1992 Marine Ree

Marine Chemistry, 38 (1992) 185-208 185 Elsevier Science Publishers B.V., Amsterdam

Rare earth element geochemistry of ferromanganese deposits from the Indian Ocean

B. Nagender Nath a'~, V. Balaram b, M. Sudhakar c'l and W.L. PliJger a aAbteilung fur Angewandte Lagerstiittenlehre, Aachen University of Technology, Siisterfeldstrasse 22,

D-5100 Aachen, Germany bGeochemistry Division, National Geophysical Research Institute, Uppal Road, Hyderabad--

500 007, India CE401, Sea-Use Programme, London School of Economics, Houghton Street, London WC2A 2AE,

UK (Received 15 October 1990; revision accepted 31 January 1992)

ABSTRACT

Nagender Nath, B., Balaram, V., Sudhakar, M. and Pliiger, W.L., 1992. Rare earth element geochemistry of ferromanganese deposits from the Indian Ocean. Mar. Chem., 38:185-208.

Fourteen manganese nodules and three ferromanganese crusts from the Indian Ocean were analysed for major and minor elements and the 14 naturally occurring rare earth elements (REE). The REE were analysed by inductively coupled plasma-mass spectroscopy (ICP-MS). The samples were selected systematically from the Western Indian Ocean and the Central Indian Basin, to represent a seamount top, slope, an abyssal hill, siliceous sediment affected by terrigenous influx, a highly pro- ductive siliceous environment, red clay and carbonate sedimentary domains.

Although REE zonation is observed in one oriented nodule, with relative enrichment in the top, evidence of top-bottom fractionation appears to have been obliterated as a result of the nodules being turned over. Correlations between Ca, P, Fe and REE in nodules suggest that the REE primarily reside in the iron oxyhydroxide and phosphatic phases. An authigenic origin is attributed to these elements. The nodules and crusts from the Western Indian Ocean and the shallower depths of the Central Indian Basin are 8-MnO2 rich, and are characterized by high concentrations of REE and higher positive cerium anomalies. These two areas are in the realm of cold Antarctic Bottom Water (AABW), which may enhance the oxidative scavenging of Ce by particles and its subsequent incorporation into manganese nodules. All the nodules and crusts show Gd-Tb anomalies. A diagenetic nodule with a pala- gonitic, smectite-rich nucleus exhibits an unusual heavy REE (HREE) enrichment with no significant Ce anomaly.

INTRODUCTION

Numerous studies of the chemical and mineralogical compositions of ferromanganese nodules have documented large variations both regionally and

Correspondence to: B. Nagender Nath, Geological Oceanography Division, National Institute of Oceanography, Dona Paula, Goa - - 403 004, India. ~Permanent address: Geological Oceanography Division, National Institute of Oceanography, Dona Paula, Goa m 403 004, India.

0304-4203/92/$05.00 1992 Elsevier Science Publishers B.V. All rights reserved.

186 B. NAGENDER NATH ET AL.

locally (see reviews by Glasby, 1977; Cronan, 1980; Baturin, 1988; Halbach et al., 1988 ). The rare earth elements (REE) in manganese nodules and their associated sediments also display considerable variability on both regional and local scales (Baturin, 1988 ). The major and minor element chemistry of Fe-Mn deposits from the Central Indian Basin has been reported in many recent papers (e.g. Cronan and Moorby, 1981; Moorby and Cronan, 1981; Ahmed and Hussain, 1987; Mukhopadhyay and Nagendernath, 1988; Sud- hakar, 1989 ). These studies have emphasized the role of hydrogenetic contri- butions, oxic and suboxic diagenesis, the thickness of the acoustically trans- parent layer (ATL), and the local topography in the geochemistry of manganese nodules.

Seawater is believed to be a major contributor of REE to manganese nodules (Goldberg, 1961; Goldberg et al., 1963). In contrast to other trace elements, REE are not believed to be contributed to nodules from porewater diffusive fluxes (Elderfield et al., 1981 a; Piper, 1988 ). Recent studies (Aplin, 1984; Ingri and Ponter, 1987; Calvert et al., 1987; Glasby et al., 1987; Kun- zendorf et al., 1987, 1989; Piper, 1988 ) have shown that a clear understand- ing of the uptake and distribution of REE in manganese nodules and associated phases may allow us to constrain models of REE cycling in the oceanic environment. Negative cerium anomalies in nodules were originally thought to be solely due to submarine hydrothermal activity (Elderfield and Greaves, 1981 ), but later reports showed the presence of such anomalies in hydrogenetic nodules also (Calvert et al., 1987; Glasby et al., 1987).

Most studies on Fe-Mn deposits have been more or less confined to the Pacific Ocean. The recent review by Baturin (1988) showed the lack of data on REE in Atlantic and Indian Ocean nodules. We have found analyses of only 22 nodules from the Indian Ocean in the published literature (Pachad- janov et al., 1963; Glasby et al., 1978; Volkov, 1979; Tlig, 1982; all referred to by Baturin ( 1988); and Ben Othman et al., 1989).

In this paper, we attempt to address the following points: ( 1 ) top-bottom variations of REE in oriented nodules and the role of dia-

genesis in the supply of REE to manganese nodules from the Indian Ocean; ( 2 ) distribution and behaviour of all 14 naturally occurring REE and their

relation with the major chemical constituents in nodules; (3) variations of the REE in suites of ferromanganese nodules from differ-

ent environments such as shallow basins, deeper abyssal plains, seamount top, and different sedimentary environments; and

(4) the role of bottom-water redox conditions on the REE geochemistry of nodules.

