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The effect of Fe-Mn minerals and seawater interface and enrichment mechanism of ore-forming elements of polymetallic crusts and nodules from the South China Sea
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Yao GUAN1, 2, Xiaoming SUN1, 2, 3, 4, *, Xiaodong JIANG3, Rina SA3, Li ZHOU1, 2, Yi HUANG3, Yating LIU1, 2, Xiaojie LI1, 2, Rongfei LU1, 2, Chi WANG1, 2
Acta Oceanologica Sinica | 2017, 36(6) : 34 - 46
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Acta Oceanologica Sinica | 2017, 36(6): 34-46
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The effect of Fe-Mn minerals and seawater interface and enrichment mechanism of ore-forming elements of polymetallic crusts and nodules from the South China Sea
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Yao GUAN1, 2, Xiaoming SUN1, 2, 3, 4, *, Xiaodong JIANG3, Rina SA3, Li ZHOU1, 2, Yi HUANG3, Yating LIU1, 2, Xiaojie LI1, 2, Rongfei LU1, 2, Chi WANG1, 2
Affiliations
  • 1 School of Marine Sciences, Sun Yat-sen University, Guangzhou 510006, China
  • 2 Guangdong Provincial Key Laboratory of Marine Resources and Coastal Engineering, Guangzhou 510006, China
  • 3 School of Earth Sciences and Geological Engineering, Sun Yat-sen University, Guangzhou 510275, China
  • 4 State Key Laboratory for Mineral Deposits Research, Nanjing University, Nanjing 210046, China
Published: 2017-02-01 doi: 10.1007/s13131-017-1004-4
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Ferromanganese crusts and nodules are important submarine mineral resources that contain various metal elements with significant economic value. In this study, polymetallic crusts and nodules obtained from the South China Sea (SCS) were determined by using X-ray power diffraction (XRD), Raman spectroscopy (RS), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS) to systematically investigate and analyze the mineralogical and spectral characteristics of the Fe-Mn minerals. XRD measurements revealed that the SCS polymetallic crusts and nodules were composed of vernadite, quartz, and plagioclase. The nodules also contained todorokite. The Fe-phase minerals of the SCS crusts and nodules were composed of amorphous Fe oxide/hydroxide, and the Mn- and Fe-phases minerals exhibited relatively poor degrees of crystallization. FTIR results showed that the Fe-Mn minerals in the crusts and nodules included a large number of surface hydroxyl groups. These surface hydroxyl groups contained protons that could provide reactive sites for complexation of ore-forming elements in seawater. XPS results indicated that the surfaces of the Fe-Mn minerals mainly contained Fe, Mn, and O. Fe was present in the trivalent oxidation state, while Mn, which may contain several bivalent oxidation state, was present in the tetravalent and trivalent oxidation states. The SCS polymetallic crusts and nodules were compared with Pacific seamount crusts, and results showed that the surface hydroxyl (-OH) groups of the SCS crusts and nodules numbered more than the lattice oxygen (O2-). But the lattice oxygen of Pacific seamount crusts numbered more than the surface hydroxyl groups. This characteristic indicated that the degree of crystallization of Fe-Mn minerals from the Pacific Ocean was higher than that of minerals from the South China Sea. Comprehensive studies showed that ore-forming elements in the interface between seawater and the Fe-Mn minerals in the submarine ferromanganese crusts and nodules employed the following enrichment mechanisms: (1) the metal ion complexed with the surface hydroxyl of Fe-Mn minerals to form hydroxyl complexes, which were connected by coordination bonds or stable inner-sphere complexes that exchanged protons on the mineral surfaces; (2) the charged surfaces of the minerals and metal cations formed outer-sphere complexes, which made up the electrostatic double layer, through electrostatic adsorption; and (3) the metal cations isomorphously exchanged the Mn and Fe ions of the mineral lattice structure.

