Mineralogy and environmental stability of metallurgical slags from the Euronickel smelter, Vozarci, North Macedonia
The laterite Ni-smelting operations at Vozarci, Republic North Macedonia have produced large amounts of smelting wastes dumped in the close vicinity of the smelter. We examined phase composition and chemistry of the various types of slags (electric furnace slags, converter slag, magnetic slag) with...
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Published in | Applied geochemistry Vol. 170; p. 106068 |
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Main Authors | , , , , , , , , , |
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01.09.2024
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Abstract | The laterite Ni-smelting operations at Vozarci, Republic North Macedonia have produced large amounts of smelting wastes dumped in the close vicinity of the smelter. We examined phase composition and chemistry of the various types of slags (electric furnace slags, converter slag, magnetic slag) with the special focus on the phases containing potentially toxic elements in terms of their mineralogy, chemical composition, and responses to weathering. Electric furnace slags contain between 35 and 47 wt.% SiO2, 21–40 wt.% Fe2O3, and 13–23 wt.% MgO; converter and magnetic slags are Fe-rich (76–77 wt.% of Fe2O3) with significant amounts of Ca (7.6–8.4 wt.% CaO) and S-portion (2–2.5 wt.% SO3). All slags contain substantial amounts of the potentially toxic elements: Co (20–87 ppm), Cr (9600–17400 ppm), Ni (170–730 ppm), and Zn (150–380 ppm). Further mineralogical analyses showed that the slags consist of silicate glass, synthetic equivalents of olivines, orthopyroxenes, clinopyroxenes, and subordinate spinel-group phases, sulfides, and intermetallic compounds. Some of the slags had been subject to weathering since their dumping in 1982. The weathering results in the release of metals from primary slag phases, particularly from glass, and the partial immobilization of these metals in secondary soluble and insoluble minerals in the slag heaps (hydroxy-iron oxides, gypsum, anhydrite, syngenite, aphthitalite). The majority of slag samples exhibited increased leaching under conditions of lower pH (2.9) compared to higher pH (4.9). The contrast between leaching treatments was particularly evident for nickel (Ni), with leaching at a low pH of 2.9 reaching up to 135 times higher (MS) than at pH 4.9. At lower pH conditions, other contaminants of interest were leached out at a rate 4 to 76 times faster compared to the leaching achieved at pH 4.9, because they are the major source of potentially toxic elements.
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•Phase composition of electric furnace slags and converter slags are distinct.•Slags contain on average 10467 ppm Cr, 1050 ppm Ni, 233 ppm Zn.•Major hosting phase for Cr are spinel-group oxides.•Major hosting phase for Ni are sulfides and intermetallic compounds.•Leaching tests demonstrated low risk of contamination referred to TCLP norm. |
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AbstractList | The laterite Ni-smelting operations at Vozarci, Republic North Macedonia have produced large amounts of smelting wastes dumped in the close vicinity of the smelter. We examined phase composition and chemistry of the various types of slags (electric furnace slags, converter slag, magnetic slag) with the special focus on the phases containing potentially toxic elements in terms of their mineralogy, chemical composition, and responses to weathering. Electric furnace slags contain between 35 and 47 wt.% SiO₂, 21–40 wt.% Fe₂O₃, and 13–23 wt.% MgO; converter and magnetic slags are Fe-rich (76–77 wt.% of Fe₂O₃) with significant amounts of Ca (7.6–8.4 wt.% CaO) and S-portion (2–2.5 wt.% SO₃). All slags contain substantial amounts of the potentially toxic elements: Co (20–87 ppm), Cr (9600–17400 ppm), Ni (170–730 ppm), and Zn (150–380 ppm). Further mineralogical analyses showed that the slags consist of silicate glass, synthetic equivalents of olivines, orthopyroxenes, clinopyroxenes, and subordinate spinel-group phases, sulfides, and intermetallic compounds. Some of the slags had been subject to weathering since their dumping in 1982. The weathering results in the release of metals from primary slag phases, particularly from glass, and the partial immobilization of these metals in secondary soluble and insoluble minerals in the slag heaps (hydroxy-iron oxides, gypsum, anhydrite, syngenite, aphthitalite). The majority of slag samples exhibited increased leaching under conditions of lower pH (2.9) compared to higher pH (4.9). The contrast between leaching treatments was particularly evident for nickel (Ni), with leaching at a low pH of 2.9 reaching up to 135 times higher (MS) than at pH 4.9. At lower pH conditions, other contaminants of interest were leached out at a rate 4 to 76 times faster compared to the leaching achieved at pH 4.9, because they are the major source of potentially toxic elements. The laterite Ni-smelting operations at Vozarci, Republic North Macedonia have produced large amounts of smelting wastes dumped in the close vicinity of the smelter. We examined phase composition and chemistry of the various types of slags (electric furnace slags, converter slag, magnetic slag) with the special focus on the phases containing potentially toxic elements in terms of their mineralogy, chemical composition, and responses to weathering. Electric furnace slags contain between 35 and 47 wt.