ARTICLE IN PRESS
Deep-Sea Research I 54 (2007) 85–98
www.elsevier.com/locate/dsr
Geochemistry of lithium in marine ferromanganese
oxide deposits
Xuejun Jianga,b,, Xuehui Linb, De Yaoc, Shikui Zhaia, Weidong Guod
a
College of Geoscience, Ocean University of China, 266071 Qingdao, China
b
Qingdao Institute of Marine Geology, 266071 Qingdao, China
c
Shandong University of Technology, 255049 Zibo, China
d
Department of Oceanography, Xiamen University, 361005 Xiamen, China
Received 11 December 2005; received in revised form 15 September 2006; accepted 5 October 2006
Abstract
We have measured lithium content of marine ferromanganese oxide deposits of different origins and conducted a
sequence of selective dissolution experiments on them. There is more lithium in diagenetic and transitional marine
ferromanganese nodules than in hydrogenic ferromanganese crusts. Lithium in diagenetic and transitional nodules is in the
10 Å-manganate phase rather than in the lithiophorite or other phases, as shown by the sequential selective dissolution
results. The different contents of lithium in the different generic types of marine ferromanganese oxide deposits are
attributed to the varying mineralogy. Ten Å manganates, the main minerals in diagenetic and transitional marine
ferromanganese nodules, can incorporate significant amounts of lithium because of their distinct structure and can be
regarded as an important scavenger of lithium in the oceans. The diagenetic and transitional marine ferromanganese
nodules may play a role in the mass balance of lithium in the oceans. On the other hand, it appears that lithium is present
in hydrogenic marine ferromanganese crusts in an aluminosilicate phase rather than in other phases such as vernadite (dMnO2) or ferric oxide/hydroxide. Vernadite (d-MnO2) and ferric oxide/hydroxide adsorb very small amounts of lithium in
the oceans.
r 2006 Elsevier Ltd. All rights reserved.
Keywords: Lithium; Selective dissolution experiment; Diagenetic ferromanganese nodules; Hydrogenic ferromanganese crust; Existing
phase
1. Introduction
The lithium concentration of seawater has not
varied significantly over the last 40 Ma (Delaney
and Boyle, 1986), while rivers discharge a large
Corresponding author. Present address: Qingdao Institute of
Marine Geology, China Geological Survey, Qingdao 266071,
China. Tel.: +86 532 85755851; fax: +86 532 85773903.
E-mail address: [email protected] (X. Jiang).
0967-0637/$ - see front matter r 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.dsr.2006.10.004
quantity of lithium into the oceans (Stouffyn-Egli
and Machenzie, 1984) and hydrothermal activity at
ridge crests supplies a considerable amount of
lithium to oceanic waters (Edmond et al., 1979).
Lithium is regarded as a sensitive indicator of
sediment–water interaction, and the significance
of sediment diagenesis and adsorption as sinks of
oceanic Li has been evaluated (Zhang et al., 1998).
Stouffyn-Egli and Machenzie (1984) suggested that
basalt–seawater reactions play an important role in
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the mass balance of dissolved Li in the oceans. The
alteration minerals of submarine basalts can
incorporate lithium from seawater (Chan and
Edmond, 1988). Many reports have assumed that
authigenic clays such as smectite and phillipsite can
remove lithium from seawater by isomorphic substitution of Mg2+ and Li+ for Al3+ or of Li+ for
Mg2+ or Fe2+ in the octahedral positions of layer
silicates (Huh et al., 1998; Stouffyn-Egli and
Machenzie, 1984) to play an important role in the
mass balance of lithium (Pistiner and Henderson,
2003; Chan et al., 1992; Zhang et al., 1998; Huh et
al., 1998). One important type of authigenic
structure, marine ferromanganese oxide deposit,
has been overlooked in the studies of the mass
balance of lithium in the oceans. Also overlooked
has been the geochemistry of lithium in the oxide
deposits themselves.