GENERAL FEATURES OF THE STUDY AREA

Nodules were collected from both the Central Indian Basin and the Mas- carene Basin. The Central Indian Basin is bordered onthe west by the Cha-

REE GEOCHEMISTRY OF FERROMANGANESE NODULES 187

TABLE 1

Sampling station details and description of samples

Sample Type Latitude Longitude Depth Description no. (S) (E) (m)

GAR-EN Encrustation 12.500 76.333 5050-5100

649H Encrustation 12.644 76.282 5000

PSET Encrustation 14.500 75.000 4881-5173

MAR- 1 Large nodule from shallow basin

MAR-3 Small nodule from shallow basin

MAR-22 Small nodule from an abyssal hill of shallow basin

198-0 Nodule from flank of seamount

142-0 Nodule from top of a seamount

14.988 54.983 4300

16.016 55.980 4300

16.000 55.983 4130

11.000 73.250 5031

11.000 73.000 3580

Thin brownish oxide layer firmly encrusted over greyish ( < 1 cm) brown consolidated mud underlain by mottled brown hardened mud &MnO2 dominant Black very thin oxide layer ( < 1 cm). Rough (fine granular) surface texture. Loosely encrusted over brownish pala- gonitic material ~-MnO2 dominant with todorokite traces Oxide and substratum are visually distinct, but firmly attached. Oxide black ( 1.5 cm thick). Rough (coarse granular) surface texture. Substratum - - light brown hard mud/palagonite with speckles &MnO2 dominant Irregular elongated slab ( 10-11 cm). Gritty/Knobbley surface. Smooth and rough surface texture. Nucleus - - irregular, elongated, dispersed yellowish brown altered hardened mud, extend- ing almost entire length of the nodule ~-MnO2 dominant, feldspar and quartz present Rectangular, irregular, small (3-4 cm); smooth texture (granular). Nucleus-- elongate, large, dispersed, yellowish brown hardened mud. Definite control of shape by nucleus ~MnO2 with todorokite and quartz Spheroidal to cubical (smoothed edges); smooth surface texture. Nu- cleus - - triangular, unconsolidated material. No control of nucleus on overall shape Only ~-MnO2 Discoidal, medium-sized (5.3 cm) with subcircular outline; surface very rough (coarse granular). Nucleus - - clay (with quartz and illite) ~-MnO2 dominant with minor amounts of todorokite. Rhombohedral, small ( 3.8 cm) with smooth (fine granular) surface. Nu- cleus - - clay (feldspar, phillipsite ) MnO2 dominant with minor amounts of todorokite

188

TABLE 1 (Continued)

B. NAGENDER NATH ET AL.

Sample Type Latitude Longitude Depth Description no. (S) (E) (m)

219-O Base of a 12.750 76.250 5350 seamount

320A Nodule from 12.248 75.501 5269 siliceous clay/ ooze

284A Diagenetic 10.997 74.249 5204 nodule

75C Hydrogenetic 17.998 78.000 4904 nodule

134/l 0 Nodule from Somali-Seychelles Basin shallow basin

O-1T Top of an ori- 13.087 75.019 5270 ented nodule

O- 1B Bottom of the above nodule

O-2T

O-2B

Top of second oriented nodule from the above location

Bottom of second oriented nodule

Granular to coarse granular surface texture. Nucleus - - weathered rock frag- ment (phillipsite, feldspar and pyroxene ) Todorokite dominant, ~MnO2 present Rough textured medium-sized nodule. Nucleus - - fibrous palagonite with phillipsite crystals (?) and smectite Todorokite and &MnO2 in almost equal quantities Todorokite with minor ~-MnO2

Triangular, irregular, small (3.2 cm) nodule. Surface texture smooth. Nu- cleus - - altered rock material Minor amounts of fi-MnO2. No major peaks observed Smooth textured nodule &MnO2 only Medium-sized ( 5-6 cm ) nodule with uneven top surface and flat bottom (half-hamburger shape). Serpulid growths on surface. Surface texture smooth (fine granular). Nucleus - - brownish yellow altered rock No mineralogy data Discoidal, medium-sized (4-5 cm) nodule with a hump on top. Three- fourths of the nodule is stained with sediment. Serpulid growths on top. Sur- face texture smooth (fine granular) 6-MnO2 with minor todorokite Todorokite and ~-MnO2

Description of samples 198-0, 142-0 and 219-0 is from Mukhopadhyay ( 1988 ).

gos-Laccadive and Mid-Indian Oceanic Ridges, on the south by the South- eastern Indian Ridge, on the east by the Ninety East Ridge, and merges in the north into the Bay of Bengal (Schlich, 1982). The Mascarene Basin lies between Madagascar to the west and the Mascarene Plateau to the east. This Basin corresponds to the northwest extension of the Madagascar Basin. The two basins are separated by the Mauritius Fracture Zone. To the south, the Mascarene Basin abuts the northeastern flank of the Madagascar Ridge. To


50*E 70* 90 110" 130

20N

0

2 oOs

50 70 90 1100 130"

Fig. 1. Sample location map.

the north, the basin extends towards the Farquhar Group, the Amirante Trench and the Seychelles Bank (Schlich, 1982 ).

The nodules were recovered from the vicinity of Tromelin Island, midway between Madagascar and Cargados Carajos. The volcanic outcrops of this island may be contributing nuclei for this suite of nodules. The depths observed in this area are above the carbonate critical depth when compared with those of most of the Central Indian Basin (Kolla and Kidd, 1982 ).

A brief description of the samples is presented in Table 1 and their locations are shown in Fig. 1.

ANALYTICAL METHODS

The major and minor elements were analysed at the Rheinisch-Westf~il- ische Technische Hochschule (RWTH, Aachen, Germany by X-ray fluores, cence spectrometry (XRF) using glass beads which were prepared with a Specpure lithium tetraborate flux, the sample-to-flux ratio being 1 : 7. Miner- alogy of the manganese nodules and crusts was determined by a Siemens X- ray diffractometer using a molybdenum target.

