Trace and REE Geochemistry of Bauxite Deposit of Darai–Daldali Plateau, Kabirdham District, Chhattisgarh, India

J. Earth Syst. Sci. (2020) 129:117 Ó Indian Academy of Sciences

https://doi.org/10.1007/s12040-020-1377-1 (0123456789().,-volV)(0123456789().,-volV)

Trace and REE geochemistry of bauxite deposit of Darai–Daldali plateau, Kabirdham district, Chhattisgarh, India

1 1, 2 BHUMIKA DAS ,MWYKHAN * and HARISH DHRUW 1SOS in Geology and WRM, Pt. RSU, Raipur, Chhattisgarh, India. 2Regional ODce, Directorate of Geology and Mines, Jagdalpur, Chhattisgarh, India. *Corresponding author. e-mail: [email protected] MS received 4 August 2019; revised 19 January 2020; accepted 21 January 2020

The Darai–Daldali plateau preserves well developed laterite type bauxite deposits as a result of in-situ weathering of basaltic rocks (Deccan Traps). The bauxite ore is essentially composed of gibbsite and boehmite in subordinate amount, along with anatase and brookite as accessory minerals. Kaolinite, goethite, hematite, ilmenite, gibbsite and brookite are found in lateritic bauxite and laterite samples in variable amounts. SiO2–Al2O3–Fe2O3 diagram illustrates strong bauxitization resulting from desilication in the early stage. The disilication was followed by bauxitization and deferruginization at late stages as a result of reducing and oxidizing conditions, respectively, due to Cuctuating water table, which is evidently supported by A–L–F plot. Progressive loss/gain in FMTE, LILE, HFSE and REE during bauxitization process of basalt through lateritic bauxite facies is observed. La/Y varying from 1.17 to 4.11 suggests prevalence of alkaline conditions. Positive Eu/Eu* anomaly in these samples is suggestive of colloidal precipitation of gibbsite from pore water of lateritic residuum. Mass increase of Ce in laterite samples further supports to its sorption on goethite and hematite mineral phases. Keywords. Trace and REE; bauxite Darai–Daldali plateau; Kabirdham.

1. Introduction models based on their respective investigations. In India, a vast area of west-central part covering states Bauxite has long been investigated globally, for its of Maharashtra, parts of Madhya Pradesh, Gujrat significance as an ore of alumina, as well as in and Chhattisgarh is underlain by continental Cood understanding the mobility of elements in weather- basalts of Paleocene age (Deccan Traps), which host ing processes. A number of scientists have investi- numerous important bauxite deposits, resulting gated the mineralogical and petrographical aspects from lateritization processes (Meshram and Ran- of bauxite, such as Kangarani et al. (2007), Taylor dive 2011; Kale et al. 2013; Patel et al. 2014). These et al. (2008), Bayiga et al. (2011). Further, Aagaard deposits have been studied in detail as regards to (1974), Didier et al. (1983), Boulange and Colin their mineralogy, geochemistry and genesis (Bala- (1994), Braun (1991), and Braun et al. (1990) have subramaniam et al. 1984; Patel et al. 2014 and many worked on the geochemical aspects including others). However, as regards to mass balance chan- mobility behaviour of rare earth and trace elements ges related to trace elements in lateritic type baux- during the transformation of parent rock to bauxite. ites of basaltic parentage is not given much These investigators have also proposed genetic attention, except Sastri and Sastry (1982) who dealt 117 Page 2 of 15 J. Earth Syst. Sci. (2020) 129:117 with major element composition. Therefore, we 2. Geological setting carried out detailed mineralogical and geochemical studies of the bauxite deposits of Darai–Daldali The present study area is situated in SOI toposheet plateau; district Kabirdham, Chhattisgarh, India, in no. 64 F/3 is bounded by latitudes 22°2203000– order to evaluate the mobility of major, trace and 22°2703000N and longitudes 81°1000000–81°1203000E, REE in the lateritic proBle, wherein bauxite ores having maximum elevation of 940 m above mean have developed over Deccan traps. sea level. A sequence of Deccan lava Cows capped

Figure 1. Geological map of Darai–Daldali plateau, Kabirdham district, Chhattisgarh, (modiBed after Mathur 2005). (1) Chilpi Group, (2) Deccan Traps (Basalt), (3) Laterite with bauxite, (4) Bauxite pits (G: Gamdapara, K: Kesmarda, M: Mahaveer Minerals), and (5) soil cover. J. Earth Syst. Sci. (2020) 129:117 Page 3 of 15 117 by laterite and lateritic bauxites constitutes the Inspectorate GrifBth India Pvt. Ltd., Bhuba- topmost geological formation, unconformably neswar, India (tables 2, 3). Fourteen samples of overlying the slates and phyllites of Chilpi Group. bauxite and laterite, and one sample of basalt was The Deccan lava Cows, which are almost hori- analyzed for trace elements (table 4) using induc- zontal, are generally massive. The total thickness tively coupled plasma mass spectrometry (ICPMS) of laterite is about 15–20 m in Darai–Daldali at National Geophysical Research Institute, plateau and comprises several recognizable litho- Hyderabad, India following methods of Mani- logical units (Bgure 1). The low lying areas and kyamba et al. (2012). Detailed mineralogical anal- interCuves of small streams are occupied either by ysis of 18 samples representing bauxite, lateritic phyllites, slates with interbedded quartzite of bauxite and laterite was performed by X-ray Chilpi Group (Middle Proterozoic) or covered by diAraction (XRD) at MMIT, Bhubaneswar using alluvium. The rocks of Chilpi Group uncon- Cu Ka radiation operating at 40 KV and 20 mA by formably overly the Nandgaon Group (Mathur means of Phillips X-ray diAractometer (PW-1710). 2005). The samples were run for 2h between 10° and 70° corresponding to d-values between 9 and 1.68 A. The d-values were compared with JCPDS data 3. Methodology book. Petrographic studies were carried out under transmitted and reCected light on an Axiopol-40 Field investigations comprise study of laterite/ microscope Btted with digital camera. bauxite proBle in different mine pit sections and For the convenience of presentation, these collection of representative samples (table 1). samples have been classiBed using major element Twenty samples were collected from mine pits and composition into bauxite (Al2O3: [ 40%, Fe2O3: 10 samples from three drill-hole cores. Out of which 3.0–5.0% and SiO2: \ 2.0%); lateritic bauxites 23 samples of bauxite and laterite, and two samples (Al2O3: 20.0–35.0%, Fe2O3: 20.0–40.0% and of basalts were analyzed for determination of SiO2: \ 30.0%) and laterite (Al2O: 15.0–30.0%, major elements using wet chemical methods at Fe2O3: [ 40.0%, SiO2: \ 20%).