Marine ferromanganese deposits can be grouped
into nodules and crusts according to their morphology. Although the marine manganese minerals have
low crystallinity, sub-micro size and intergrowth
and are hydrous (Burns et al., 1983; Burns and
Burns, 1977; Ostwald, 1984), the mineralogy is one
of the most important criteria used for determining
the origin of marine ferromanganese deposits (Usui
et al., 1993). Many studies, therefore, classify
marine ferromanganese deposits into the diagenetic,
hydrothermal and hydrogenic according to the
mineralogy (Halbach et al., 1988; Skornyakova
and Murdmaa, 1992; Jeong et al., 1994; Jung et
al., 1998), the classification being based on three
principal minerals: diagenetic (buserite (10 Å manganates)), hydrogenic (d-MnO2) and hydrothermal
(todorokite) (Burns et al., 1983; Stouff and Boulégue, 1988; Usui et al., 1989). The basal d-spacings of
diagenetic 10 Å manganates that are poor in
transition metals other than Mn in the interlayers
contract from about 10 and 5 Å to about 7 and
3.5 Å after drying at 110 1C, while the 10 Å
manganates with sufficient amounts of interlayer
transition metal cations remain structurally unaltered (Mellin and Lei, 1993; Usui et al., 1989). On
the other hand, the structure of todorokite dried at
110 1C remains unaltered (Arrhenius and Tsai, 1981;
Usui et al., 1989, 1997). Diagenetic nodules with
abrasive and gritty surfaces enriched in Mn, Ni, Cu
and 10 Å manganates are generally embedded in
surface sediments (Jeong et al., 1994; Aplin and
Cronan, 1985; Martin-Barajas et al., 1991; Kasten
et al., 1998; Bonatti et al., 1972; Dymond et al.,
1984; Halbach et al., 1982) and have a high ratio of
Mn/Fe(44 generally) ( Usui et al., 1993; Skornyakova and Murdmaa, 1992). Hydrogenic nodules
and crusts, which are composed mostly of d-MnO2
and ferric hydroxide, are generally exposed on the
seafloor to seawater containing abundant Fe and
Co (Jeong et al., 1994; Martin-Barajas et al., 1991;
Kasten et al., 1998), have a low ratio of Mn/Fe
(o2.5 generally) and are poor in Cu, Ni and Zn
(Jeong et al., 1994). Hydrothermal nodules are
characterized by a high ratio of Mn/Fe and by being
poor in Cu, Ni and Co relative to the diagenetic and
hydrogenic counterparts (Usui et al., 1997; Hodkinson et al., 1994; Hein et al., 1987; Moorby et al.,
1984; Moorby and Cronan, 1983). In addition to the
three types mentioned above, a transitional manganese nodule occurs. Its chemical composition and
minerals vary depending on contact with either
surface or deeper sediments (Moore et al., 1981;
Reyss et al., 1985). At the bottom the chemical
composition and minerals are similar to those of
diagenetic manganese nodules, while at the top the
chemical composition and minerals are similar to
those of the hydrogenic nodules and crust (Skornyakova and Murdmaa, 1992; Jeong et al., 1994).
Many elements, such as transitional elements Cu,
Co, Ni and Zn, have different geochemistries in
different types of ferromanganese oxide deposits.
We will investigate the geochemistry of lithium in
the ferromanganese deposits in terms of chemistry
and mineralogy.
2. Sample description
Locations and descriptions of the ferromanganese
oxides deposits studied here are given in Tables 1
and 2, and locations of the sampling sites shown in
Fig. 1. The ferromanganese crust was discovered
and collected by dredging on a seamount surface
during cruise DY-10 with the ‘‘Haiyang VI’’ in
2002. Obvious ripples of surficial sediments on the
seamount surface, caused by currents, were observed with an underwater camera. The diagenetic
ferromanganese nodule, which was buried under the
sediments, was collected by dredging, and
the transitional nodule, which was embedded
in the uppermost sediment was collected from the
abyssal plain with free-fall grab during a cruise of
the ‘‘Dayang I’’ in 2003.
The hydrogenic ferromanganese crust, with a
smooth dark gray surface, was about 5.2 cm thick
with seven visible layers. Samples were taken from
each layers (Table 2, Fig. 2).
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Table 1
Details of the managaese nodules and crust analysed in this investigation
Samples
Location
Sediment type
Water depth (m)
Depth of nodule
in sediment (mm)
Water mass
Mn-Fe-Nod
Mn-Fe-TranNod
Mn-Fe-Cru
81350 0100 N, 1541030 0600 w
10107.470 N, 154126.280 w
13152.050 N, 169138.020 w
Siliceous ooze
Siliceous ooze
—
5135
5156
2800
0–10
Surface
—
AABW
AABW
—
Table 2
Descriptions of the samples collected from the crust and the diagenetic nodule
Samples
Property
Thickness
Mn-Fe-Cru-1
Mn-Fe-Cru-2
Mn-Fe-Cru-3
Mn-Fe-Cru-4
Mn-Fe-Cru-5
Mn-Fe-Cru-6
Mn-Fe-Cru-7
Dark gray
Dark gray with clay interlayer in brown
Brownish-yellow with loose structure
Dark gray with brownish-yellow
Grayish-yellow with brownish-yellow interlayer
Dark gray with fine brownish-red vein and a little clay in yellow, loose structure
Dark gray with pitchy luster
0.4
0.5
0.5
0.6
0.5
1.4
1.3
Mn-Fe-Nod-1
Mn-Fe-Nod-2
Mn-Fe-Nod-3
Mn-Fe-Nod-4
Mn-Fe-Nod-5
The spherical core in brownish-yellow with dense structure
Gray with intercalated ooze and somewhat loose structure
The same as Mn-Fe-Nod-2
The same as Mn-Fe-Nod-2
Dark gray with dense structure
0.6
0.5
1.2
0.9
0.8
The diagenetic nodule was spherical with a radius
of 4.0 cm and an abrasive and gritty surface covered
by yellow clays. There were five laminations from
the center to the periphery (Table 2, Fig. 2). Besides
the 5 diagenetic samples, a transitional nodule
sample of ellipsoid shape with micro-axis, meanaxis and minor-axis of 3.5, 2.2 and 1.1 cm,
respectively, was collected to compare the amount
of lithium and 10 Å manganates to those of the
diagenetic nodule sample.