For the determination of REE, the samples including two replicates were


TABLE 2

REE determinat ions (values in ppm ) obtained using ICP-MS compared with results obtained by ion-exchange ICP-OES, SSMS and INAA

Nodule s tandard La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

P-I ( ICP -MS) 105 318 27.5 114 27.2 7.44 33.8 4.53 25.99 4.73 13.3 1.72 13.26 1.75 P-I ( ICP -OES) 103 288 - 135 33.8 7.75 27.0 - 29.20 5.13 15.2 - 12.30 1.89 P-I ( ICP -OES) 107 296 - 143 35.3 9.04 32.5 27.00 4.93 13.4 - 11.50 1.66 P-1 ( INAA) 120 289 - 113 30.4 6.57 29.4 - - - 13.80 1.85 P-1 (SSMS) 82 280 27.0 110 28.0 6.80 24.0 4.20 25.00 5.10 13.0 - 13.00 - A-I ( ICP -MS) 115 656 21.7 94 20.4 5.81 34.3 4.20 25.80 5.09 15.6 2.19 15.40 2.21 A-1 ( ICP -OES) 112 676 105 24.7 6.10 23.6 - 22.40 4.70 14.4 - 11.80 1.92 A-I ( INAA) 133 668 85.3 20.9 4.48 26.5 - - - 16.30 2.16 A-I (SSMS) 130 >300 23.0 94 21.0 4.80 22.0 3.80 22.00 5.30 15.0 - 13.50 -

ICP -MS values are f rom this study. ICP -OES values are from Ingri and Ponter ( 1987 ), INAA values are from Flanagan and Gottfr ied (1980) and SSMS values are from Rankin and Glasby ( 1979 ).

digested in a mixture of HCI, HC104 and HF in an open digestion system. The resulting dried residue was dissolved in HNO3. The REE were measured by inductively coupled plasma-mass spectrometry (ICP-MS) using a VG Plasmaquad at the National Geophysical Research Laboratory, Hyderabad. The details of the method and instrumental settings have been described in detail by Balaram and Saxena ( 1988 ). In contrast to IDMS (isotope dilution mass spectrometry), which can be used only for polyisotopic elements, and ICP, which generally requires prior chromatographic separation from the matrix, ICP-MS offers very low detection limits for all 14 REE, simple spectra and relatively fast analytical turnaround (Jarvis, 1988 ). Considering its low abundance in geological material, 115in was used as an internal standard and to monitor the signal drift during analysis; 100 ng ml- 1 of indium was added to all the samples and standards. After optimizing the ~ 15in signal, the system was operated covering a mass range of m/z 113-176.

The analytical accuracy of the analysis was checked by preparing duplicates of US Geological Survey nodule standards A-1 and P-1. The results obtained are shown in Table 2, and are compared there with the published values. The precision was better than _+ 1% for all the major elements except for Mg ( _+ 3%), and better than _+ 6% for REE except Ho ( _ 8%).

RESULTS AND DISCUSSION

The results of the major element and REE analyses are presented in Tables 3 and 4.

Top-bottom fractionation or REE zonation

Elderfield et al. (1981a) and Murphy and Dymond (1984) have found significant variation in the REE concentrations of tops and bottoms of Pacific


TABLE 3

Major element data (concentration in wt.%) of manganese nodules and crusts (analysis performed on samples dried at 110 C)

Sample no. Fe Mn Ti Ca K P Si Al Mg

GAR-EN a 14.53 8.70 0.61 1.34 1.74 0.19 14.43 5.12 1.21 649H a 17.17 19.39 0.70 2.00 0.63 0.22 6.60 1.37 1.30 PSET a 10.14 19.01 0.55 1.49 1.21 0.19 8.57 3.58 2.01 MAR-I 17.25 14.85 0.83 2.28 0.93 0.25 9.84 3.11 1.40 MAR-3 18.23 13.48 0.95 2.08 1.09 0.28 10.00 3.38 1.28 MAR-22 20.32 16.80 1.08 2.17 0.50 0.30 6.17 1.98 1.19 198-O 8.48 27.99 0.36 1.92 0.66 0.12 6.58 1.78 1.66 142-O 13.82 21.47 0.47 1.88 0.92 0.20 8.21 2.18 1.54 219-O 8.99 28.46 0.36 1.85 0.69 0.14 6.36 1.96 1.57 320A 8.11 24.58 0.33 1.45 0.81 0.09 8.95 2.99 2.03 284A 7.51 25.24 0.34 1.59 0.85 0.09 9.00 2.73 1.98 75C 10.94 6.47 0.61 0.65 2.74 0.07 18.84 6.32 1.65 134/10 19.04 17.09 0.70 2.08 0.64 0.25 7.79 1.75 1.19 O-1 T b 14.72 23.27 0.47 1.83 0.57 0.21 5.85 1.79 1.53 O-1 B b 14.51 22.45 0.46 1.69 0.59 0.18 6.49 2.13 1.57 O-2T b 20.19 26.97 0.83 2.03 0.36 0.23 5.06 1.42 1.51 0-2 B b 15.98 30.76 0.95 2.09 0.32 0.18 5.15 1.80 1.80

aFerromanganese crusts. bTops and bottoms of two oriented nodules.