Table 1. Details of sample locations.

Map no. Drill hole no. Latitude Longitude Sample nos. Depth (m) DH-1 DN4W8-1 22°24012.800N81°11028.1600E B-1 Bauxite 3.60 B-2 Bauxite 5.80 LB-3 Lateritic bauxite 7.25 L-4 Laterite 10.40 DH-2 DN5W6-III 22°24012.2000N81°11025.3700E B-5 Bauxite 3.30 LB-6 Lateritic bauxite 5.50 L-7 Laterite 11.60 DH-3 DN31W3-B 22°24048.0300N81°11021.1800E B-8 Bauxite 1.80 B-9 Bauxite 2.40 LB-10 Lateritic bauxite 3.0 L-11 Laterite 4.20 G-1 Gamdapara Mine 22°26048.500N81°10048.100E LB-12 Lateritic bauxite Surface samples B-13 Bauxite 50 m apart B-14 Bauxite B-15 Bauxite K-1 Kesmarda Mine 22°27011.1000N81°11018.400E LB-16 Lateritic bauxite Surface samples B-17 Bauxite 50 m apart B-18 Bauxite B-19 Bauxite M1 Mahavir Mines 22°23050.200N81°9040.400E L-20 Laterite Surface samples B-21 Bauxite 10 m apart LB-22 Lateritic bauxite B-23 Laterite 117 Page 4 of 15 J. Earth Syst. Sci. (2020) 129:117

Table 2. Major element composition of basalt (BS), bauxite (B), lateritic bauxite (LB) and laterite (L) samples from Darai–Daldali plateau, Kabirdham district.

Core no. DN4W8-I Core no. DN5W6-III Core no. DN31W3-B Gamdapara Mine Element LB- LB- wt.% B-1 B-2 LB-3 L-4 B-5 LB-6 L-7 B-8 B-9 10 L-11 12 B-13 B-14 B-15

SiO2 0.36 0.46 5.27 20.44 0.60 21.74 16.44 0.66 1.94 18.38 10.38 29.20 0.63 0.38 1.36

Al2O3 59.54 58.90 39.46 21.45 59.58 24.25 22.74 59.01 57.45 24.75 16.65 29.30 58.20 58.02 48.67

Fe2O3 3.29 3.19 28.43 43.08 4.20 36.40 43.30 3.20 5.60 39.16 58.14 21.38 3.98 3.99 13.66

TiO2 6.30 8.23 5.51 4.12 6.26 4.65 4.53 9.49 6.29 3.79 4.37 2.34 5.66 7.73 9.11 CaO 0.26 0.17 0.26 0.29 0.21 0.14 0.12 0.15 0.15 0.19 0.31 0.36 0.20 0.24 0.20 MgO 0.04 0.05 0.04 0.04 0.05 0.04 0.05 0.04 0.05 0.02 0.05 0.04 0.04 0.03 0.05

K2O 0.01 0.01 0.03 0.02 0.01 0.03 0.03 0.01 0.01 0.03 0.00 0.52 0.01 0.00 0.02

Na2O 0.02 0.01 0.02 0.02 0.02 0.02 0.01 0.01 0.02 0.01 0.00 0.05 0.00 0.00 0.00 MnO 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.01 0.02 0.03 0.01 0.01 0.02 LOI 25.98 26.24 23.76 11.83 27.70 8.54 15.05 27.50 27.80 13.58 10.85 16.72 27.80 29.50 27.65 Total 95.81 97.26 102.78 101.29 98.63 95.81 102.27 100.08 99.30 99.92 100.77 99.99 96.53 99.90 100.74

Kesmarda Mine Mahavir Mine Basalt Element wt.% L-16 B-17 B-18 B-19 L-20 B-21 LB-22 B-23 BS-1 BS-2

SiO2 14.85 0.62 0.52 0.34 7.31 0.20 4.99 0.50 45.51 45.87 Al2O3 24.33 56.93 58.49 58.27 26.52 58.25 31.47 63.48 15.98 14.12

Fe2O3 41.75 4.42 3.61 3.61 46.52 3.21 38.51 3.21 14.73 16.10

TiO2 4.66 8.29 8.75 7.26 3.41 7.04 5.55 5.87 2.89 3.14 CaO 0.34 0.33 0.15 0.17 0.21 0.17 0.17 0.17 10.36 11.13 MgO 0.05 0.02 0.03 0.01 0.01 0.02 0.03 0.01 6.18 6.76

K2O 0.01 0.00 0.01 0.01 0.02 0.01 0.03 0.01 0.41 0.38

Na2O 0.01 0.00 0.01 0.01 0.01 0.01 0.01 0.01 1.95 1.96 MnO 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.11 0.19 LOI 13.85 28.55 28.45 29.55 14.99 30.05 19.80 28.50 0.88 0.03 Total 99.86 99.17 100.02 99.24 99.02 98.97 100.57 101.76 100.00 99.68

Table 3. Average major element composition in bauxite, massive hard and mottled in nature. Under the lateritic bauxite and laterite samples. microscope, bauxite appears as dull-white coloured paste of aluminous minerals due to colloidal pre- Element Average Average Average cipitation, along with goethite and secondary quartz wt.% bauxite lat. bauxite laterite (Bgure 3a). At places, well developed gibbsite crys- SiO2 0.66 15.928 13.884 tallites are also observed, suggesting their precipi- Al2O3 58.06 29.846 22.338 tation in cavities (Bgure 3b). XRD scanning of these Fe2O3 4.55 32.776 46.558 samples reveals abundance of gibbsite followed by TiO2 7.41 4.368 4.218 brookite, ilmenite and anatase, (Bgure 4)inBauxite CaO 0.20 0.224 0.254 samples. The lateritic bauxite and laterite samples MgO 0.03 0.034 0.04 reveal occurrence of gibbsite, hematite, goethite, K2O 0.01 0.128 0.016 kaolinite, ilmenite and quartz in variable abundance Na2O 0.01 0.022 0.01 MnO 0.01 0.014 0.012 (table 5). Boehmite is observed in two samples. LOI 28.25 16.88 13.314 Total 99.19 100.216 100.642 5. Geochemistry