polymetallic crust and nodule  /  mineralogy characteristic  /  interface effect  /  element enrichment  /  surface complexation
Yao GUAN, Xiaoming SUN, Xiaodong JIANG, Rina SA, Li ZHOU, Yi HUANG, Yating LIU, Xiaojie LI, Rongfei LU, Chi WANG. The effect of Fe-Mn minerals and seawater interface and enrichment mechanism of ore-forming elements of polymetallic crusts and nodules from the South China Sea[J]. Acta Oceanologica Sinica, 2017 , 36 (6) : 34 -46 . DOI: 10.1007/s13131-017-1004-4
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1 Introduction
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Seafloor ferromanganese crusts and nodules are important mineral resources. These seafloor features are concentrated with an abundance of metal elements, such as Mn, Co, Cu, Ni, Mo, Te, rare earth elements (REE), and platinum group elements (PGE). China, along with many other countries has investigated the seabed ferromanganese crusts and nodules of the world’s oceans (He et al., 2011a), and the genesis of these sea features has been extensively discussed (Xue, 2007; He et al., 2011b; Hein and Koschinsky, 2014; Hein et al., 2015; Guan et al., 2017). While the pronounced degree of enrichment of ore-forming elements in seafloor crusts and nodules is of great interest, the enrichment mechanism of these elements in ferromanganese crusts and nodules has not yet been well elucidated. Hein et al. (2000) and Kuhn et al. (1998) suggested that the obvious enrichment of some trace elements in hydrogenetic ferromanganese minerals is related to their slow growth rates, thereby implying a time-dependent enrichment process. Several studies have indicated that the enrichment of many redox-sensitive metals is due to redox reactions occurring through uptake of Fe-Mn mineral phases during their formation. Surface oxidation during adsorption on the Fe-Mn mineral phases has been suggested for Pt (Halbach et al., 1989), and the pronounced enrichment of Te in the ferromanganese crusts and nodules has been explained by the surface oxidation mechanism (Hein et al., 2003), as well as Tl (Bidoglio et al., 1993). And other studies have suggested that the Fe-Mn colloids can strongly and effectively adsorb ore-forming elements dissolved in seawater, such as Co, Ni, Cu, Zn, Mo, and REE. Ferrihydrite was found to be the most effective scavenger of Mo from seawater (Koschinsky et al., 2003), and REE are adsorbed by Fe-Mn colloids (Bau et al., 1996; Jiang et al., 2011).
Many interface reactions, such as surface adsorption, redox reactions, and surface ectopic catalytic reactions, occur between Fe-Mn minerals and seawater (Hochella, 1990; Stumm, 1992). Surface adsorption and complexation, as well as redox reactions, are the main mechanism through which Fe-Mn minerals accumulate metal cations. Previous studies have mainly discussed the degree of enrichment of various metal elements using phase separation and sequential leaching experiments, and enrichment models of surface adsorption and complexation have been established (Koschinsky and Halbach, 1995; Koschinsky and Hein, 2003; Jiang et al., 2011). However, the original interface of the metallogenic processes in the interface of Fe-Mn minerals and seawater should be considered to determine the enrichment mechanism of ore-forming elements in ferromanganese crusts and nodules as aquatic minerals. The geochemical properties of the mineral surface are closely related to the mineral type, crystal structure, surface structure, and micromorphology. Trace elements exist in seawater systems as dissolved ions, inorganic complexes, and organic coordination polymers. The geochemical behavior of the trace elements is controlled by the reactions of a variety of solutes on the solid particle surface. Therefore, this article focuses on the systematic analysis of the mineralogy and interface effects between Fe-Mn minerals and seawater using X-ray diffraction (XRD), Raman spectroscopy (RS), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). The crystal structure and surface chemical properties of the Fe-Mn minerals were analyzed and discussed to reveal the relationship between Fe-Mn minerals and the seawater interface and the enrichment mechanism of the ore-forming elements.