3. Experimental details
Samples were dried in air and finely ground in an
agate mortar for chemical analysis. The powders
produced by grinding were digested with HCL,
HNO3 and HClO3 to determine the macro and trace
elements by inductively coupled plasma/atomic
emission spectrometry (ICP/ES) (Table 3), while Si
was determined by atomic absorption spectroscopy
(AAS). The mineral composition of nodule and
crust samples was determined on the powder after
air-drying at room temperature. The nodule samples were also analyzed after heating at 110 1C with
an X-ray diffractometer (XRD) (Fig. 3, Fig. 4).
We analyzed the existing phases of lithium in
various ways because of the great differences of
lithium concentration among the ferromanganese
deposits. It is difficult to analyze the lithium phase
in the hydrogenic crust by chemical methods because of the very small amounts of lithium (Table 3),
though the statistics are available and are useful to
some extent. On the other hand, the lithium phase in
the diagenetic and transitional nodules could be
analyzed by chemical methods because of the
high content. The analytical methods were based
on the following strategy: first, to determine
whether the lithium is present in the lithiophorite
phase in the diagenetic and transitional nodules,
because lithiophorite is an important mineral
bearing some lithium; second, if the lithium was
not present in the lithiophorite phase, the selective
dissolution experiments were conducted further to
investigate the existing phase.
A selective dissolution experiment was conducted
as a reference (Tokashiki et al., 2003) to determine
whether the lithiophorite was present: 50 mg of the
o2 mm diagenetic and transitional ferromanganese
nodule samples were placed in each of six 50 ml
Teflon centrifuge tubes, and 40 ml of 0.1 M hydroxylamine hydrochloride solution was put into each
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X. Jiang et al. / Deep-Sea Research I 54 (2007) 85–98
Fig. 1. Location map of the nodule samples Fe–Mn-Nod and Fe–Mn-TranNod in a manganese nodule province and the crust sample
Fe–Mn-Cru near Line Island. Contours with hatched lines denote 6000 m water depth and others 4000 m.
Fig. 2. Morphology of manganese deposits. Both of the samples are greyish black. (A) The crust sample has seven visible layers and
samples were taken from each. The layers in the actual sample were far more distinct than in the photo. (B) The nodule sample has five
discernible laminations from the center to the periphery, and each was sampled.
tube; the tubes were shaken for 30 min at ambient
temperature (16–25 1C) and centrifuged at 2000g for
10 min; the supernatant was decanted for analysis
by ICP/ES with the results shown in Table 4.
Additional dissolution experiments were conducted to investigate the phase of lithium in the
diagenetic and transitional nodule samples. A twostep procedure was used.
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Table 3
Concentrations of the elements in transitional nodule Mn-Fe-TranNod, diagenetic nodule Mn-Fe-Nod and hydrogenic crust Mn-Fe-Cru
Samples
Mn (%) Fe (%) Ca (%) Mg (%)
Al (%)
Na (%) Li (106) K (%) Si (%) Ni (%) Cu (%)
Co (%)
Mn-Fe-TRanNod
Mn-Fe-Nod-1
Mn-Fe-Nod-2
Mn-Fe-Nod-3
Mn-Fe-Nod-4
Mn-Fe-Nod-5
Mn-Fe-Cru-1
Mn-Fe-Cru-2
Mn-Fe-Cru-3
Mn-Fe-Cru-4
Mn-Fe-Cru-5
Mn-Fe-Cru-6
Mn-Fe-Cru-7
27.06
25.46
34.68
33.59
34.12
29.04
23.93
27.38
25.02
25.71
24.28
19.82
23.80
2.91
3.22
1.96
2.29
2.15
1.75
0.59
0.35
0.54
0.36
0.70
1.74
0.50
2.06
2.19
1.82
1.73
2.41
2.83
1.46
1.61
1.55
1.59
1.60
1.63
1.57
0.27
0.14
0.11
0.11
0.14
0.21
0.28
0.41
0.41
0.49
0.50
0.41
0.72
7.75
6.87
3.01
2.90
3.39
8.17
17.93
18.61
20.15
18.52
18.51
18.70
19.51
0.92
0.98
0.75
0.39
0.77
0.91
1.24
1.44
1.33
1.34
1.29
1.44
1.20
2.05
1.82
2.43
2.62
2.44
1.65
0.97
1.04
1.05
1.02
1.02
1.00
1.01
143.5
95.4
226.4
219.3
305.1
318.7
2.08
1.18
1.65
1.25
1.87
5.68
2.16
1.05
1.39
1.09
1.16
0.93
0.75
0.47
0.44
0.44
0.42
0.51
0.69
0.42
13.49
13.33
8.30
8.14
8.48
6.93
3.74
1.83
2.82
2.02
3.36
5.37
2.23
1.17
1.00
1.40
1.36
1.72
1.19
0.46
0.51
0.47
0.49
0.41
0.36
0.36
0.92
1.00
1.51
1.53
1.49
0.84
0.20
0.20
0.20
0.19
0.17
0.14
0.10
Fig. 3. The powder XRD patterns of nodule samples (A: Mn-Fe-Nod-1; B: Mn-Fe-TranNod; C: Mn-Fe-Nod-2. Because the samples from
Mn-Fe-Nod-2 to Mn-Fe-Nod-5 have the same XRD patterns except the ratio of 10 Å manganates/d-MnO2, the XRD patterns of Mn-FeNod-2 to Mn-Fe-Nod-5 are not shown here.)
Step 1. Elements in soluble, exchangeable or
carbonate states.