4. Mineralogy and petrography Among the major oxides, average SiO2 content in bauxite samples is recorded as 0.66%, in lateritic In the study area, bauxite occurs in the form of bauxite samples 15.92% and in laterite samples boulders in pockets enclosed within the laterite 13.88%. Average Al2O3 in bauxite samples is (Bgure 2). Mostly, the bauxite is dull-pink coloured, recorded as 58.06%, in lateritic bauxite samples .ErhSs.Sci. Syst. Earth J. Table 4. Trace and REE element composition of basalt (BS), laterite (L), lateritic bauxite (LB) and bauxite (B) samples from Dari–Daldali Plateau, Kabirdham district. Core no. DN4W8-I Core no. DN5W6-III Core no. DN31W3-B Mahavir Mine Element Gamdapara Basalt (ppm) B-1 B-2 LB-3 L-4 B-5 LB-6 L-7 B-8 B-9 LB-10 B-13 B-21 LB-22 B-23 BS-1 Sc 13.65 24.71 48.98 50.52 20.27 49.58 51.15 25.76 37.25 68.38 19.06 20.15 39.76 14.11 31.18 V 521.38 616.13 1625.55 1005.05 508.37 1424.40 2047.34 613.56 979.43 1525.34 469.46 451.40 1243.14 405.60 333.81 Cr 234.10 252.47 404.98 194.56 252.69 311.53 307.85 391.97 272.79 273.81 233.17 211.78 213.59 198.27 36.16 Co 4.56 3.25 4.96 7.61 4.74 4.38 4.91 4.70 3.70 6.10 3.49 3.30 4.23 3.09 50.41 Ni 39.85 45.71 49.21 67.85 44.19 57.06 60.12 47.00 41.65 63.51 42.77 44.02 49.07 41.63 20.75 (2020) 129:117 Cu 28.09 28.05 33.50 56.71 18.93 37.93 33.90 39.56 31.95 56.62 21.37 21.21 33.06 19.72 222.61 Zn 66.15 91.20 50.59 47.94 38.07 43.78 53.94 70.85 44.00 67.07 49.84 64.13 57.57 37.46 93.25 PGa 40.30 82.56 71.99 43.78 57.02 53.36 49.57 58.78 54.71 41.45 51.41 47.26 46.07 41.12 22.50 FMTE 948.07 1144.08 2289.76 1474.01 944.28 1982.02 2608.78 1252.18 1465.47 2102.28 890.57 863.25 1686.50 761.00 810.67 Ba 31.07 33.37 32.52 30.19 31.4 30.91 32.22 30.78 31.42 31.37 31.93 33.31 31.88 31.83 172.03 Sr 30.82 33.27 29.19 25.35 24.6 31.65 17.04 35.16 31.15 35.48 25.81 31.02 54.65 41.21 192.72 Rb 0.65 4.65 1.96 2.03 1.37 1.62 2.19 2.88 1.15 2.57 1.29 1.29 1.38 0.99 2.17 Th 5.06 9.79 16.3 9.01 8.66 13.7 11.64 10.8 10.07 10.12 6.36 7.86 7.51 7.1 0.49 PU 1.24 2.45 5.29 4.39 3.14 4.24 6.34 5.12 3.54 4.76 2.02 2.13 3.21 1.46 0.15 LILE 68.85 83.53 85.27 70.98 69.17 82.12 69.44 84.75 77.32 84.3 67.42 75.62 98.62 82.58 367.55 Zr 289.19 542.9 606.57 402.98 616.29 467.57 491.11 530.65 497.09 401.29 455.6 484.03 448.96 376.28 63.34 Nb 26.63 40.95 30.61 21.03 31.3 23.46 22.04 31.79 31.23 19.04 24.86 30.48 29.11 20.47 13.02 Hf 7.96 15.49 17.56 10.84 17.1 12.68 14.14 14.82 14.31 11.57 13.07 13.85 13.06 11.08 1.77 Ta 2.03 3.36 2.28 1.48 2.54 1.58 1.53 2.7 2.51 1.54 2.01 2.14 2.41 1.74 1 PY 1.83 4.18 6.88 7.66 4.32 7.11 7.69 5.02 3.89 7.12 3.89 3.81 7.56 3.29 30.62 HFSE 327.64 606.88 663.9 444 671.55 512.4 536.51 584.99 549.02 440.56 499.43 534.31 501.11 412.85 109.76 La 3.74 11.47 13.74 9 8.91 11.91 14.31 10.92 13.76 12.85 11.3 8.61 31.08 5.66 8.75 Ce 8.67 34.51 53.33 47.77 17.21 32.64 32.37 16.37 52.11 51.31 23.41 16.39 58.88 21.6 24.17 Pr 0.67 2.16 2.54 1.84 1.5 2.37 2.85 2.01 2.63 2.48 1.9 1.66 7.34 1 3.28 Nd 2.37 7.44 9.08 7.12 4.96 8.77 10.81 6.71 9.28 9.29 5.9 5.71 29.7 3.48 15.2 Sm 0.89 1.51 2.18 2.6 1.97 2.82 3.53 2.21 2.91 2.84 2.05 2.13 6.4 1.7 3.89 PEu 0.6 0.9 0.92 0.84 0.71 0.9 1.09 0.77 0.93 0.92 0.81 0.89 1.95 0.92 1.25 LREE 0.94 57.99 81.79 60.17 26.35 59.41 64.96 28.07 67.86 66.84 34.07 26.78 104.27 28.7 56.54 Gd 0.29 0.92 1.12 0.89 0.63 1.06 1.37 0.85 1.1 1.13 0.83 0.8 3.56 0.58 5.04 Tb 0.05 0.17 0.22 0.2 0.11 0.22 0.28 0.14 0.19 0.22 0.13 0.14 0.57 0.09 0.91 Dy 0.34 1.15 1.56 1.45 0.77 1.53 1.86 0.96 1.16 1.47 0.9 0.9 2.5 0.65 6.03 Ho 0.08 0.24 0.34 0.33 0.19 0.33 0.39 0.22 0.23 0.32 0.2 0.19 0.44 0.16 1.15 Er 0.22 0.64 0.9 0.87 0.52 0.86 1 0.62 0.63 0.85 0.56 0.54 1.25 0.45 3.18 ae5o 15 of 5 Page Tm 0.04 0.11 0.16 0.16 0.1 0.15 0.17 0.11 0.11 0.15 0.1 0.1 0.15 0.08 0.42 Yb 0.31 0.85 1.18 1.15 0.75 1.1 1.24 0.84 0.83 1.1 0.77 0.71 1.11 0.62 2.5 PLu 0.05 0.14 0.2 0.19 0.13 0.18 0.2 0.14 0.13 0.18 0.12 0.12 0.17 0.1 0.36 PHREE 1.38 4.22 5.68 5.24 3.2 5.43 6.51 3.88 4.38 5.42 3.61 3.5 9.75 2.73 19.59 REE 17.71 61.31 86.54 73.56 37.74 63.94 70.39 42.1 85.06 84.19 48.18 38.01 143.16 36.18 76.13 La/Y 2.05 2.74 2 1.17 2.06 1.68 1.86 2.18 3.54 1.8 2.91 2.26 4.11 1.72 0.29