TABLE 4

REE concentrations (in ppm) in ferromanganese nodules and crusts

Sample no. La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

GAR-EN 126 546 26.70 110 24.14 6.23 31.37 4.40 22.35 4.51 11.32 1.92 11.02 1.72 649H 243 860 49.93 201 48.82 12.49 58.24 7.33 40.53 6.90 19.76 2.74 16.76 2.38 PSET 107 872 22.57 93 20.94 5.29 32.17 3.68 21.21 3.72 10.21 1.48 10.17 1.41 MAR-1 160 989 34.21 137 28.64 7.52 38.58 5.20 28.57 5.44 15.30 1.91 13.34 1.93 MAR-3 197 1384 41.22 165 35.78 8.95 49.97 6.18 34.36 6.13 17.43 2.40 15.91 2.25 MAR-22 228 1517 44.75 176 37.64 9.45 55.54 6.53 36.37 6.74 18.16 2.57 17.17 2.32 198-O 125 347 31.38 128 30.05 8.02 36.04 4.87 26.42 4.51 12.26 1.72 11.90 1.64 142-O 180 616 41.65 164 36.50 9.64 44.72 6.35 32.90 5.48 15.59 2.06 13.91 1.97 219-O 121 446 32.38 133 33.88 8.33 36.56 5.25 27.35 4.63 13.30 1.87 11.76 1.73 320A 90 241 27.39 130 55.53 17.02 63.15 8.13 41.35 9.84 30.58 6.57 41.33 8.52 284A 87 245 21.54 88 21.24 5.50 25.30 3.t7 17.38 3.21 8.43 1.12 7.68 0.92 75C 57 341 12.24 49 10.51 3.19 16.79 2.09 10.43 2.01 5.52 0.68 4.73 0.62 134/10 168 910 36.75 148 32.25 8.13 44.98 6.00 32.01 5.85 15.95 2.16 14.86 2.05 O-1 T 181 715 43.74 177 41.22 10.96 53.35 7.21 37.84 6.50 17.17 2.49 16.21 2.07 O-I B 175 726 41.35 170 38.64 10.49 52.40 6.81 35.90 6.26 17.55 2.39 16.03 2.24 O-2T 216 835 49.61 206 48.43 12.31 63.56 8.10 44.75 7.96 20.53 2.90 19.23 2.69 O-2B 147 549 34.27 139 30.81 8.33 40.29 5.21 29.71 5.27 13.96 1.65 13.45 1.71

Sample details are as described in Table 3.

192 B. NAGENDER NATH ET AL

I

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manganese nodules. To confirm the prevalence of such a variation in the nodules from the Indian Ocean, tops and bottoms of two oriented nodules were analysed for REE in the present study.

The analytical results and the shale-normalized REE patterns of these samples are shown in Tables 3 and 4 and Fig. 2, respectively. The shale values of REE used to normalize are from Piper (1974b) and Sholkovitz ( 1988 ), and represent a mean value of North American, European and Russian shales. The Mn/Fe ratios in these samples vary from 1.3 to 1.9. Of the two nodules studied for top-bottom fractionation, one nodule (O-2) has a composition- ally distinct top and bottom zonation similar to that reported initially by Raab (1972) and later by other workers (Calvert et al., 1978; Moore, 1984; Dy- mond et al., 1984; Friedrich et al., 1988). In contrast, nodule O-1 shows almost equal Mn/Fe ratios (Table 5 ).

TABLE5

Important elemental ratios used for genetic interpretations

Sample no. Mn/Fe Ce/La Ce/Nd La/Sm Yb/Sm

GAR-EN 0.6 4.32 4.98 5.24 0.45 649H I. 1 3.54 4.28 4.98 0.34 PSET 1.8 8.17 9.41 5.10 0.49 MAR-1 0.9 6.17 7.20 5.59 0.47 MAR-3 0.7 7.01 8.41 5.51 0.45 MAR-22 0.8 6.67 8.63 6.05 0.46 198-O 3.3 2.77 2.72 4.16 0.40 142-0 1.6 3.43 3.76 4.91 0.38 219-0 3.2 3.70 3.35 3.56 0.35 320A 3.0 2.69 !.85 1.62 0.74 284A 3.4 2.81 2.76 4. l0 0.36 75C 0.6 6.01 6.95 5.40 0.45 134/10 0.9 5.41 6.14 5.21 0.46 O-1 T 1.6 3.95 4.05 4.39 0.39 O-1 B 1.5 4.14 4.27 4.53 0.42 0-2 T 1.3 3.87 4.06 4.76 0.40 0-2 B 1.9 3.75 3.96 4.42 0.44

Sample details are as given in Table 3.

Fig. 2. Shale-normalized patterns of the samples studied. (A) Tops and bottoms of the oriented nodules O- l and 0-2. (B) Nodules from the seamount environment. The sample from the seamount top (142-O) shows the maximum REE concentration. (C) Patterns for three varieties of nodules. Sample 75C is a typical hydrogenetic nodule from a red clay region and shows the biggest possible cerium anomaly. Sample 284A is representative of a diagenetic nodule with a low positive Ce anomaly. Smectite-containing nodule 320A is enriched in HREE. (D) Patterns of ferromanganese encrnstations. (Note the strong positive cerium anomalies.) (E) Nodules recovered from the Western Indian Ocean. All of them have identical patterns and higher REE concentrations than the nodules from the Central Indian Basin.


1OOO-

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. . . . . . . . . I . . . . . . . . . t . . . . . . . . . I . . . . . . . . . i . . . . . . . . .

14 16 18 20 22

IRON

Fig. 3. Diagram showing the relationship between Fe (%), Ce and other REE (ppm) in the oriented nodules. B and T represent bottoms and tops, respectively.

The oxide layers from the top and bottom of nodule 0-2 have differing mineralogy. Whereas there is more 6-MnO2 than todorokite in the top part of the nodule, no significant differences are found between 6-MnO2 and todorokite in the bottom of the nodule. A strong quartz peak and higher concentrations of AI and Si (Table 3 ) indicate the presence of larger amounts of aluminosilicate debris in the bottom of the nodules.

Similar to the results found by Elderfield et al. ( 1981 a), a positive co-variation between REE and Fe (Fig. 3 ) is observed. Fe enrichment in the nodule tops and Mn phase enrichment in nodule bottoms (as found in this study, and by Banakar (1990) and Pattan and Mudholkar (1990) for the same area) indicate the role of diagenesis. Apart from Si and A1 (aluminosilicate phase ), and Mn, P is the only major element which shows a consistent zonation. The zonation of P and Fe are similar. The association of REE with Fe and P could be due to two competing phases - - Fe oxyhydroxide and P phase from phosphatic fish debris (Elderfield et al., 1981b; Calvert and Piper, 1984) - - or could be caused by incorporation in a single iron (phosphate) oxyhydroxide phase alone (Glasby and Thijssen, 1982; Glasby et al., 1987 ).