2 Experiments
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2.1 Samples
The samples studied in this paper were dredged from regional surveys of the Zhongjian Islands, Zhongsha Islands, Huangyan Islands and Shantou areas in the South China Sea in 2011 and 2012 by R/V Haiyangsihao of the Guangzhou Marine Geological Survey (Fig. 1 and Table 1). Sampling depths ranged from 800 m to 2 300 m. All Fe-Mn layers presented as single layers, and the samples were classified as ferromanganese crusts and ferromanganese nodules based on their morphological structures and sedimentary environments. Two seamount ferromanganese crusts from the West Pacific Ocean were also examined for comparison to enhance the analytical results of this study. The two Pacific seamount crusts were obtained from the DY105-13 voyage survey by R/V Haiyangsihao. The Fe-Mn minerals of the crusts and nodules were directly analyzed.
2.2 Instruments and parameters
XRD: Mineralogical compositions were determined by XRD. This analysis, along with other spectroscopic techniques, was conducted at the Instrumental Analysis and Research Center in Sun Yat-sen University. Bulk XRD analyses were conducted at 40 kV and 150 mA to record diffraction patterns at 2θ ranging from 3° to 90°. The divergence and scattering slits were both 1°, and the receiving slit was 0.3 mm. The step length was 0.02°, and X-ray wavelength λ was 1.541 78 Å. XRD with Ni-filtered CuKα radiation was conducted at a scan speed of 3°/min (2θ).
RS: Raman spectral analysis was performed using a microscopic confocal Raman spectrometer. The clear surfaces of the samples were directly analyzed, and Renishaw InVia was used to record the Raman spectra. The spectrum excitation wavelength was 785 nm, and the best spectral resolution was 1 cm–1. The scanning range was from 50 cm–1 to 2 000 cm–1.
FTIR: The KBr powder tablet samples were tested, using a Nicolet6700 Contiuμm (Thermo Scientific). Wave numbers ranged from 4 000 cm–1 to 400 cm–1, and the spectral resolution was better than 0.09 cm–1. A DTGS detector and a KBr beam splitter were used.
XPS: X-ray photoelectron spectra were recorded using an ESCALAB 250 system (Thermo Fisher Scientific). The vacuum worked at –2×10–9 mbar (under the condition of an open X-ray source), and the X-ray source of monochromatic Al Kα had energies of 1 486.6 eV, 15 kV, and 150 W. The beam spot size was 500 μm, and the scanning mode was CAE. The lens mode was large area XL. Qualitative and quantitative analyses were performed using the Wagner (Al target) Library. Full spectrum scanning was conducted with energy of 100 eV and energy step size of 1 eV/step. Narrow spectrum scanning was conducted with an energy of 20 eV and energy step size of 0.05 eV/step. C1s (284.8 eV) was used as the standard for energy correction (energy scale).
3 Results
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3.1 XRD
XRD results show that the diffraction curves of the SCS polymetallic crusts and nodules were consistent (Fig. 2). The minerals of the SCS polymetallic crusts were composed of vernadite (δ-MnO2), quartz, and feldspar, while the polymetallic nodules contained todorokite, vernadite, quartz, and feldspar. No obvious diffraction peaks of clay minerals and Fe-phase minerals were observed, probably because the crystallinity of the Fe oxides/hydroxides (amorphous ferrihydrite) was very poor or these minerals existed in disperse phases (Shi et al., 1995).