Eu/Eu* 3.65 2.33 1.80 1.69 1.94 1.58 1.51 1.59 1.90 1.58 1.90 2.08 1.25 2.84 0.86 117 Ce/Ce* 1.56 1.99 2.55 3.18 1.38 1.70 1.39 1.02 2.46 2.55 1.53 1.25 1.03 2.60 1.12

FMTE = Ferromagnesian trace element, LILE = Large ion lithophile element, HFSE = High Beld strength elements, REE = Rare earth elements. 117 Page 6 of 15 J. Earth Syst. Sci. (2020) 129:117

Figure 2. Field photograph showing outcrop of bouldery bauxite capped by laterite – Gamdapara Mine, Darai–Daldali Plateau, Kabirdham district.

29.85% and in laterite samples 22.34%, while Figure 3. (a) Dense massive gibbsite due to colloidal precip- average Fe2O3 content in bauxite samples is itation. Note faintly developed colloidal bands along the cavity recorded as 4.55%, in lateritic bauxite samples wall. Under transmitted cross nicols. Scale bar 50 lm. 32.77% and in laterite samples 46.56%. The aver- (b) Well developed euhedral gibbsite crystallites masked with age content of TiO2 in bauxite is recorded as goethite (brownish colured) and cavity Blled with amorphous clay. Under transmitted polarized light. Scale bar 100 lm. 7.41%, which is higher than average TiO2 content in lateritic bauxite (4.37%) and laterite samples (4.22%) (table 3). Positive correlation between TiO2 and Al2O3 (cc = 0.75; table 8) and negative The chondrite normalized REE patterns of correlation between TiO2 and Fe2O3 (cc = –0.76) bauxite, lateritic bauxite and laterite samples (Bgure 5a and b, respectively) suggest its coherence (Bgure 6) reveal an overall depleted pattern with with alumina hydroxide. Higher concentrations of strong depletion in HREEs, compared to parent Cr (av. 255.90), Zr (av. 474.0), Nb (av. 29.71) and rock (basalt), along with marginal enrichment of Ga (av. 54.14) compared to parent Basalt are LREE as a result of positive Ce anomaly observed in these bauxites. Trace elements such as (1.02–3.18) in laterite and lateritic bauxites. An Nb and Ta exhibit positive correlation with TiO2 increasing trend in the average RREE is observed (cc = 0.77 and 0.82, respectively, Bgure 5d and e), from bauxite (RREE 52.33) through lateritic while Nb and Ta have strong positive inter-element bauxite (RREE 78.22) to laterite (RREE 95.70). correlation (cc = 0.96) (Bgure 5f). The enrichment Positive Eu/Eu* anomaly values (1.25–3.65) in of Nb and Ta in bauxite and lateritic bauxite these samples demonstrate strong fractionation of samples is inferred on the basis of their strong LREE. Moreover, positive Eu anomaly in our positive correlation with TiO2 bearing anatase or samples is exceptional, as in most of the lateritic ilmenite (table 5). The association of Nb and Ta proBles, negative Eu anomaly is reported (Calagari with anatase/ilmenite could have been conBrmed et al. 2010; Abedini et al. 2014; Babechuk et al. through SEM-EDX analysis, had these minerals 2014). The positive Eu anomaly in present case were not occurring in indiscriminate size. most probably is accounted for precipitation of J. Earth Syst. Sci. (2020) 129:117 Page 7 of 15 117

relative to Al for quantifying the degree of lateritization. Further, to quantify redox dependent weathering behaviour of Fe/Al in lateritic/ bauxitic proBle, Babechuk et al. (2014) factored MIA into MIA (o) and MIA (R) applicable to enrichment of Fe and Al, respectively, in the weathering proBle. Schellmann (1981, 1986) proposed SiO2–Al2O3–Fe2O3 ternary diagram to quantify degree of lateritization and distinguish between kaolinitized, weakly-, moderately-, and strongly lateritized and bauxitized weathering residue. Babechuk et al. (2014) also proposed that SiO2/(Al2O3 +Fe2O3) ratio be used as index of lateritization ‘IOL’, which can be obtained using the weight % ratio of SiO2,Fe2O3(T) and Al2O3 as per following equation: ÂÀÁ IOL ¼ 100 Â Al O þ Fe O = ÀÁÃ2 3 2 3ðTÞ SiO2 þ Al2O3 þ Fe2O3ðTÞ : We have attempted to quantify lateritization/ bauxitization using SiO2–Al2O3–Fe2O3 ternary plot of Schellmann (1981, 1986) accompanied with IOL values (Bgure 7), wherein an overlap- ping in samples of laterite and lateritic bauxites is observed in the moderately lateritized Beld. The parent basalt samples of this area with IOL values of 39.75 are comparable with unweathered Deccan basalt samples (35.7) reported by Babechuk et al. (2014). An increasing trend in the mean IOL values is observed from laterite (av. IOL 82.98) and lateritic bauxite samples (av. IOL 82.57) to bauxite Figure 4. X-ray diAraction patterns of selected samples of samples (av. IOL 99.13). Higher IOL values in bauxite, lateritic bauxite and laterite. bauxite samples most probably are due to excessive desilication and release of iron during the bauxitization process. The A–L–F plot (Bgure 8) trivalent Fe and Al hydroxides due to percolating and mass balance diagram of major elements pore water Cuids (Ma et al. 2011), or due to the (Bgure 9) unequivocally support the contention dust introduced during lateritization (Babechuk that desilication was a continuous process et al. 2014). Further investigation in this regard is throughout the development of bauxite. However, needed. deferruginization took place in the late stage of bauxite formation. 6. Discussion 6.2 Mass change and mobility of elements 6.1 Extent of lateritization/bauxitization during bauxitization

In order to quantify chemical changes during the Since bauxite being an in-situ product of exogenic processes of weathering, chemical index of alter- hydrogeochemical processes, provides avenues to ation (CIA: Nesbitt and Young 1982, 1984) has examine mass changes of elements. It is believed been widely used. Recently, Babechuk et al. that elements such as Nb, Ti, Zr, Al, Th, and Hf (2014) introduced ‘maBc index of alteration’ are immobile during weathering processes, and are (MIA), similar to CIA but incorporating beha- used as monitor immobile elements (White et al. viour of Fe and Mg in addition to Ca, Na and K 2001; Wimpenny et al. 2007). However, their 117 Page 8 of 15 J. Earth Syst. Sci. (2020) 129:117

Table 5. Order of abundance of Minerals based on XRD peak intensity.