To each of six 50-ml Teflon centrifuge tubes we
added 200 mg of o2 mm powder from each of the
six diagenetic and transitional nodule samples
and 20 ml 1 M acetic acid. The six tubes were
placed on a mechanical shaker at ambient
temperature and at medium speed for 20 min.
The solid and liquid phase were then
separated by centrifuging at 1500g for 10 min.
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Fig. 4. The XRD patterns of sample Fe–Mn-Nod-3 (A: air drying at room temperature; B: drying at 110 1C for 4 h. The 10 Å spacing of
the 10 Å manganates remained unaltered after heating at 110 1C with a slight decrease in the ratio 10 Å/7 Å. Other nodule samples have
almost the same patterns despite various slight decrease in the ratio 10 Å/7 Å, only Fe–Mn-Nod-3 is shown here).
Table 4
Bulk chemical composition and amounts of elements leached with hydroxylamine hydrochloride of the diagenetic and transitional nodule
samples
Elements
Mn-Fe-Nod-1
Mn-Fe-Nod-2
Mn-Fe-Nod-3
Mn-Fe-Nod-4
Mn-Fe-Nod-5
Mn-Fe-TranNod
Bulk chemical composition
Amounts of elements Leached with hydroxylamine hydrochloride
Li (ppm)
Mn (%)
Fe (%)
Al (%)
Li (ppm)
Mn (%)
Fe (%)
Al (ppm)
95.4
226.4
219.3
305.1
318.7
143.5
25.46
34.68
33.59
34.12
29.04
27.06
6.87
3.01
2.90
3.39
8.17
7.75
3.22
1.96
2.29
2.15
1.75
2.91
85.8
217.3
204.6
310.8
299.5
132.8
21.92
32.85
29.98
32.15
25.64
24.34
0.26
0.00
0.02
0.02
0.42
0.17
83.5
132.7
107.3
114.8
100.8
79.1
The supernatants were decanted for analyzing
the elements, and the residues were then rinsed
with 10 ml distilled water and centrifuged again.
The supernatants were discarded. The solid
residues were reserved for the next step of the
selective dissolution experiments.
Step 2. Elements bound to manganese oxides.
Twenty ml 0.1 M NH2OH HCL–0.01N HNO3
was poured into each of the six Teflon centrifuge
tubes holding the solid residues reserved from
Step 1. The tubes were placed on the mechanical
shaker at ambient temperature and at medium
speed for 30 min. The solid and liquid phase were
then separated by centrifuging at 2500g for
15 min. The supernatants were decanted for
analysis.
The chemical compositions of the supernatants
from Steps 1 and 2 were analyzed by ICP/ES
(Table 5).
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Fe (106)
35
111
46
137
84
35
Mn (%)
23.41
32.16
31.02
31.75
26.23
24.85
Li (106)
46.2
114.0
80.4
116.7
131.5
78.0
Al (106)
659
566
451
536
383
672
Li (106)
43.0
109.4
127.2
219.2
170.3
64.8
Li (106)
95.4
226.4
219.3
305.1
318.7
143.5
Elements
Mn-Fe-Nod-1
Mn-Fe-Nod-2
Mn-Fe-Nod-3
Mn-Fe-Nod-4
Mn-Fe-Nod-5
Mn-Fe-TranNod
Mn (%)
25.46
34.68
33.59
34.12
29.04
27.06
Fe (%)
6.87
3.01
2.90
3.39
8.17
7.75
Al (%)
3.22
1.96
2.29
2.15
1.75
2.91
Mn (%)
0.07
0.21
0.23
0.06
0.16
0.06
Fe (106)
69
78
11
25
8
14
Amounts of elements Leached with acetic acid
Bulk chemical composition (measured
seperately)
Samples
Table 5
Bulk chemical composition and consequences of the sequential leaching experiments
Amounts of elements leached with
hydroxylamine hydrochloride
Al (106)
28
26
33
24
75
35
X. Jiang et al. / Deep-Sea Research I 54 (2007) 85–98
91
4. Results
The manganese contents of the nodule samples
ranged from 25.46 to 34.68 wt% with an average of
30.66 wt%, whereas the averages for Fe and Al were
5.35 and 2.38 wt%, respectively; the Mn/Fe ratio
ranged from 3.49 to 11.58 (Table 3). The contents of
Fe and Al as well as the Mn/Fe ratio were all higher
than those of hydrothermal nodules (Table 6). Ni
and Cu contents ranged from 0.84 to 1.72 wt%,
distinctively different from those of hydrothermal
Mn deposits (Table 6). Hydrothermal deposits are,
in general, markedly enriched in Mn but depleted in
Fe, Al, Co, Cu and Ni compared with hydrogenetic
or diageneitc manganese deposits. These compositional features indicate that the nodule samples are
in categories other than hydrothermal.
XRD analysis of the nodule samples, measured
after air drying, shows that they are composed
mainly of 10 Å manganates with minor d-MnO2 and
minimal 7 Å manganates, quartz and feldspar
(Fig. 3). The nodule samples are diagenetic and
transitional manganese deposits according to chemical composition, mineral constituents and morphology. The X-ray intensity ratio 10 Å/7 Å is
variable among the six nodule samples but within
a narrow range. The thermal treatment at 110 1C, to
discriminate todorokite from buserite, revealed that
the 10 Å spacing is retained with a slight decrease in
the ratio 10 Å/7 Å (Fig. 4). The stable structure of
10 Å manganates indicated that the 10 Å manganates have incorporated sufficient amounts of the
interlayer transition metal cations, such as Cu and
Ni, to retain the structure unaltered after heating at
110 1C (Mellin and Lei, 1993; Martin-Barajas et al.,
1991; Usui et al., 1989).