3.2 RS
Micro RS can nondestructively analyze the molecular compositions, molecular groups, and crystal structures of minerals. The Raman and standard mineral spectra are shown in Fig. 3. Combined with our XRD results and a previous study (Little et al., 2014), the present results show that the peak should correspond to the crystal lattice vibration of the Mn-O bond with a relatively low bond energy. The main mineral phase was close to a disordered hexagonal birnessite, i.e., δ-MnO2, which is a mineral unit that forms a sheet (layer)-like stack at the edge of the [MnO6] octahedron. A lattice vacancy exists in every six [MnO6] octahedrons in layered structure because of the presence of Mn(Ⅲ) in the [MnO6] octahedron. The negative charge of the entire octahedral layer is due to this lattice vacancy and the charge is compensated by cations and/or protons between layers through electrostatic interactions (Drits et al., 1997). The peak Raman spectral positions of the Fe-phase reference minerals mainly appeared at wave numbers below 500 cm–1. The main peak position of goethite appeared near 386 cm–1. However, no obvious peak was observed in the range from 0 to 500 cm–1, which indicates that the bond strength of Fe-O in the Fe-phase minerals is very weak. Therefore, the degree of crystallization the Fe-phase minerals in the SCS polymetallic crusts and nodules was very poor. The SCS polymetallic crusts and nodules were mainly amorphous Fe oxides/hydroxides.
3.3 FTIR spectroscopy
The FTIR spectra of the SCS polymetallic crusts and nodules are shown in Figs 4 and 5. The FTIR spectra of the two features were identical and showed minimal differences. Absorption peaks at 3 377–3 388 cm–1 indicated -OH stretching vibration. These vibrations could be attributed to free hydroxyl groups and hydration of the Fe-Mn mineral surfaces. H-O-H bending vibrations, which are attributed to the adsorptive H2O molecule (Russell, 1979), were evidenced by a peak at 1 630 cm–1. The vibration absorption peaks of Fe/Mn oxides/hydroxides were different from those of hydrate-hydroxyl groups. The former mainly appeared in the fingerprint zone of the spectra. The absorption peaks of Mn(Ⅲ)-OH vibrations were found in 1 078–1 086 cm–1. The surface hydroxyl (Mn-OH) group of δ-MnO2 showed peaks at 1 032–1 038 cm–1 (Nakamoto, 1978; Liu et al., 2009). The stretching vibrations of Mn-O-Mn, which confirmed the existence of [MnO6] cell, were evidenced by a peak at 694 cm–1 (Naidja et al., 2002). The stretching vibrations of Fe-O-Fe and Fe-OH were evidenced as peaks at 471 cm–1 and 775–798 cm–1, respectively (Singh et al., 2000). However, the peak of the bending vibrations of the Fe-OH-Fe surface hydroxyl of goethite, i.e., at 890 cm–1 (Liao et al., 2006), was not identified in the spectra, probably because of the presence of numerous surface hydrogen bonds (Fe-OH), which weakened the bond strength of Fe-OH-Fe.
3.4 XPS
The full X-ray photoelectron spectra of the SCS polymetallic crusts and nodules are shown in Fig. 6. Two seamount crusts from the Western Pacific Ocean were also analyzed for comparison, and the spectra of these crusts are shown in Fig. 7. Table 2 lists the atomic percentage compositions of the main elements of the mineral surfaces. The results revealed that all of the mineral surfaces in the SCS polymetallic crusts and nodules, as well as those of the Pacific seamount crusts, were mainly composed of Fe, Mn, and O. The mineral surfaces of the SCS crusts and nodules had lower Mn contents but much higher Si, Al, and Ca contents than those of the Pacific seamount crusts. Si, Al, and Ca on the mineral surfaces represented detrital mineral components. This characteristic indicates that the SCS polymetallic crusts and nodules were strongly affected by the epicontinental environment, and they exhibited the sedimentary characteristics of marginal sea. Therefore, the fitting spectra of the element narrow spectra for the major elements Fe, Mn, and O on the mineral surfaces were analyzed. Moreover, the chemical valence states and structural patterns of the major elements in the samples were determined.