Sample no. Sample type Order of abundance of minerals based on peak intensity B-1 Bauxite Gibbsite [[[ Brookite B-2 Bauxite Gibbsite [[[ Brookite B-5 Bauxite Gibbsite [[[ Anatase B-8 Bauxite Gibbsite [[[ Brookite = Anatase B-9 Bauxite Gibbsite [[[ Anatase B-13 Bauxite Gibbsite [[[ Brookite B-14 Bauxite Gibbsite [[[ Brookite B-21 Bauxite Gibbsite [[[ Brookite [ Anatase [ Boehmite B-23 Bauxite Gibbsite [[[ Brookite LB-3 Lateritic Bauxite Gibbsite [[[ Brookite LB-6 Lateritic Bauxite Hematite [ Kaolinite [ Goethite = Gibbsite LB-10 Lateritic Bauxite Gibbsite [[ Hematite LB-12 Lateritic Bauxite Hematite [ Quartz LB-22 Lateritic Bauxite Gibbsite [[ Hematite [ Quartz [ kaolinite L-20 Lateritic Bauxite Gibbsite [[[ Hematite [ kaolinite [ Boehmite L-7 Laterite Hematite [ kaolinite [ Goethite L-4 Laterite Hematite [[[ kaolinite G-5 Laterite Hematite [[[ Kaolinite B: bauxite, LB: lateritic bauxite, L: laterite.

relative mobility being dependent on weathering 1. Average loss of SiO2 from laterite and bauxite conditions is questioned by a number of workers facies is observed as 36.28% and 45.91% respec- (Malpas et al. 2001; Braun et al. 2005). Others have tively. While, an average loss of 13.60% Fe2O3 used an isovolumetric calculation model (Millot in bauxite and a gain of 18.58% in laterite and Bonifas 1955). In the present case, we have samples is observed. followed MacLean and Kranidiotis (1987) and 2. A progressive gain of 1.39%, 7.51% and 9.57% MacLean (1990) formulae (equation 1) to calculate Al2O3 in laterite, lateritic bauxite and bauxite mass balance in major and trace elements samples, respectively, is observed. The enrich- employing TiO2 as monitor elements; as TiO2 ment of Al2O3 in bauxite samples is at the shows maximum positive correlation with Al2O3 expense of loss of iron and silica. (table 8). Mass balance calculations for respective 3. Significant gain in LOI is observed in laterite elements in laterite, lateritic bauxite and bauxite samples (av. 9.38%) in lateritic bauxite (av. samples are carried out using mean values of 12.33%) and bauxite samples (av. 11.48%). basalt. Less gain in LOI in the bauxite samples compared to lateritic bauxite samples is pre- ðÞAl2O3 D sumed due to replacement of hydrated phyl- Al2O3 ¼ Â ðÞTiO2 P ÀðÞAl2O3 P; ðÞTiO2 D losilicates by alumina sesquioxides during ð1Þ bauxitization process (Duzgoren-Aydin et al. 2002; Babechuk et al. 2014). Similarly, less where D denotes concentration of an element in gain of LOI in laterite samples compared to weathered rock, while P denotes concentration in lateritic bauxite most probably is a result of parent rock. dehydration of kaolinite resulting in formation of laterite. 6.2.1 Major elements 4. Total loss of CaO, MgO, K2O, Na2O and MnO is observed in laterite and bauxite samples, From the mass balance calculations (table 6) based however, with insignificant loss of K2O (av. on TiO2 as immobile element (as mentioned above) 0.25%) in lateritic bauxite samples, which and their graphical presentation (Bgure 9), follow- suggests their retention in kaolinite and other ing observations are made: clay minerals (Wilson 1994) in this facies. J. Earth Syst. Sci. (2020) 129:117 Page 9 of 15 117

Figure 5. (a) TiO2 vs.Al2O3;(b) TiO2 vs. Fe2O3;(c) TiO2 vs. Zr; (d) TiO2 vs. Nb; (e) TiO2 vs. Ta; and (f)Nbvs. Ta diagrams to show inter-element relationship.

6.2.2 Trace elements where element D denotes for the weathered rock (laterite/lateritic bauxite/bauxite) and element The mass change calculations for trace and REE P denotes for the parent rock. The mass changes so have been carried out using MacLean and Krani- calculated (table 7) are discussed group wise: diotis (1987) and MacLean (1990) formulae (equation 1). 6.2.2.1 Ferromagnesian trace elements (FMTE) ðÞAl2O3 D Al2O3 ¼ Â ðÞTiO2 ÀðÞAl2O3 ; Bauxite of this area is characteristically depleted ðÞTiO D P P 2 in FMTE compared to laterite and lateritic ð1Þ bauxites, however enriched compared to parent 117 Page 10 of 15 J. Earth Syst. Sci. (2020) 129:117

Figure 6. Chondrite normalized REE patterns of bauxite (8), Figure 9. Mass balance diagrams showing gain or loss in lateritic bauxite (3) and laterite (3) samples compared with major elements with reference to TiO as immobile element. parent Deccan Trap basalt. 2

rock (table 7). Moderate to strong enrichment of V, Cr, Ni and Ga is observed in laterite and lateritic bauxite, while Co and Zn are depleted in all rock types (Bgure 10a). Strong positive correlation (table 8) between Fe2O3 and Sc, V, Co and Ni (c.c. 0.88, 0.86, 0.68 and 0.89, respectively); and between SiO2 and Sc (0.86), V (0.79), CO (0.57) and Ni (0.87) is suggestive of their alike geochemical behaviour in weathering environment and their Bxation in goethite, hematite and kaolinite mineral phases as reported by Calagari et al. (2010) from Iran. Further, the mobility of above elements is controlled by pH-Eh under humid oxidizing and acidic conditions (Thornber

Figure 7. Al2O3–Fe2O3–SiO2 ternary diagram after Schell- 1992). It is observed that Ni, Cr, Co and V mann (1981, 1986), showing distribution of samples in strong behave like Fe, hence these are mainly controlled bauxitization Beld. by Fe-oxyhydroxides (Marques et al. 2004; Mongelli et al. 2014), and are easily substituted for Fe3+ in the crystal structure of Fe-oxyhydroxides (Schwertmann and Pfab 1996). Hence these elements show a negative correlation with Al2O3.