The depletion of the REE in the bottoms of nodules may be explained as follows. Enhanced concentrations of REE in porewater compared with seawater and upward diffusion into overlying sedimentary layers has been observed in anoxic, reducing nearshore sediments (Elderfield and Sholkovitz, 1987; German and Elderfield, 1989; Sholkovitz et al., 1989). There is a lack of porewater REE data in the deep-sea pelagic areas to suggest a contribution of REE through early diagenetic processes, but the similarity in vertical and

REE GEOCHEMISTRY OF FERROMANGANESE NODULES 19 5

interoceanic REE distributions to nutrients in seawater (Elderfield and Greaves, 1982; De Baar et al., 1983, 1985a,b; Klinkhammer et al., 1983 ) may be suggestive of a significant upward diagenetic flux of REE from the sediments (De Baar et al., 1988 ). In spite of these findings, most of the nodule bottoms studied so far (in this study, and by Elderfield et al. (1981a) and Mushy and Dymond (1984) ) show REE depletion. Similarly, many of the nodule bottoms studied so far (including those studied in this work) have lower iron contents (see, e.g. Banakar (1990) and Pattan and Mudholkar ( 1990 ), who considered the same study area); by implication, fewer iron oxyhydroxide surfaces may be available for adsorptive scavenging, which could lead to a lesser enrichment of REE in bottoms.

No REE zonation is observed in the O-1 nodule of this study (Table 4 ) and Nodule 2 of Elderfield et al. (198 l a). The similarities in metal concentrations in tops and bottoms and the mineralogy (~MnO2 and todorokite of roughly equal intensities) seems to be due to turning over of the nodule. Based on studies of 226Ra/23Th and 23Th/232Th activity ratios, differences in 23Th and 231pa, and inconsistent transition metal top/bottom variations, Krish- naswamy and Cochran ( 1978 ) and Moore ( 1984 ) have concluded that nodules turn over on a 1000-10 000 year time-scale in Pacific. Evidence for the turnover of nodules from the Central Indian Basin has also been found by Banakar (1990). At the same time, we do not visualize the possibility of nodule 0-2 turning over, as three-fourths of this nodule was stuck in the sediment (Table 1 ).

Interelement relations and their implications

Correlation matrices have been prepared for three data subsets and are presented in Tables 6 and 7. Table 6 shows the correlation between bulk chemical data and the major elements and elemental ratios of nodules and encrustations. Such elemental ratios were previously used for genetic interpretations (e.g. Addy, 1979; Elderfield et al., 1981a,b; Aplin, 1984; Calvert et al., 1987; Glasby et al., 1987; Kunzendorf et al., 1987 ). The relations among REE are shown in Table 7. It is known that there is an indeterminate tendency for negative correlations between variables of similar compositions (Skala, 1979; Glasby et al., 1985 ). However, our data do show non-trivial positive correlations between Fe and Ti, Fe and P, Ca and P, Si and K, A1 and K, etc. Al- though the postulated relationships as shown below may exist, they are likely to be weaker than the magnitude of correlations indicated.

Although Mn is not related to any other element, other major associations noticed are as follows: a group comprising Fe, Ti, P and the light REE up to Nd (La, Ce, Pr and Nd ), and a group consisting of Si, AI and K. We designate the above associations as Mn-oxide phase, Fe-oxide/oxyhydroxide phase and aluminosilicate phase respectively. Mn has no strong association with REE

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>

REE GEOCHEMISTRY OF FERROMANGANESE NODULES

TABLE 7

Correlation coefficient matrix for REE

197

La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

La 1 0.74 0.96 0.93 0.60 0.45 0.72 0.70 0.76 0.54 0.44 0.14 0.15 -0 .02 Ce 1 0.58 0.53 0.19 0.06 0.41 0.32 0.40 0.27 0.20 -0 .03 -0.01 -0 .13 Pr 1 0.99 0.74 0.61 0.82 0.83 0.87 0.66 0.57 0.27 0.29 0.11 Nd 1 0.82 0.70 0.88 0.89 0.92 0.74 0.65 0.38 0.39 0.22 Sm 1 0.98 0.96 0.97 0.96 0.95 0.94 0.82 0.82 0.72 Eu 1 0.92 0.93 0.90 0.96 0.97 0.90 0.90 0.83 Gd 1 0.98 0.99 0.96 0.92 0.75 0.76 0.63 Tb 1 0.99 0.95 0.91 0.74 0.76 0.63 Dy 1 0.94 0.89 0.70 0.71 0.57 Ho 1 0.99 0.89 0.90 0.81 Er 1 0.94 0.95 0.88 Tm 1 0.99 0.98 Yb 1 0.98

n= 17; values above 0.61 are significant at 99% level.

(Table 6 ), except for a statistically insignificant relation with middle REE (Sm and Eu ). Strong negative correlations are displayed between Si, A1 and K and REE (mostly significant at 99% confidence level). The three major groups observed here are in accordance with the Pacific nodules (Calvert and Price, 1977). The first, second and third elemental groups may represent the diagenetic, hydrogenetic and aluminosilicate phase, respectively.