The O1s spectra of the Fe-Mn mineral surfaces of samples from the South China Sea and Pacific Ocean are shown in Fig. 8. The peak positions of the O1s spectra presented abnormal distributions. The SCS polymetallic crusts and nodules revealed a sharp main peak in the vicinity of 530.01–532.09 eV with a wide shoulder peak on the right side. Some individual samples demonstrated relatively sharp shoulder peaks. However, the Pacific seamount crusts showed main peaks at around 529.94–529.89 eV with a wide shoulder peak on the left side. These findings suggest that the oxygen exhibited different chemical states on the surfaces of the Fe-Mn minerals, and the main chemical state of surface oxygen in the SCS polymetallic crusts and nodules differed from that of the Pacific Ocean. Previous studies (Knipe et al., 1995; Pratt et al., 1994; Kloprogge et al., 2006) have shown that oxygen has three chemical states namely, lattice oxygen (O2–), hydroxyl (-OH), and hydration oxygen (H2O). These states correspond to Mn/Fe-O, Mn/Fe-OH, and H-O-H with electron binding energy values of 530, 531, and 533 eV, respectively. The fitting spectra of O1s (Fig. 9) show that the SCS polymetallic crusts and nodules contained a significant amount of hydroxyl (-OH) groups, whereas the Pacific seamount crusts primarily contained lattice oxygen (O2–). This finding indicates that the degree of crystallization of the Fe-Mn minerals of the Pacific seamount crusts was higher than that of minerals from the South China Sea. The hydroxyl (-OH) groups of the mineral surfaces could provide adsorption sites for dissolved metal cations and complex ions in the seawater and release H+ or hydrated ions during adsorption (Tamura et al., 2001).
The Fe2p spectra of the Fe-Mn mineral surfaces of samples from the South China Sea and Pacific Ocean are shown in Fig. 10. Two obvious peaks of Fe2p were detected at 705–740 eV, including the peak of Fe2p1/2 on the left and the peak of Fe2p3/2 on the right. The results show that the binding energies and peak strengths of Fe2p of the crusts and nodules surfaces from the South China Sea and the Pacific Ocean are consistent. The binding energy of Fe2p1/2 was between 724.9 and 725.6 eV, whereas that of Fe2p3/2 was between 711.01 and 712.46 eV. Fe2p1/2 and Fe2p3/2 had higher binding energies than Fe2p1/2 and Fe2p3/2 of Fe2O3, respectively (Mathieu and Landolt, 1986; Tan et al., 1991). This phenomenon is probably due to the higher binding energy of the Fe and -OH combination than the Fe and O2– combination. This characteristic suggests that Fe exists with a +3 valence in Fe-phase minerals from the South China Sea and Pacific Ocean. Furthermore, according to crystal field energy theory, the occurrence of Fe in a very weak crystal condition implies that the Fe of the mineral phase surfaces mainly combines with the hydroxyl group.
The Mn2p spectra of the Fe-Mn mineral surfaces of samples from the South China Sea and Pacific Ocean are shown in Fig. 11. The binding energy and peak strength of Mn2p of the Fe-Mn mineral surfaces from the South China Sea were similar to those in the Pacific Ocean in the range of 635–660 eV. This result suggests that the chemical states of Mn on the mineral surfaces of the crusts and nodules were consistent. Mn2p was split into a main peak of Mn2p3/2 at 642.43–643.06 eV because of spin angular momentum coupling (Fig. 11). The peak of Mn2p1/2 was appeared at approximately 654 eV, and the peak shapes of Mn2p showed abnormal distributions. The Mn of the mineral surfaces presents various chemical states. We fit only the peak positions of Mn2p3/2 because of the mutually corresponding relationship between Mn2p3/2 and Mn2p1/2. The fitting spectra are shown in Fig. 12. The peak positions of the standard binding energy of various chemical states of Mn were located at 640.3–641.1, 641.3–641.7, and 641.7–642.2 eV, which corresponded to Mn2+, Mn3+, and Mn4+. Figure 12 shows that the Mn chemical states of the Mn-bearing mineral phases are mainly Mn (IV) and Mn (III). These results are consistent with the results from synchrotron radiation X-ray generated photo emission electron microscopy (Xue, 2007). Nevertheless, irradiation may cause reductions in the chemical state of Mn during the test process (Garvie and Craven, 1994), but the possibility of the existence of Mn (II) cannot be ruled out. Mn (II) and Mn (III) may exist in the octahedral vacancy and maintain the stability of the mineral crystal structure through electrostatic interactions (Friedrich and Schmitz-Wiechowski, 1980).