6.2.2.2 Large ion lithophile elements (LILE)

Among LILEs, Ba, Sr, and Rb having low ionic potential (\3) are soluble in surBcial environ- ments, hence are strongly depleted in all the three facies. Very low enrichment of Th and U is observed (Bgure 10b) in lateritic bauxite [ laterite and bauxite, which probably accounts for its least mobile nature in weathering environment (Taylor and McLennan 1985). Mass depletion of Ba, Sr, and Rb most likely is due to Figure 8. Al2O3–CaO+Na2O+K2O+MgO–Fe2O3 (A–L–F) plot after Babechuk et al. (2014), displaying concentration of leaching of these elements in weathering solu- bauxite samples near Al2O3 apex. tions due to alteration of feldspars in the parent J. Earth Syst. Sci. (2020) 129:117 Page 11 of 15 117

Table 6. Mass gain/loss in major elements compared to parent basalt (in %).

Bauxite Elements wt.% B-1 B-2 B-5 B-8 B-9 B-13 B-14 B-15 B-17 B-18 B-19 B-21 B-23

SiO2 –46.02 –46.02 –45.90 –45.98 –45.25 –45.85 –46.04 –45.74 –45.96 –46.01 –46.05 –46.10 –45.93

Al2O3 13.68 6.71 13.88 3.85 12.72 16.21 7.77 1.19 5.83 5.27 9.35 10.10 17.83

Fe2O3 –13.83 –14.24 –13.38 –10.70 –12.71 –17.56 –13.85 –10.86 –13.80 –14.17 –13.91 –14.03 –13.76 CaO –10.62 –10.69 –10.65 –10.70 –10.68 –10.64 –10.66 –10.68 –10.63 –10.70 –10.68 –10.68 –10.66 MgO –6.76 –6.76 –6.76 –6.77 –6.76 –6.76 –6.77 –6.76 –6.77 –6.77 –6.78 –6.77 –6.77

K2O –0.40 –0.40 –0.40 –0.40 –0.40 –0.39 –0.40 –0.39 –0.40 –0.40 –0.40 –0.40 –0.39 Na2O –1.95 –1.96 –1.95 –1.96 –1.95 –1.96 –1.96 –1.96 –1.96 1.08 –1.96 –1.96 –1.95 MnO –0.15 –0.15 –0.15 –0.15 –0.15 –0.14 –0.14 –0.14 –0.15 –0.15 –0.15 –0.15 –0.14 LOI 12.08 9.23 12.99 8.35 12.98 15.55 11.14 8.77 10.01 9.42 11.91 12.52 14.30 Total –53.97 –64.27 –52.30 –64.45 –52.20 –51.55 –60.91 –66.58 –63.83 –62.41 –58.64 –57.46 –47.49

Lateritic bauxite Laterite Elements wt.% LB-3 LB-6 LB-10 LB-12 LB-22 L-4 L-7 L-11 L-16 L-20

SiO2 –43.28 –31.98 –31.45 –8.18 –43.46 –31.11 –35.16 –38.97 –36.50 –39.67

Al2O3 6.72 0.80 4.80 23.01 2.19 0.78 0.21 –3.47 0.82 8.59

Fe2O3 0.266 8.38 15.99 12.36 5.67 16.37 13.64 25.03 11.82 26.05 CaO –10.61 –10.66 –10.60 –7.71 –10.66 –10.54 –10.67 –10.53 –10.53 –10.56 MgO –6.76 –6.75 –6.76 –6.73 –6.76 –6.75 –6.75 –6.75 –6.75 –6.77

K2O –0.38 –0.38 –0.38 0.28 –0.38 –0.39 –0.38 –0.40 –0.39 –0.38

Na2O –1.95 –1.95 –1.95 0.01 –1.95 –1.95 –1.95 –1.96 –1.95 –1.95 MnO –0.14 –0.14 –0.14 –0.11 –0.14 –0.14 –0.14 –0.14 –0.14 –0.14 LOI 12.65 6.43 10.43 21.26 10.39 8.27 9.64 7.09 8.58 12.90 Total –43.49 –36.25 –20.05 34.20 –45.11 –25.45 –31.56 –30.10 –35.06 –11.93

rock, basalt. U and Th show positive correlation during lateritization has been reported by many (table 8)withFe2O3 (0.68; 0.45), SiO2 (0.64; workers, such as Ronov et al. (1967), Nesbitt 0.50), Sc (0.79; 0.63), V (0.82; 0.69) which (1979), and Duddy (1980) highlighting enrichment implies their adsorption on goethite and kaolinite of LREEs and depletion of HREEs. Positive Ce present in the lateritic bauxite and laterite anomaly in lateritic ferricrete over amphibolites (Braun et al. 1998). and basaltic breccias and gabbros has also been reported by Steinberg and Courtois (1976). Mass balance calculations reveal an accumulation of La 6.2.2.3 High Beld strength elements (HFSE) in laterites and Ce in lateritic bauxite and laterite samples (Bgure 10d). Although negative Eu Mass balance calculations of FMTE reveal strong anomaly as a function of weathering intensity has enrichment of Zr, in all the facies. While very low been reported previously (Huang and Gong 2001; to low enrichment of Ta, Nb, and Hf is observed in Ma et al. 2011; Babechuk et al. 2014), in this study all these samples, however, with decreasing trend average Eu/Eu* values are recorded as 2.27 in towards bauxite (Bgure 10c). Strong to moderate bauxite, 1.65 in lateritic bauxite and 1.48 in laterite positive correlation of Nb and Ta with TiO 2 samples. La/Y ratios have been used to ascertain (table 8; Bgure 5d and e) is most probably due to pH conditions during weathering by Maksimovic their incorporation in anatase or ilmenite. and Panto (1991). Values of La/Y \ 1 imply prevalence of acidic conditions, while La/Y [ 1 6.2.2.4 Rare earth elements indicate alkaline conditions. In the bauxites of this area, La/Y ratios vary between 1.17 and 4.11, The behaviour of REEs during weathering pro- suggesting overall alkaline conditions during the cesses depends on Eh-pH and other factors (Can- development of lateritic proBle, wherein both trell and Byrne 1987). Fractionation of REEs alumina and iron hydroxides precipitated 117

Table 7. Mass change in trace and REE concentrations in bauxite, lateritic bauxite and laterite samples.