% SiO2, 21–40 wt.% Fe2O3, and 13–23 wt.% MgO; converter and magnetic slags are Fe-rich (76–77 wt.% of Fe2O3) with significant amounts of Ca (7.6–8.4 wt.% CaO) and S-portion (2–2.5 wt.% SO3). All slags contain substantial amounts of the potentially toxic elements: Co (20–87 ppm), Cr (9600–17400 ppm), Ni (170–730 ppm), and Zn (150–380 ppm). Further mineralogical analyses showed that the slags consist of silicate glass, synthetic equivalents of olivines, orthopyroxenes, clinopyroxenes, and subordinate spinel-group phases, sulfides, and intermetallic compounds. Some of the slags had been subject to weathering since their dumping in 1982. The weathering results in the release of metals from primary slag phases, particularly from glass, and the partial immobilization of these metals in secondary soluble and insoluble minerals in the slag heaps (hydroxy-iron oxides, gypsum, anhydrite, syngenite, aphthitalite). The majority of slag samples exhibited increased leaching under conditions of lower pH (2.9) compared to higher pH (4.9). The contrast between leaching treatments was particularly evident for nickel (Ni), with leaching at a low pH of 2.9 reaching up to 135 times higher (MS) than at pH 4.9. At lower pH conditions, other contaminants of interest were leached out at a rate 4 to 76 times faster compared to the leaching achieved at pH 4.9, because they are the major source of potentially toxic elements. [Display omitted] •Phase composition of electric furnace slags and converter slags are distinct.•Slags contain on average 10467 ppm Cr, 1050 ppm Ni, 233 ppm Zn.•Major hosting phase for Cr are spinel-group oxides.•Major hosting phase for Ni are sulfides and intermetallic compounds.•Leaching tests demonstrated low risk of contamination referred to TCLP norm. |
ArticleNumber | 106068 |
Author | Boev, Ivan Pędziwiatr, Artur Đorđević, Tamara Aicher, Claudia Tasev, Goran Lengauer, Christian L. Potysz, Anna Boev, Blažo Nagl, Peter Serafimovski, Todor |
Author_xml | – sequence: 1 givenname: Tamara orcidid: 0000-0003-0429-2584 surname: Đorđević fullname: Đorđević, Tamara email: tamara.dordevic@tuwien.ac.at organization: Vienna University of Technology, E057-02 USTEM, Stadionallee 2, 1020, Vienna, Austria – sequence: 2 givenname: Goran surname: Tasev fullname: Tasev, Goran organization: Goce Delcev University, Faculty of Natural and Technical Sciences, Str. Goce Delčev 89, 2000, Stip, North Macedonia – sequence: 3 givenname: Claudia surname: Aicher fullname: Aicher, Claudia organization: University of Vienna, Department of Mineralogy and Crystallography, Josef-Holaubek-Platz 2, 1090 Vienna, Austria – sequence: 4 givenname: Anna surname: Potysz fullname: Potysz, Anna organization: University of Wrocław, Faculty of Earth Sciences and Environmental Management, Institute of Geological Sciences, Pl. M. Borna 9, 50-204, Wrocław, Poland – sequence: 5 givenname: Peter surname: Nagl fullname: Nagl, Peter organization: University of Vienna, Department of Lithospheric Research, Josef-Holaubek-Platz 2, 1090 Vienna, Austria – sequence: 6 givenname: Christian L. surname: Lengauer fullname: Lengauer, Christian L. organization: University of Vienna, Department of Mineralogy and Crystallography, Josef-Holaubek-Platz 2, 1090 Vienna, Austria – sequence: 7 givenname: Artur surname: Pędziwiatr fullname: Pędziwiatr, Artur organization: Warsaw University of Life Sciences (WULS-SGGW), Institute of Agriculture, Department of Soil Science, Nowoursynowska Str. 159/37, 02–787 Warszawa, Poland – sequence: 8 givenname: Todor surname: Serafimovski fullname: Serafimovski, Todor organization: Goce Delcev University, Faculty of Natural and Technical Sciences, Str. Goce Delčev 89, 2000, Stip, North Macedonia – sequence: 9 givenname: Ivan surname: Boev fullname: Boev, Ivan organization: Goce Delcev University, Faculty of Natural and Technical Sciences, Str. Goce Delčev 89, 2000, Stip, North Macedonia – sequence: 10 givenname: Blažo surname: Boev fullname: Boev, Blažo organization: Goce Delcev University, Faculty of Natural and Technical Sciences, Str. Goce Delčev 89, 2000, Stip, North Macedonia |
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Keywords | Euronickel Weathering Slag mineralogy Laterite Ni-Ore Macedonia Nickel smelting |
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SubjectTerms | anhydrite calcium oxide chemical composition electric furnaces Euronickel geochemistry glass gypsum Laterite Ni-Ore laterites Macedonia magnetism nickel Nickel smelting Republic of North Macedonia silicates Slag mineralogy slags toxicity Weathering |
Title | Mineralogy and environmental stability of metallurgical slags from the Euronickel smelter, Vozarci, North Macedonia |
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