Negative correlations between REE and the aluminosilicate phase indicate that the surface transfer of continental detritus or the occlusion of detrital material (Ehrlich, 1968 ) is an unlikely mechanism for the incorporation of REE into manganese nodules in the present study. This gains support from Sr and Nd isotope studies reported initially by Goldstein and O'Nions ( 1981 ) and recently by Ben Othman et al. (1989). The 87Sr/S6Sr ratios for manganese nodules from various oceans studied (Ben Othman et al., 1989) range between 0.70895 and 0.70918 and cluster close to, with a slight deviation from, the seawater value (0.70919). Also, the Crqd value is reported to be - 8.9 for Indian Ocean nodules and therefore similar to the seawater value ( -8 ) for this region (Ben Othman et al., 1989). In addition, higher aluminosilicate contents seem to dilute the REE concentrations, as is evidenced by nodule 75C (Tables 3 and 4).

The lack of correlation between the REE and the Mn phase, and their inverse relationship with Mn/Fe ratios (T~tble 6), supports the idea that the nodules with marked diagenetic signature (higher Mn/Fe ratios) show a depletion of REE (Calvert et al., 1987 ), or may be due to the preference of REE for the Fe phase. Sample 284A in this suite of samples is taken as a represent-


ative of diagenetic nodules (with todorokite dominant). This sample shows the lowest concentrations of REE (except for sample 75C).

As designated above, the Fe-bearing phase may represent a hydrogenetic component. There are two schools of thought regarding the correlation between Fe, P and REE in the manganese nodules. Based on elemental correlations and leaching experiments, Elderfield et al. ( 198 lb) suggested that two phases govern the REE distribution in the manganese nodules: (a) a phosphatic phase from fish debris and (b) an Fe-oxyhydroxide phase. In contrast, Calvert and Price ( 1970, 1977 ) suggested that Fe and P are present as a fer- riphosphate phase. Later Glasby and Thijssen ( 1982 ) and Glasby et al. ( 1987 ) similarly attributed this association to a single mineral phase - - iron phosphate. However, none of the above works considered the calcium data of nodules in their REE interpretations. As mentioned above, the REE in this study are associated with Fe and P, either as an iron phosphate phase or as two separate phases. However, it may be noted that the trivalent REE co-vary well with Ca (Table 6). In ferromanganese nodules, the REE are bound initially by two phases: a phosphatic phase and a surface layer of phosphate which had previously been adsorbed onto hydrous iron oxides. Upon diagenesis, the REE may be incorporated into recrystallized biogenic apatite (Jonasson et al., 1985 ). The association of REE with Ca may thus be due to their presence in minor biogenic apatite (calcium phosphate). Liu et al. (1988) have attributed the striking peak for Sm enrichment in a manganese nodule observed by Goldberg et al. (1963) to apatite co-precipitation with the Mn-Fe oxyhy- droxides and replacement of Ca 2 by the middle REE, particularly Sm 3+ whose ionic radius is similar to that of Ca 2+. The proportion of REE associated with biogenic apatite could not be detected, as no apatite peak could be observed from X-ray diffractograms. As calcium and phosphate contents added together form less than 5% (Table 3 ), standard X-ray diffraction tech- niques may not reveal any apatite peaks.

Following Calvert et al. ( 1987 ), La/Sm and Yb/Sm ratios have been used (Tables 5 and 6) to study the REE fractionations. La/Sm ratios for this suite of samples indicate that the nodules from the Western Indian Ocean (Mas- carene and Seychelles Basins ) are LREE enriched compared with the nodules from the Central Indian Basin. The La/Sm ratio varies from 5.0 to 5.2 in crusts and from 1.6 to 5.4 in manganese nodules of the Central Indian Basin (Table 5 ). Among the nodules from the Central Indian Basin, only those from the top of the seamount (Sample 142-0 ) and from the pelagic clay (Sample 75C ) have high La/Sm ratios (Table 5 ). On the other hand, the three nodules from the Western Indian Ocean (Mascarene Basin) all show a higher La/Sm ratio than the shale ratio. The nodule from the shallowest depth (Table 1 ) shows markedly the highest La/Sm ratio (Table 5 ). Therefore, only the nodules and encrustations from shallower depths (Table 1 ) show LREE enrichment in concurrence with the findings by Calvert et al. ( 1987 ).


The HREE behave as a separate entity in this work. HREE are correlated well among themselves (Table 7); they relate only to middle REE (mainly Sm and Eu) and do not exhibit any relationship with major elements (Table 6 ). Such an observation suggests a possible fractionation of REE in this group of samples. The shale-normalized patterns (Fig. 2 ) depict a convex structure with enriched middle REE compared with LREE or HREE (excluding Ce and excepting Sample 320A, which is discussed below). HREE fractionation is further supported by Yb/Sm ratios. None of the samples have a higher Yb/ Sm ratio (except Sample 320A--Table 5 ) than that of shale (0.47; Sholkov- itz, 1988 ). This indicates an HREE depletion in these nodules. This is in contrast to the HREE enrichment in seawater (Goldberg et al., 1963; Hogdahl et al., 1968; Elderfield and Greaves, 1982; De Baar et al., 1983, 1985a,b; Elder- field, 1988; Piepgras and Jacobsen, 1988 ) compared with the shale REE pattern (Gromet et al., 1984). HREE enrichment in seawater has often been attributed to their greater complexing capacities (Turner et al., 1981; Cantrell and Byrne, 1987 ) and to the greater stability of HREE complexes in seawater (Goldberg et al., 1963; Elderfield and Greaves, 1982). Hence, LREE compared with HREE are more susceptible to removal from seawater and to subsequent incorporation into manganese nodules. This may explain why we find LREE enrichment and HREE depletion in these nodules.