4 Discussion
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4.1 Mineral crystallization characteristics
The XRD results reveal evident diffraction peaks of quartz and feldspar in the SCS polymetallic crusts and nodules. The diffraction peaks of vernadite and todorokite, which are the main Mn-phase minerals, were not sharp, but the peaks were wide and gradual, which indicates that the crystallinities of vernadite and todorokite were relatively poor. Moreover, comparative results of the diffraction curves of the polymetallic crusts and nodules show that the crystallinity of vernadite in the nodules was better than that in the crusts in the South China Sea.
The higher the degree of mineral crystallization, the stronger the bond between elements of groups, and the more likely the Raman spectra will show a peak with small half height-width ratio. Previous studies (Chukhrov et al., 1979; Potter and Rossman, 1979) have indicated that only high-order crystal-structured Mn-phase minerals show evident infrared (IR) spectra characteristics. Mn minerals with different degrees of crystallization show different IR spectral characteristics. This difference can be proven mainly by the quantities of the absorption peak and the ratio of half-peak width and peak height. Therefore, the degree of mineral crystallization of polymetallic crusts and nodules from the South China Sea were very low in the Raman spectra and IR spectra.
The particle size under weak crystallization conditions can strongly influence the surface energy and surface properties of minerals. When the diameter of mineral particles is below 1 nm, the ratio of atomic number of mineral surfaces exceeds 90% (Wang et al., 2003) and nearly all of the atoms are distributed on the surfaces of the nanoparticles. Such a high specific surface area leads to a rapid increase in the atomic number of mineral surfaces and surface energy of minerals. The atomic coordination number of mineral surfaces is insufficient. This phenomenon causes the mineral surfaces to bear very high and unstable chemical activities. The surface atoms of minerals easily bond with other ions (Xue, 2007). Both vernadite and amorphous ferrihydrite have very high specific active surface areas, which are 206 m2/g for δ-MnO2 (Yao and Millero, 1996) and approximately 200–300 m2/g for amorphous ferrihydrite (Dzombak and Morel, 1990). The activity of surface atoms of nanoparticles not only changes the surface atomic configuration of the minerals, but also alters the electron spin conformation and electronic energy spectrum of mineral surfaces (Cao et al., 1999).
Therefore, the presence of amorphous Fe-Mn minerals, which exhibits a pronounced specific surface area and unique nanopores, strengthens the surface energy of these weak crystallization minerals. This characteristic facilitates the occurrence of the interfacial effect between Fe-Mn minerals and seawater.
4.2 Mineral structure and surface characteristics
XPS results reveal that the main chemical states of Mn on the Mn-phase mineral surface of the crusts and nodules from the South China Sea and Pacific Ocean were in tetravalent and trivalent states, and may contain a small amount of the divalent state. The crystal chemistry of Mn is influenced by the split of the d orbit in the crystal field, so high-spin state Mn ions present overwhelming superiority. High-spin Mn4+, Mn3+, and Mn2+ require crystal field stabilization energies of 12, 6, and 0 dq, respectively, during their octahedral coordination. These ions usually coordinate octahedrally with O2–, OH–, and H2O, but Mn3+ and Mn2+ also present tetrahedron coordination (Xue, 2007). The Mn oxides, which were the main Mn-phase minerals of ferromanganese crusts and nodules, can form surface hydroxylation with water molecules. These hydroxyl sites mainly exist in the forms of Mn-OH2+, Mn-OH, and Mn-O–, and these forms can reciprocally transform in the following reactions:
$\text{Mn-OH}^{2 + }\rightleftarrows \text{Mn-OH+}{\rm H^ + },\\ \text{Mn-OH} \rightleftarrows \text{Mn-}{\rm O^ - } + \text{H}^ +. $
The XPS results further show that Fe in the Fe-phase minerals of the crusts and nodules presents in the form of a trivalent ionic bond, similar to that in amorphous goethite and/or lepidocrocite. The surface of goethite exhibits four kinds of surface hydroxyls (Sposito, 1984). Three of these hydroxyl sites are oxo(hydroxo), μ-oxo(μ-hydroxo), and μ3-oxo(μ3-hydroxo), which are named according to the IUPAC rules and structural characteristics. These sites are bonded with 1, 2, and 3 Fe(III) ions, respectively. The fourth hydroxyl site is the Lewis acid, wherein the Fe(III) in the mineral surface shares an electron pair with the -OH in the water molecule. Fe-OH and Fe-OH-Fe in the lattice structure of goethite have their own surface activities because the coordination conditions of the hydroxyl-oxygen vary. The former has a greater hydroxyl chemical activity and higher electronegativity than the latter. Thus, Fe-OH is easier to react with metal cations than Fe-OH-Fe (Xiong and Chen, 1990).