The hydrogenic ferromanganese crust samples
were composed mainly of d-MnO2, amorphous
ferric oxide/hydroxide with minimal quartz,
goethite and silicate minerals and were enriched in
Mn and Fe with minor Al, Ca, Na, K, Co and trace
element Li (Table 3, Fig. 5). Unlike the diagenetic
nodule samples, each layer of the hydrogenic
ferromanganese crust had very similar chemical
compositions and minerals.
There is more lithium in the nodules than in the
ferromanganese crust, and the average abundance
of lithium in the crust samples is only about 1% of
that in the diagenetic nodule samples. Lithium
concentrations in the laminations of the diagenetic
nodule samples ranged from 95.4 to 318.7 ppm
with an average of 229.1 ppm (s ¼ 80.2). In the
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Table 6
Average chemical composition of the hydrothermal marine Mn deposits
Mn (%) Fe (%) Ca (%) Mg (%) Al (%) Na (%) Li (106) K (%) Ni (%) Cu (%) Co (%)
Areas
Hydrothermal
Hydrothermal
Hydrothermal
Hydrothermal
Hydrothermal
(hot-spot volcano)a
(island-arc olcanoes)b
(backarc rift)c
(MOR rifts)d
(remnant arc)a
44.0
40.4
46.1
47.0
44.8
0.07
1.51
0.42
0.66
0.36
2.02
2.48
1.65
0.98
1.74
2.12
1.80
1.70
1.60
2.20
0.21
1.13
0.34
0.24
0.46
3.03
2.35
2.40
—
1.44
16
—
769
100
249
0.24
1.12
0.78
0.71
1.28
0.012
0.022
0.027
0.012
0.099
0.003
0.010
0.008
0.008
0.035
0.003
0.006
0.002
0.001
0.007
a
Pitcairn Is. hot spot, S. Pacific. N ¼ 10. Hodkinson et al. (1994).
Mariana arc, W. Pacific. N ¼ 5–11. Hein et al. (1987).
c
Havre rift, S. Pacific. N ¼ 24. Moorby et al. (1983).
d
Galapagos rift, EPR. Moorby and Cronan (1983).
b
Fig. 5. Mineralogy of the sample Mn-Fe-Cru-2. The sample was composed mainly of d-MnO2 and amorphous ferric oxides and
hydroxides (no peaks) with minor quartz, feldspar, goethite and chlorite. Only the XRD pattern of Mn-Fe-Cru-2 is shown, other crust
sample patterns are similar.
transitional nodule sample lithium concentration
reached 143.5 ppm, far higher than that of the
hydrogenic crust samples, which have an average of
2.27 ppm (Table 3). This feature is related closely to
the mineralogy of the two types of ferromanganese
oxides and will be discussed later.
An average of 95% of the lithium and 91% of the
Mn were extracted by 0.1 M hydroxylamine hydrochloride solution at 18 1C from the diagenetic and
transitional nodule samples. On the other hand, the
average percent of Fe and Al extracted by 0.1 M
hydroxylamine hydrochloride solution was only
2.8% and 0.4%, respectively. The average concentration of lithium present in soluble, exchangeable or
carbonate (extracted in step 1) was 56% of the total
amount of lithium, while the average value of lithium
present in manganese oxide states reached 43% of
the total amount of lithium (Table 5). Only about
0.4% (average) of the Mn was extracted in Step 1 by
acetic acid, while about 92.1% of the Mn was
extracted in Step 2. This indicates that the experiments were effective, because the Mn and Li were
separated completely from other minerals or oxides.
Each lamination of the diagenetic nodule samples
can be considered as a different nodule, and so can
each layer of the ferromanganese crust sample. This
can help us to treat the data on the basis of
statistics.
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5. Discussion
5.1. Geochemistry of lithium in the diagenetic and
transitional ferromanganese nodules
It appears that the lithium in the diagenetic and
transitional nodules was held in the manganese
oxides rather than ferric oxide or other minerals.
This is indicated by the nearly complete extraction
of lithium and manganese from the diagenetic and
transitional nodules by 0.1 M hydroxylamine hydrochloride (Table 4).
Lithiophorite (LiAl2[Mn(IV) Mn(III)]O6(HO)6)
(Post, 1999) is commonly found in weathered zones
of Mn deposits, ocean-floor manganese crust,
certain acid soils and low-temperature hydrothermal veins (De Villers, 1983; Post and Appleman,
1994). Published chemical analyses of lithiophorite
samples from a variety of localities show that the Li
content ranges from 0.2 to 3.3 oxide weight percent
(Ostwald, 1988). It is difficult to differentiate
between lithiophorite and 10 Å manganates by Xray diffraction because of the overlap of their
diffraction peaks. On the other hand, the chemical
method is available to determine whether lithiophorite is present. It is impossible for lithiophorite
to be dissolved in hydroxylamine hydrochloride
solution below 25 1C (Tokashiki et al., 2003).