Cerium anomaly variations

Large positive Ce anomalies have been often reported in manganese nodules from various locations (see Fleet (1984) for an earlier review and Brookins (1989) for a recent review). They are attributed to the oxidation of Ce(III) to CeO2(s) (Goldberg, 1961 ), although negative Ce anomalies are also reported for a few cases (Courtois and Clauer, 1980; Elderfield and Greaves, 1981; Calvert et al., 1987; Glasby et al., 1987 ). Many workers (e.g. Glasby, 1973; Piper, 1974a; Addy, 1979; Elderfield et al., 1981 a,b; Shaw and Wasserburg, 1985, and others) concur with the idea of Goldberg ( 1961 ) that Ce is preferentially taken up by nodules. All the samples studied here except Sample 320A show positive Ce anomalies (Figs. 2 and 4) between 0.12 (Sample 198-O) and 0.62 (crust PSET) (Fig. 4).

The Central Indian Basin nodules, except the hydrogenetic nodule recovered from the red clay sedimentary domain, show low positive Ce anomalies (Fig. 4). All the nodules from the Western Indian Ocean (Mascarene and Somali-Seychelles Basins) show markedly high Ce anomalies. Ce anomalies show a negative relation with Mn/Fe (Fig. 5 ), implying that they are lowest in the nodules with the maximum diagenetic signature. Strong correlations between Ce and Ti, and between P and Fe (Table 6 ) indicate that Ce may be hosted by the Fe oxyhydroxide phase, and is probably removed from seawater in its higher valence state together with Co and Ti. A weak correla-


MAR 1

MAR 3

MAR 22

134/10

GAR-EN

649H

PSET

198-0

142-0

219-0

320A

284A

75C

0-1T

0-1B

0-2T

0-2B

l 1

I

~ WlO nodu les [ ] crusts

~ i ! i . [ ] ClB nodu les

ii!iiii :jiiiiiiiiiiiiiii!i!iiiill ii! !i iiiiii/ iiiii[

I I I I I 1 I 1 0 0.1 0.3 0.5 0.7

Fig. 4. Magnitude of cerium anomalies. Ce anomalies are calculated following Elderfield and Greaves (1981), using the formula log (3 Ce,/2 (La,+Ndn)), where subscript n represents shale-normalized values. They are highest in all the samples from the Western Indian Ocean, but in the Central Indian Ocean are high only in the encrustations and the hydrogenetic nodule.

tion between Ce and Ca in this study and the commonly observed negative Ce anomalies of the phosphatic phases (Fleet ( 1984 ) and references therein) favours the partitioning of most of the Ce into the Fe phase. The samples with 6-MnO2 (vernadite) as the major ferromanganese mineral have the highest Ce anomalies and all these 6-MnO2-bearing nodules are recovered from the shallower depths (Table 1 ). 6-MnO2 is the main phase in the hydrogenetic substance forming in the well-oxygenated deep-sea environment and is inti- mately intergrown with FeOOH.nH20 and aluminosilicates (Halbach, 1986). The association of an enhanced Ce anomaly with 6-MnO2 could be due to its presence in the Mn phase (Koeppenkastrop and De Carlo, 1988, 1990) or may be due to a probable catalysing effect of the MnO2 surface on the oxidation of Ce 3+.

The variation of Ce anomalies, 6-MnO: contents and LREE/HREE fractionations with geographic locations has been correlated with the bottom-water


m m

E 0

m

0 0

I I , I J J i l " '~ ' . . . . . . . . . . . . .

mm

m m

[]

m

m mm m

u

I

. . . . I . . . . . . . . .

i

IB

f l l

. . . . . . . . . I . . . . . . . . . I . . . . . . . I . . . . . . . . .

1 2 3 4

Mn/Fe

Fig. 5. Scatter plot between cerium anomalies and Mn/Fe ratios showing a negative relationship, which seems to be driven by the dominant mineral present in these nodules. Nodules with higher Mn/Fe ratios, i.e. todorokite-bearing nodules, have lower Ce anomalies.

temperatures. Bottom-water potential temperatures in the Indian Ocean are governed to a large extent by the movement of Antarctic Bottom Water (AABW). The lowest bottom-water potential temperature is - 0.6 C ( Kolla et al., 1976 ) in the Atlantic-Indian Basin (in the west) and the South Indian Basin (in the east ), and the highest temperature is 1.2 C in the Arabian Basin (in the west) and the Central Indian Basin (in the east). Reported temperature values for the Central Indian Basin (0.96-1.2 C ) are much higher (Kolla et al., 1976 ) than those found in the Mascarene Basin (0.6-0.9 C). Kolla et al. (1976) have suggested that although the AABW enters the Central Indian Basin through sills in the Ninety East Ridge and Southeast Indian Ridge, the influx of AABW is less in the Central Indian Basin than in other basins of the Indian Ocean. On the other hand, the low bottom-water temperatures suggest definite AABW effects in the Mascarene Basin. On the whole, it has been observed (by Kolla et al. ( 1976, 1980) and Kolla and Kidd (1982) and references therein) that the AABW effects are more marked on the seafloor in the southern and western regions of the Indian Ocean. In addition, the bottom-water dissolved oxygen levels of the Central Indian Basin are lower than in the Mascarene Basin (Wyrtki, 1971 ).

The Central Indian Basin nodules with higher bottom-water temperatures and low dissolved oxygen contents show lesser REE enrichments, low degree of fractionation and lower Ce anomalies. On the other hand, the nodules from the Mascarene and Somali-Seychelles Basins show enriched REE contents relative to those of the Central Indian Basin (enrichment represented by Western Indian Ocean to Central Indian Basin ratios is in the order Ce


(2.24)>La (1.31)>Lu ( l .24)>Er ( l .21)>Tm, Yb (1.2)>Ho ( 1.19 ) > Gd, Pr ( 1.15 ) > Nd ( 1.13 ) > Sm ( 1.04) ), and Ce anomalies. The Ce anomaly of the Somali-Seychelles nodule is lower (0.43) than that of Mascarene Basin nodules (0.49-0.55), reflecting the flow of AABW from south to north. These findings lead us to assume that in addition to the mineralogical control, hydrographic features and redox conditions also play a role in the REE concentrations.