Bauxite Lateritic bauxite Laterite 15 of 12 Page Elements B-1 B-2 B-5 B-8 B-9 B-13 B-21 B-23 LB-3 LB-6 LB-10 L-4 L-7 L-22 Sc –24.66 –20.89 –21.43 –20.83 –13.35 –21.04 –22.56 –23.95 –4.42 0.91 23.13 5.73 2.81 –9.61 V –84.71 –77.30 –329.29 –87.24 –325.14 –84.15 –140.81 –125.83 554.19 588.22 877.61 400.46 1026.57 340.40 Cr 75.69 68.95 85.34 121.36 94.38 87.84 54.39 65.51 185.07 165.50 181.30 105.99 168.40 79.68 Co –48.23 –49.06 –48.13 –48.52 –48.64 –48.56 –49.00 –48.83 –47.70 –47.58 –45.56 –44.85 –47.15 –48.12 Ni –1.71 –1.72 0.50 –1.86 –0.82 2.00 –1.93 0.60 6.13 16.19 29.69 28.82 19.20 5.87 Cu –209.19 –210.93 –213.51 –206.71 –207.32 –211.24 –213.54 –212.50 –222.61 –198.06 –177.65 –181.18 –200.09 –204.68 Zn –61.65 –55.28 –74.95 –64.78 –72.20 –66.75 –65.83 –74.04 –65.62 –64.92 –39.99 –58.23 –57.41 –62.03 Ga –3.25 11.87 4.91 1.12 3.68 4.84 –2.29 –1.42 16.83 12.04 10.42 9.48 10.43 2.49 Ba –157.19 –158.14 –156.94 –159.66 –157.00 –155.05 –157.79 –155.71 –154.26 –147.12 –152.02 –149.97 –150.62 –154.74 Sr –177.99 –178.87 –180.89 –178.59 –177.81 –178.99 –179.45 –171.59 –176.77 –164.54 –172.23 –174.19 –181.40 –163.08 Rb –1.85 –0.23 –1.51 –1.01 –1.62 –1.48 –1.61 –1.66 –1.09 –0.12 –1.12 –0.68 –0.71 –1.42 Th –0.49 –0.49 –0.49 –0.49 –0.49 –0.49 –0.49 –0.49 –0.49 –0.49 –0.49 –0.49 –0.49 –0.49 U 0.45 0.87 1.37 1.91 1.55 0.93 0.76 0.60 2.75 3.63 2.60 3.06 4.07 1.59 Zr 74.83 162.68 232.99 149.91 174.54 178.95 143.61 129.61 268.02 239.32 255.36 231.07 262.98 180.15 Nb –0.29 4.03 2.03 –0.24 1.93 0.21 0.01 –2.52 3.70 2.17 2.10 2.35 1.63 2.77 Hf 2.03 4.68 6.45 4.18 5.07 5.18 4.15 3.91 7.82 6.43 7.42 6.15 7.62 5.31 Ta –0.04 0.39 0.22 0.08 0.20 0.06 –0.09 –0.11 0.24 0.02 0.22 0.08 0.01 0.30 Y –29.75 –28.88 –28.54 –28.61 –28.76 –28.56 –29.00 –28.94 –26.87 –26.02 –24.97 –25.02 –25.51 –26.52 Sci. Syst. Earth J. La –6.97 –3.98 –4.47 –4.36 –2.17 –2.74 –5.07 –5.85 –1.24 –1.04 1.45 –2.17 0.76 8.11 Ce –20.02 –9.80 –15.89 –17.59 0.77 –11.72 –17.16 –13.09 4.97 –3.04 16.58 10.74 –2.66 7.77 Pr –2.96 –2.38 –2.56 –2.47 –2.02 –2.27 –2.57 –2.77 –1.89 –1.74 –1.31 –1.94 –1.39 0.70 Nd –14.07 –12.11 –12.82 –12.51 –10.76 –12.07 –12.76 –13.42 –10.24 –9.52 –7.82 –10.00 –8.02 0.91 Sm –3.47 –3.26 –2.94 –3.00 –2.50 –2.80 –2.98 –3.02 –2.70 –2.07 –1.63 –2.00 –1.54 –0.42 Eu –47.49 –31.53 –38.68 –39.93 –16.68 –31.59 –40.54 –38.14 –11.12 –17.42 7.27 –5.37 –12.85 17.06

Gd –0.96 –1.25 –0.91 –0.94 –0.80 –0.82 –0.87 –0.77 –0.75 –0.67 –0.51 –0.64 –0.52 –0.19 (2020) 129:117 Tb –4.91 –4.66 –4.74 –4.70 –4.52 –4.60 –4.70 –4.75 –4.44 –4.36 –4.15 –4.40 –4.13 –3.11 Dy –0.88 –0.84 –0.86 –0.85 –0.82 –0.84 –0.85 –0.86 –0.79 –0.77 –0.73 –0.76 –0.72 –0.60 Ho –5.86 –5.55 –5.65 –5.64 –5.47 –5.54 –5.64 –5.69 –5.18 –5.03 –4.86 –4.97 –4.79 –4.67 Er –1.11 –1.05 –1.06 –1.06 –1.04 –1.04 –1.07 –1.07 –0.97 –0.94 –0.90 –0.91 –0.89 –0.92 Tm –3.08 –2.91 –2.93 –2.93 –2.88 –2.88 –2.95 –2.95 –2.69 –2.62 –2.51 –2.54 –2.51 –2.50 Yb –0.40 –0.37 –0.37 –0.38 –0.37 –0.37 –0.38 –0.38 –0.33 –0.32 –0.30 –0.31 –0.31 –0.34 Lu –2.35 –2.15 –2.14 –2.16 –2.11 –2.09 –2.20 –2.18 –1.86 –1.79 –1.63 –1.66 –1.68 –2.49 J. Earth Syst. Sci. (2020) 129:117 Page 13 of 15 117 0.8 0.68 0.59 – – – 0.18 0.11 0.8 – – – 0.60 0.53 – – 0.9 – 0.14 0.09 – – 0.81 – 0.27 0.33 0.78 0.33 0.82 0.69 0.10 0.53 0.13 0.61 – – 0.85 – 0.14 0.46 – – 0.440.600.58 0.550.44 0.72 0.70 0.50 0.53 0.66 0.65 0.71 0.50 0.84 0.80 0.70 0.61 0.83 0.78 0.75 0.60 0.86 0.79 0.60 0.77 – 0.23 0.50 0.64 0.22 0.45 0.68 – – 0.58 – 0.15 0.15 – – 0.45 – 1.00 0.43 0.50 0.50 0.75 0.12 0.22 – – 0.39 – 1.00 0.84 0.66 0.92 – – 0.56 – 0.52 0.69 – – 0.46 – 0.13 – 0.44 0.61 0.23 0.85 – – – Sc V Cr Co Ni Cu Zn Ga Th U Zr Nb Hf Ta 0.66 0.90 0.62 – – – cient (Spearman). B 2 0.73 0.86 0.79 0.18 0.57 0.87 0.69 1.00 0.76 0.88 0.86 0.12 0.68 0.89 0.71 0.43 TiO – – – Figure 10. Mass balance diagrams showing gain/depletion in 3