Because almost all of the lithium in the nodule
samples was extracted by 0.1 M hydroxylamine
hydrochloride solution below 20 1C, it can be
concluded that the lithium was present in a phase
other than lithiophorite.
Little lithium is adsorbed by suspended particles
because of the low energy of adsorption of this
element onto clay minerals and colloidal particles
(Lebedev, 1957; Grim, 1968). This has been
confirmed by laboratory experiments that showed
that the Li concentrations of seawater samples is not
affected by even large amounts of clay (1 g/L) or
iron hydroxide (E4 mg/L) in suspension (Egli,
1979). The extremely low lithium concentration
(average 2.27 ppm (s ¼ 1.55)) in the hydrogenic
crust also reveals that d-MnO2 and ferric oxide/
hydroxide can adsorb only a very small amount of
lithium. This indicates that the lithium in the
diagenetic and transitional nodules was in close
association with the 10 Å manganates rather than
other minerals or oxides.
Todorokite shows much the same interlayer
strength as marine high-temperature hydrothermal
and metal-rich diagenetic 10 Å manganates (Usui
93
et al., 1989; Mellin and Lei, 1993). Burns et al.
(1983) summarized the observations of tunnel
structures of both terrestrial and marine 10 Å
manganates and recommended that the name
todorokite be universally adopted for the predominant marine 10 Å manganates. Lei (1996) suggested
that marine and synthetic 10 Å manganates and
terrestrial todorokite have similar tunnel structures.
As a matter of fact, buserite can be transformed into
todorokite (Shen et al., 1993). The heating experiment revealed that the 10 Å spacing of the 10 Å
manganates remained unaltered after heating at
110 1C. It appears that the initial 10 Å manganates
obtain structural stability by incorporation of
transition metals, the oxidation of Mn2+ to Mn4+
ions and the simultaneous change of OH to O2
ligands in the walls of the tunnel structure of the
10 Å manganates (Lei, 1996).
Diagenetic ferromanganese nodules enriched in
Cu, Ni and 10 Å manganates are formed from
reprecipitation of the remobilized manganese ions
from solid Mn4+ to soluble Mn2+ in the interstitial
water due to the reduced micro-environment in the
sediments where the diagenetic nodules are formed
(Dymond et al., 1984; Halbach et al., 1981;Calvert
and Price, 1977). In the structure of 10 Å manganates, ½Mn4þ O2
6 octahedral layers are orderly
stacked along the C-axis to form the ceiling or
floor of the tunnel, while the wall of the tunnel is
constructed of three edge-shared octahedral strings
constructed
by
two
[(Mn4+,
Me(2+,3+),
2+
2
Mn )O3þx ðOH Þ3x ] octahedra (0pxp3) with a
[(Mn4+, Me(2+,3+), Mn2+)O2
2x ðOH Þn2x ] unit
(n ¼ 6 or 8) (Fig. 6) (Lei, 1996). The ½Mn4þ O2
6 octahedral layers of the 10 Å manganates are bound
by hydrated interlayer cations with Van der Waal’s
forces and weak coordination links (Mellin and Lei,
1993). The tunnel is filled by water (Feng et al.,
1998; Post et al., 2003) and ions with a large radius
such as Na+, Ca2+, K2+ and Mg2+ (Lei, 1996; Post
et al., 2003; Shen et al., 1993). The magnesium ions
are located at both tunnel sites (Post et al., 2003;
Shen et al., 1993) and octahedral Mn sites (Post and
Bish, 1988; Post et al., 2003; Feng et al., 1998). The
ions Cu2+, Co2+ and Ni2+ can substitute for Mg2+
and Mn2+ in the octahedral [(Mn4+, Me(2+,3+),
4+
Mn2+)O2
, Me(2+,3+),
3þx ðOH Þ3x ] and [(Mn
2+
2
Mn )O2x ðOH Þn2x ] in the walls, resulting in
higher crystal field stabilization energy (CFSE)
and shorter coordination bonding bridges between
½Mn4þ O2
6 octahedral layers, thus enhancing the
stability of early formed 10 Å manganates (Mellin
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X. Jiang et al. / Deep-Sea Research I 54 (2007) 85–98
Fig. 6. The model for the structural frameworks of marine diagenetic 10 Å manganates (Lei, 1996) (Highly hydrated Cu2+ and Ni2+ ions
can enter the walls of the tunnel to stabilize the structure; lithium ions can fill in the tunnel to substitute to form [Li+(H2O, OH)6] and can
2þ 2
substitute for many Mg2+ ions in the walls of the tunnel in the form ½Mg2þ O2
3þx ðOH Þ3x (0pxp3) or ½Mg O2x ðOH Þn2x (n ¼ 6 or 8)
þ 2
ðOH
Þ
(0pxp3)
or
½Li
O
ðOH
Þ
(n
¼
6
or
8).
to form ½Liþ O2
3x
n2x
3þx
2x
and Lei, 1993; Martin-Barajas et al., 1991; Shen
et al., 1993).