Gadolinium-terbium anomalies

When compared with the neighbouring elements, the shale-normalized Gd value shows a positive departure, with a corresponding negative Tb anomaly, in all the nodules and crusts studied here (Fig. 2 ). Similar distinct Gd positive anomalies and depressed Tb values have been reported for seawater by De Baar et al. (1985b). They have also been previously reported in Fe-Mn oxide crusts from the Pacific Ocean by Hein et al. (1988) and De Carlo (1990). Gd anomalies in seawater have been attributed to a higher degree of complexation of Gd, resulting in reduced scavenging of dissolved Gd relative to its neighbours Eu and Tb (De Baar et al., 1985b). It may therefore be expected that marine authigenic deposits would, on average, exhibit a com- plementary negative Gd anomaly (De Baar et al., 1985b), whereas the REE patterns observed in the present study are similar to the seawater pattern. Such an observation is of interest, as the REE patterns of nodules are generally a mirror image of the seawater pattern. For example, there is a gradual increase in the shale-normalized HREE pattern of seawater but a decrease in the pattern for the nodules studied here. If the aqueous complexing capacity of Gd is as high as reported by De Baar et al. (1985b), the nodules should have shown a depleted behaviour similar to that of HREE. Additional data from various locations are needed to explain the behaviour of Gd in the oceanic environment.

The mechanism leading to this similarity in the shale-normalized Gd patterns of seawater and manganese nodules may be analogous to the process of retention of negative cerium anomalies from seawater by manganese nodules at certain locations (Piper, 1974a; Courtois and Clauer, 1980; Elderfield and Greaves, 1981; Calvert et al., 1987; Glasby et al., 1987).

HREE enrichment in Sample 320A

Sample 320A shows an REE pattern (Fig. 2 ) markedly different from those of other nodules, with a significant HREE enrichment and no Ce anomaly. The interior of this nodule, including the type of nucleus, was found to be different from that of other nodules. This sample is composed of brownish, fibrous material with disseminated shining phillipsite (?) crystals. X-ray dif-


fraction studies revealed quartz, illite, smectite, plagioclase and kaolinite. Smectite was confirmed by the usual method of glycolation (Warshaw and Roy, 1961). Furthermore, this material was identified as palagonite. Pala- gonite is a mixture of altered, hydrated, oxidized glass, and composed of a dioctahedral smectite with significant Mg in the octahedral sheet (Eggleton and Keller, 1982 ). Palagonites are the common alteration products of submarine basalts and glasses (Honnorez, 1981, and references therein; Miihe and Frenzel, 1989; Zhou and Fyfe, 1989 ). However, there is little agreement on the overall magnitude or the potential for fractionation among REE during the low-temperature alteration of basalts (McLennan, 1989, and references therein; Grauch, 1989, and references therein). The halmyrolytic minerals formed from basalts, such as smectite and phillipsite, display REE patterns similar to those of seawater (Piper, 1974a,b; Bernat, 1975; Courtois and Hof- fert, 1977; Desprairies and Bonnot-Courtois, 1980). The REE pattern of Sample 320A (Fig. 2), with no Ce anomaly and HREE enrichment, is com- parable with that for the smectites from the South Pacific which are formed from halmyrolitic reactions involving volcanic lithogenous material and seawater (Piper, 1974a; Courtois and Hoffert, 1977). These variations under- line the importance of REE in nucleus material and the potential effects of the nucleus material on the bulk REE contents. The importance of the nucleus may be more significant in the nodules with low oxide/nucleus ratios. This further suggests that one should be cautious in comparing the results of separated oxide and bulk analyses of whole samples.

SUMMARY

The REE distributions in the nodules and crusts from the Western Indian Ocean exhibit notable enrichments (of 10-30%) relative to the nodules from the more diagenetic environment of the Central Indian Basin. For Ce, the enrichments are more pronounced (up to 220%). The preferential enrichment of Ce and other REE in the nodules from the Western Indian Ocean is consistent with the oxygenated conditions created by the AABW flow. Super- imposed on these oceanographic conditions are redox conditions within the sedimentary environment. The restriction of higher REE contents and higher Ce anomaly values to &MnO2 nodules and crusts, and of the opposite pattern to todorokite nodules, and the inverse relation between some of the REE (es- pecially Ce) and Mn/Fe suggest that nodule REE chemistry may also be linked to sediment diagenesis.

Interelement correlations between Ca, Fe, P and trivalent REE support the idea of Elderfield et al. (198 lb) that REE probably reside in two phases, an iron oxyhydroxide phase with phosphate chemisorbed onto it, and a minor apatitic phase. On the other hand, Ce seems to be associated with vernadite


that is richer in iron oxyhydroxide than todorokite, with MnO2 catalysing the oxidation of Ce to an insoluble tetravalent form.

ACKNOWLEDGEMENTS

The sampling work was carried out with the financial support of the De- partment of Ocean Development, Government of India, as part of their programme 'Polymetallic Nodules Survey'. B.N. thanks the German Academic Exchange Service (DAAD) for support while writing this paper. We thank the Directors of the National Institute of Oceanography, Goa, the National Geophysical Research Institute, Hyderabad, and the Institut f'tir Mineralogie und Lagerst~ttenlehre, Aachen, for providing facilities. B.N. and M.S. thank R.R. Nair, Project Leader, for encouragement to undertake this work, Dr. R. Mukhopadhyay for providing the three samples from seamount environment and unpublished data, and M. Shyam Prasad for crust samples and for his help during microscopic work on Sample 320A. Jai Sankar is thanked for word-processing work. We wish to express our sincere thanks to Drs. H. Kun- zendorf, G.P. Glasby, P.M. Herzig, A.C. Aplin, S.E. Calvert and E.D. Shol- kovitz for helpful suggestions and comments on an earlier version of the man- uscript; and Professor P.J. Wangersky and two anonymous reviewers for their work on a later version.

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