(a) FMTE, (b) LILE, (c) HFSE, and (d) REE. O 2 1.00 0.99 0.75 YLaCePrNdSmEuGdTbDyHoErTmYbLu – 0.93 0.49 0.66 0.50 0.53 0.62 0.47 0.52 0.65 0.82 0.88 0.85 0.86 0.85 0.82 0.92 Fe – simultaneously. However, selective leaching of 3

iron-oxyhydroxide causing the development of O 2 1.00 0.91 0.86 bauxite is most likely controlled by development of – reducing conditions. Mass increase of Ce in laterite Inter-element correlation coef samples further support to its sorption on goethite 3 3 3 3 2 2 O O and hematite mineral phases (Koeppenkastrop and O O 2 2 2 2 Th U Ni Cu Elements Al Table 8. Al ScVCrCoNi Cu 1.00 0.88 0.33 1.00 0.66 0.45 0.86 0.45 1.00 0.81 0.69 0.10 0.54 0.07 1.00 0.19 0.81 0.84 0.63 0.79 0.69 0.82 Al TiO Fe Fe de Carlo 1993). SiO 117 Page 14 of 15 J. Earth Syst. Sci. (2020) 129:117

7. Conclusion Abedini A, Calagari A A and Mikaeili K 2014 Geochemical characteristics of laterites: The Ailibaltalu deposit; Iran. The laterite type bauxite deposits of Darai–Daldali Bull. Min. Res. Expl. 148 69–84. Babechuk M G, Widdowson M and Kamber B S 2014 plateau are developed as a result of in-situ weath- Quantifying chemical weathering intensity and trace ele- ering of basaltic rocks. Gibbsite is the major mineral ment release from two contrasting basalt proBles, Deccan in bauxite ore with goethite, anatase as minor Traps, India; Chem. Geol. 363 56–75. accessory minerals, while laterite and lateritic Balasubramaniam K S, Surendra M and Kumar T V 1984 bauxite predominantly comprise hematite, goethite, Genesis of certain bauxite proBles from India; Chem. Geol. kaolinite, quartz and gibbsite. Well developed 60 227–235. Bayiga E C, Bitom D, Ndjigui P and Bilong P 2011 Miner- lateritic proBle demonstrates downward advancing alogy and geochemical characterization of weathering weathering front under warm humid climate, products of amphibolites at SW Eseka (northern border of wherein chemical decomposition of plagioclase and the Nyoung unit, SW Cameroon); J. Geol. Min. Res. 3(10) pyroxene (augite) resulted in leaching (loss) of 281–293. mobile elements SiO (–31.67%), CaO + MgO Boulange B and Colin F 1994 Rare element mobility during 2 conversion of nepheline syenite into lateritic bauxite at +K2O+Na2O+MnO (–18.61%) along with Passo-Quatro Minas Gerais, Brazil; Appl. Geochem. 96 enrichment (gain) of Fe2O3 (8.53%), and Al2O3 701–711. (7.51%) and addition of 12.23% water (LOI) giving Braun J J, Pagel M, Muller J P, Bilong P, Michard A and rise to development of lateritic bauxite, at the Brst Guillet B 1990 Cerium anomalies in lateritic proBles; Geochim. Cosmochim. Acta 5 781–795. stage. Minor enrichment of Al2O3 is suggestive of preservation of kaolinite. In the next stage, under Braun J J 1991 Geochemical and mineralogical behaviour of rare earths, thorium and uranium in laterite proBle of reducing conditions, breakdown of kaolinite and Akongo (south-west Cameroon); Thesis Doctorate, Univ. deferruginization along with desilication took place Nancy I., 236p. causing enrichment of alumina (9.57%) resulting in Braun J J, Viers J, Dupre B, Polve M, Ndam J and Muller J the formation of bauxite; while under oxidizing 1998 Solid/liquid REE fractionation in the lateritic system conditions, dehydration (loss of LOI compared to of Goyoum, East Cameroon: The implication for the present dynamics of the soil covers of the humid tropical lateritic bauxite) took place to concentrate iron regions; Geochim. Cosmochim. Acta 62 273–299. (18.58%) resulting in the formation of laterite. The Braun J J, Ngoupayou J R N, Viere J, Dupre B, Bedimo J P processes of bauxitization and lateritization were B, Boeglin J L, Robain H, Nyeck B, Freydier R, Nkamdjou most probably controlled by the Cuctuation of water L S, Rouiller J and Muller J P 2005 Present weathering table, during the development of the laterite/ rates in a humid tropical watershed: Nsimi, South bauxite proBle. Prevalence of Ce anomaly in laterite Cameron; Geochim. Cosmochim. Acta 69 357–387. 4+ Calagari A A, Kangarani F and Abedini A 2010 Geochemistry and lateritic bauxites suggest its adsorption as Ce of major, trace and rare earth elements in Biglar Permo- on goethite and clay minerals under oxidizing con- Triassic Bauxite Deposit, northwest of Abgarm, Ghazvin ditions (Roaldset 1974;Braunet al. 1990). Province, Iran; J. Sci. 21 225–236. Cantrell K J and Byrne R H 1987 Rare earth element complexation by carbonate and oxalate ions; Geochim. Acknowledgements Cosmochim. Acta 51 597–606. 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