Lithium is an alkali metal, but because of its small
ionic radius it behaves more like Mg2+ in nature. It
substitutes for Al3+, Fe2+ and especially Mg2+ in
crystal structures rather than for Na+ (Huh et al.,
1998). Li+ has the weakest sorption chemistry of all
the alkalis (Heier and Billings, 1978), and the
enrichment of lithium is considered to be due to
isomorphic substitution. Although the ionic radius of
Li+ (0.76 Å, octahedral coordination (Shannon,
1976)) is similar to that of Mn2+ (0.83 Å, octahedral
coordination (Shannon, 1976)), Li+ can’t substitute
for Mn2+ because of the valence state difference and
the different ionic configuration. In addition, the
CFSE of Li+ in octahedral coordination can be
regarded as zero and is lower than that of many
transitional ions, such as Mn2+ and Mn4+, which are
the dominant ions, and Cu2+, Co2+ and Ni2+, which
are the main substitutional transitional ions. On the
other hand, Li+ can substitute for a small amount of
Mg2+ in the wall to form ½Liþ O2
3þx ðOH Þ3x (0px
þ 2
p3) or ½Li O2x ðOH Þn2x (n ¼ 6 or 8), and this
may result in further imbalance of the charge of the
structure and enhance the absorbability of large
cations into the tunnel. It is difficult for H+ to
substitute for the Li+ ions located in the octahedral
strings, and this part of the lithium wasn’t extracted
by acetic acid solution. Of course, the amounts of the
Li+ ions in the octahedral strings vary greatly,
depending on different individual nodules and
different formation conditions, such as the number
of Mg2+ ions in the octahedral strings and the
number of Li+ ions supplied by the ocean.
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X. Jiang et al. / Deep-Sea Research I 54 (2007) 85–98
Although the ionic radius of Li+ is smaller than
those of Na+, Ca2+ and K+, all alkali metals can
enter the tunnel of the structure (Feng et al., 1998).
Lithium ions can enter the tunnel to form
[Li+(H2O, OH)6] as other metal ions such as
Na+, Ca2+, K+ and Mg2+ do. However, it is
impossible for Li+ ions to enter the tunnel without
limit because of the low concentration of lithium
in seawater (about 0.18 ppm (Stouffyn-Egli and
Machenzie, 1984; Gieskes et al., 1998)) and in pore
waters of the upper sediments on the bottom of the
oceans (Zhang et al., 1998) compared to those of
Na+, Ca2+, K+ and Mg2+. The low valence of Li+
ions is a disadvantage to the balance of the charge
of the structure, and mg2+ ions are more suitable
for the tunnel because of the high valence, which
can bring about the charge balance of the structure.
The size of the tunnel is more suitable for caitons
with large ionic radius such as Na+, Ca2+, Ba2+
and K+. The metal ions in the tunnel can be
replaced during ion exchange (Shen et al., 1993) and
can be easily extracted by acid treatment (Feng et
al., 1998). Lithium ions in the tunnels in the
octahedral [Li+(H2O, OH)6] can be extracted by
acetic acid. This part of the lithium can be regarded
as soluble or exchangeable Li in the diagenetic and
transitional ferromanganese nodules.
The interstitial water Li concentrations within the
upper 10 m of marine sediments sometimes is only
about half of the seawater value (Zhang et al., 1998;
Gieskes et al., 1998). On the other hand, Li
concentrations in the diagenetic and transitional
nodules can reach several hundreds of ppm in wt%,
and this value is one to two thousands times as large
as in the interstitial water. This indicates that the
diagenetic nodules take up Li, and this is attributed
to the incorporation capability of 10 Å manganates.
The 10 Å manganates of the diagenetic and transitional ferromanganese nodules can be regarded as
an important scavenger of lithium in the ocean.
The Li fluxes into and out of the ocean have been
estimated, and it has been concluded that the uptake
by weathered basalt is insufficient to balance the
riverine and hydrothermal inputs (Seyfried et al.,
1984; Stouffyn-Egli and Machenzie, 1984). The
maximum diffusive flux into the sediment due to
volcanic matter alteration can be no more than 5%
of the combined inputs from rivers and submarine
hydrothermal solutions (Zhang et al., 1998). It is
generally believed that the deficit is balanced by
marine sediments, possibly with authigenic clays as
the dominant sinks (Stouffyn-Egli and Machenzie,
95
1984). However, the incorporation of Li into
authigenic clay minerals from volcanic matter
alteration in the sediment column and Li adsorption
on sediments are relatively minor sinks (Zhang et
al., 1998). It seems that other sinks should be
explored. The diagenetic and transitional ferromanganese nodules may play a role in the mass balance
of lithium in the oceans.
5.2. Geochemistry of lithium in the hydrogenic
ferromanganese crust
The lithium content of the layers of the hydrogenic crust samples ranging from 5.68 to 1.25 ppm,
with an average of 2.27 ppm (s ¼ 1.55), is about 1%
of the average value of the diagenetic nodule
samples. The coefficients of correlation between Li
and Al, Mn, Fe, Si are 0.98, 0.94, 0.07 and 0.89,
respectively, indicating that there is not any
relationship between Li, Mn and Fe in the hydrogenic crust samples. The presence of Li in the
hydrogenic crust is not attributed to the d-MnO2 or
the amorphous or crystalline ferric oxide/hydroxide.
The low concentration of lithium in the crust
indicates that d-MnO2 and amorphous or crystalline
ferric oxide and hydroxide are incapable of adsorbing lithium.
