225. 1985.
34.
MookherjeeA. Distribution of minor elements in the gonditic manganese ore and its geochemical significance. Econ Geol1961; 56: 723–729.
35.
FrenzelG. The Manganese Ore Minerals. Geology and Geochemistry of Manganese. I. M. Varentsov and G. Grasselly. Stuttgart, E. Schweizerbart'sche Verlagsbuchhandlung. 1 – General Problems: Mineralogy, Geochemistry, Methods: 25–158. 1980.
36.
PostJE. Manganese oxide minerals: crystal structures and economic and environmental significance. Proc Natl Acad Sci USA1999; 96: 3447–3454.
37.
SivaprakashC. Mineralogy of manganese deposits of Koduru and Garbham, Andhra Pradesh, India. Econ Geol1980; 75: 1083–1104.
38.
OstwaldJEnglandBM. Phosphorus in Groote Eylandt ore types. BHP Research and New Technology, Central Research Laboratories, Unpublished Report CRL/TM/12/88. (Cited in Dukino et al., 2000). 1988.
39.
GutzmerJBeukesNJ. Asbestiform manjiroite and todorokite from the Kalahari manganese field, South Africa. South African J Geol2000; 103: 163–174.
40.
OstwaldJ. Some observations on the chemical composition of todorokite. Min Magazine1986; 50: 336–340.
41.
PostJEHeaneyPJHansonJ. Synchrotron X-ray diffraction study of the structure and dehydration behaviour of todorokite. Am Mineral2003; 88: 142–150.
42.
NyameFKKaseKYamamotoM. Occurrence and composition of manganese oxide minerals from the Nsuta manganese deposit, Western Ghana. Earth Sci Report-Okayama Univ1995; 2: 71–80.
43.
NiuSZhaoLNiuX, et al.The application of EPMA in the textural characterization of cryptomelane in the Xialei manganese deposit, southwest Guangxi. Rock Min Analy2022; 41: 239–250.
44.
PostJEMckeownDAHeaneyPJ. Raman spectroscopy study of manganese oxides: Tunnel structures. Am Min2020; 105: 1175–1190.
45.
PolverejanMVillegasJCSuibSL. Higher valency ion substitution into the manganese oxide framework. J Am Chem Soc2004; 126: 7774–7775.
46.
KawashimaMTainakaYHoriT, et al.Phosphate adsorption onto hydrous manganese (IV) oxide in the presence of divalent cations. Water Res1986; 20: 471–475.
47.
YaoWMilleroFJ. Adsorption of phosphate on manganese dioxide in seawater. Environ Sci Technol1996; 30: 536–541.
48.
AttanayakeCPKumaragamageDAmarawanshaG, et al.Phosphorus release and speciation in manganese (IV) oxide and zeolite-amended flooded soils. Environ Sci Technol2022; 56: 8082–8093.
49.
McKenzieR. The adsorption of lead and other heavy metals on oxides of manganese and iron. Australian J Soil Res1980; 18: 61–73.
50.
SinghVGhoshTKRamamurthyY,et al.Beneficiation and agglomeration process to utilize low-grade ferruginous manganese ore fines. Int J Min Proc2011; 99: 84–86.
51.
SinghVNagSTripathySK. Particle flow modelling of dry induced roll magnetic separator. Powder Technol2013; 244: 85–92.
52.
KivinenVKrogerusHDaavittilaJ. Upgrading of Mn/Fe ratio of low-grade manganese ore for ferromanganese production. The Twelfth International Ferroalloys Congress – Sustainable Future, June 6–9, 2010, Helsinki, Finland, 467–476. 2010.
53.
GaoYOlivas-MartinezMSohnHY, et al.Upgrading of low-grade manganese ore by selective reduction of iron oxide and magnetic separation. Metall Mater Transact B2012; 43B: 1465–1475.
54.
MphoMSamsonBAyoA. Evaluation of reduction roasting and magnetic separation for upgrading Mn/Fe ratio of fine ferromanganese. Int J Min Sci Technol2013; 23: 537–541.
55.
RathSSTripathySKRaoDS,et al.Characterization and reduction roasting studies of an iron rich manganese ore. Transac Indian Inst Met2018; 71: 861–872.
56.
TripathySKBanerjeePKSureshN. Effect of desliming on the magnetic separation of low-grade ferruginous manganese ore. Int J Min Metall Mater2015; 22: 661–673.
57.
SinghVBiswasA. Physicochemical processing of low grade ferruginous manganese ores. Int J Min Proc2017; 158: 35–44.
58.
ElliottRBaratiM. A review of the beneficiation of low-grade manganese ores by magnetic separation. Canadian Metallurgical Quarterly2020; 59: 1–16.
59.
PetersonMJKaradkalKNunnaV, et al.Demonstration of dry magnetic separation to upgrade the Mn:Fe ratio of a ferromanganese ore sample. Min Proc Ext Met Transact Inst Min Metal2023; 132: 3–4.
60.
Fisher-WhiteMJLovelRRSparrowGJ. Phosphorus removal from iron ore with a low temperature heat treatment. In: Proceedings iron ore 2009. The Australasian Institute of Mining and Metallurgy, 2009, pp.249–254.
Supplementary Material
Please find the following supplemental material available below.
For Open Access articles published under a Creative Commons License, all supplemental material carries the same license as the article it is associated with.
For non-Open Access articles published, all supplemental material carries a non-exclusive license, and permission requests for re-use of supplemental material or any part of supplemental material shall be sent directly to the copyright owner as specified in the copyright notice associated with the article.