Hydrogenic crusts are formed from the direct
precipitation of colloidal metal oxide of the seawater (Dymond et al., 1984; Halbach et al., 1981;
Calvert and Price, 1977) under oxic conditions
(Skornyakova and Murdmaa, 1992; De Carlo,
1991). The oxides are composed principally of dMnO2 with amorphous ferric oxide/hydroxide
(Alvarez et al., 1990; Martin-Barajas et al., 1991;
De Carlo, 1991; Dymond et al., 1984;Halbach et al.,
1981). In addition, minor quartz, feldspar, goethite
and chlorite are present in the crust samples
analysed in this paper (Fig. 4).
d-MnO2 is formed by the edge-shared ½Mn4þ O2
6 layers and is disordered in the layer-stacking
direction (Giovanoli and Arrhenius, 1988; Giovanoli, 1980) with no vacancy in the structure
(O’Connor et al., 2003; O’Connor et al., 2004).
There is no tunnel structure in d-MnO2; therefore
there is no site for Li to occupy d-MnO2 cannot
incorporate any Li+ into its structure. d-MnO2
can’t adsorb any Li+ into the structure during its
formation because of the greatly different charge,
type and radius between Li+ and Mn4+. On the
other hand, laboratory experiments have confirmed
that the Li concentration of seawater samples is not
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X. Jiang et al. / Deep-Sea Research I 54 (2007) 85–98
affected by large amounts of clay (1 g/L) or iron
hydroxide (E4 mg/L) in suspension (Egli, 1979). It
is reasonable to assume therefore, that lithium in the
hydrogenic crust is present in states other than the
iron oxide and hydroxide phases.
The high coefficients of correlation between Li
and Al (0.98) and Si (0.89) indicates that Li in the
hydrogenic crust is incorporated into certain types
of minerals enriched in Al and Si. The coefficient of
correlation between Al and Si in the hydrogenic
crust reached 0.92, indicating that Li in the
hydogenic crust may occur in an aluminosilicate
phase. In addition, the XRD peaks (Fig. 5)
probably reveal the presence of small amounts of
clay minerals despite the fact that clay and iron
hydroxide adsorb little Li in seawater (Egli, 1979).
Li is believed to substitute for Mg2+ and Fe2+ in
the octahedral site of chlorite and smectite or for Na
in zeolite (Berger et al., 1988). It can also occupy
exchangeable positions in interlayers of these layer
aluminosilicates (Berger et al., 1988). Therefore, it is
reasonable to assume that clay minerals, such as
chlorite, can to some extent adsorb a little lithium,
i.e., the lithium precipitated first in the clay minerals
and then was deposited with the manganese and
iron oxide/hydroxide in the ferromanganese crust.
This is in agreement with the coefficient of correlation between Li and Al (0.98), Si (0.89) in the
ferromanganese crust, and it is very different from
the geochemistry of lithium in the diagenetic
ferromanganese nodules. On the other hand, the
clay minerals can adsorb relatively very little lithium
(Grim, 1968), and the average concentration of
lithium in the ferromanganese crust sample is no
more than 2.27 ppm(s ¼ 1.55).
6. Summary and conclusions
Lithium shows different geochemistry in different
origin of marine ferromanganese deposits. There is
far more lithium in diagenetic and transitional
nodules than hydrogenic crust.
Lithium in diagenetic and transitional ferromanganese nodules is not in lithiophorite phase, which
bears a certain amounts of lithium according to the
result of the selective dissolution experiment. The
diagenetic and transitional nodules strongly incorporate lithium due to the presence of 10 Å
manganates, which are able to incorporate lithium
into their structure via ion exchange and substitution. Lithium enters 10 Å manganates structure to
fill in the tunnel and be present at octahedral sites in
the walls. However, 10 Å manganates cannot uptake
lithium without limit because the radius of lithium
ions is less than that of Na+, Ca2+ and Ba2+ that
are more suitable for the tunnel, and the low valence
of Li+ is a disadvantage to the charge balance of
10 Å manganates structure. The 10 Å manganates
can be regarded as an important scavenger of
lithium in the oceans. Diagenetic and transitional
nodules may play a role to some extent in mass
balance of lithium in the oceans.
Neither d-MnO2 nor iron oxide/hydroxides of
ferromanganese crust adsorbs lithium in seawater.
It appears that lithium is present in hydrogenic
marine ferromanganese crusts in an aluminosilicate
phase due to their capacity of ion exchange. The
aluminosilicates that adsorb a little lithium precipitate into the ferromanganese crust with the
manganese and iron oxide/hydroxides. However it
is very difficult to confirm the phase of the lithium in
the hydrogenic ferromanganese crust because of its
extremely low concentrations. Here we suggest the
present phases of the lithium in the hydrogenic
ferromanganese crust by the correlation between
lithium and other elements.
Acknowledgements
We thank the officers, crews and scientists of the
‘‘Haiyang IV’’ and ‘‘Dayang I’’ for exemplary
cooperation during long cruises. We also express our
appreciation to the anonymous reviewers for their
thoughtful comments. Thanks are given to Dr.
Michael P. Bacon for deliberate suggestions and
comments on my manuscript. This research was supported by the National Nature Science Foundation of
P.R. China Grant 40076015 and China Ocean
Mineral Resources R & D Association.
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