The Fe-Mn minerals of the polymetallic crusts and nodules in the South China Sea are mainly composed of δ-MnO2, todorokite, and amorphous Fe oxides/hydroxides. The XRD and Raman spectral results confirmed the presence of octahedral [MnO6] unit cell in the Mn phase minerals of the SCS crusts and nodules. The IR spectra further showed the chemical bonds of Mn and Fe on the mineral surfaces with O2– and OH–, respectively. These Fe-Mn minerals belong to the hydroxide mineral group, which presents surface functional groups containing protons. Thus, Fe-Mn minerals could provide an abundant of active sites for complexation of ore-forming elements. The functional groups of mineral surfaces are the basic units of reaction during mineralization complexation.
4.3 Interface effect and element enrichment
The surface properties of the SCS polymetallic crusts and nodules were analyzed, and results showed that the surface active sites of the Fe-Mn minerals were the hydroxyl groups. The specific surface area and the nanopore of the Fe-Mn minerals resulted in stronger surface free energy and activity. Moreover, the minerals also increased the bearing capacity and adsorption ability of ions and complex molecules. Many physical and chemical reactions, such as adsorption and exchange of ions, electric potential transfer, and mineral precipitation and solution, occur on mineral surfaces, and the effect of the surface/interface plays the most important role in these reactions. However, the surface effect is closely related to the surface structure and surface groups of minerals. The surface groups of minerals control the chemical activity and reaction mechanism of mineral surfaces (Liu et al., 2001). Therefore, Fe-Mn mineral surfaces could be produced in subsequent complexation reactions between the hydroxyl groups of mineral surfaces and ore-forming elements in seawater.
4.3.1 Interface inner-sphere complexation
The functional groups of the mineral surface are the basic units of minerals during participated complexation. Functional groups are the core of surface complexation theory. These groups not only affect the free energy of the complexation reactions between the dissolved state and surface functional groups but also control the chemical measurement of the adsorption reaction and adsorption as well as changes in solution chemical properties (Wei and Wu, 2000). The mineral surface reaction refers to the reaction of mineral surface groups. The types and properties of surface groups vary according to the types of minerals present. A mineral with different crystal surfaces may have diverse surface group properties. The Fe-Mn minerals of the SCS polymetallic crusts and nodules are composed of δ-MnO2, amorphous Fe oxides/hydroxides (goethite, lepidocrocite), and todorokite (nodules content). These Fe-Mn minerals are hydroxide minerals, which have surface functional groups containing protons. Surface hydroxyls are the main complexation site. Various types of hydroxyl groups are found on the mineral surface, and different surface hydroxyl groups have distinct reactivities (Davis and Kent, 1990; Hiemstra et al., 1989a, b). Of these, the oxo(hydroxo) site is the most active, and can easily interact with metal cations and complexes in the surface reactions of goethite. Thus, the oxo(hydroxo) site could be highly effective for complexation enrichment of metal cations in seawater. When the surface hydroxy (-O–) of the Fe-Mn minerals directly bonds with metal cations or complexes in seawater to generate specific adsorption, the enrichment mechanism of ore-forming elements is inner-sphere complexation (Fig. 13a), which bonds with the inner orbit. The reaction of inner-sphere complexes is as follows:
${{\rm{M}}_{{\rm{Fe\text{-}Mn}}}}{\rm{\text{-}OH + Me}}\left( {{\rm{OH}}} \right)_x^ - \to {{\rm{M}}_{{\rm{Fe\text{-}Mn}}}}{\rm{\text{-}O\text{-}Me}}\left( {{\rm{OH}}} \right)_{x - 1}^ - + {{\rm{H}}_{\rm{2}}}{\rm{O}}{\rm{.}}$
For instance, similar to some highly charged ions, such as Sb5+, and easily hydrolyzed elements, such as Ti and Th, incorporation of Zr, Hf, Nb, and Ta are suggested to occur by the initial formation of inner-sphere surface complexes, followed by surface precipitation of specific hydroxide compounds as solid solutions with the original solid (Farley et al., 1985; Mitsunobu et al., 2006), as well as some transition elements, such as Cu2+ (Motschi, 1987). W species can form inner-shpere complexes with the hexavalent state on the ferrihydrite and Mn oxides (Kashiwabara et al., 2013).
4.3.2 Interface outer-sphere complexation
Various types of metal cations and complexes in seawater have distinct chemical properties, so Fe-Mn (hydro)oxides have adsorption characteristics and complexation mechanism that may differ from those of other ions and particles. Some metal cations with great hydrated ionic radii generate nonspecific adsorption during uptake onto the surfaces of the Fe-Mn (hydro)oxides (Feng, 2004). Another enrichment mechanism of ore-forming elements in the interface of Fe-Mn minerals and seawater is outer-sphere complexation (Fig. 13b), through which adsorption occurs by the electronegativity of the outer unoccupied orbital ligand.
The Mn and Fe oxides in seawater can form hydrated ions with large surface electrostatic adsorption capacity. The surface energy (charged surface) of Fe-Mn minerals is caused by the adsorption and desorption of H+ and OH– ions from mineral surface groups such as -O, -OH, and -OH2. The charged surface of the Fe-Mn oxides/hydroxides in seawater can form an electric double layer by interacting with diverse charged ions. The surface hydroxyl groups of oxides under certain pH conditions can ionize and function as Bronsted and Lewis acids. The acidity of these groups depends on the distance of the surface hydroxyl groups from the central Fe/Mn ions and is influenced by the strength of the interface electrostatic field (Xue, 2007). Previous studies have shown that the pHpzc (pzc means the point of zero charge) of Mn oxides is 2–4 (Tonkin et al., 2004). The pHpzc of deep-sea manganese nodules is 4.5 (Parida and Mohanty, 1998), while that of vernadite in the crusts is 2.8 (Stumm and Morgan, 1996). By contrast, the pHpzc of amorphous Fe hydroxide [Fe(OH)3] is 8.5 (Stumm, 1992). Therefore, Mn oxides have a negative charge, and amorphous Fe hydroxides have a weak positive charge in seawater (pH 8.0). When the surface charge of the Fe/Mn oxides/hydroxides is neutralized because of adsorption of charged ions, electrostatic repulsion among the particles of mineral surfaces disappears and the particles condense to form outer-sphere complexes. Positively charged species, such as free cations (e.g., Ni2+, Co2+, Zn2+, and Pb2+), and complexes, such as YCO3+ and LREE(OH)2+, are electrostatically attracted by strongly negatively charged Mn oxide phases. By contrast, negatively charged species of AsO43–, PO43–, MoO42–, and HREE(CO3)2–, as well as uncharged /neutral complexes, such as SiO2·nH2O, Al(OH)·H2O, and Ti(OH)40, tend to bind to slightly positively charged FeOOH phases (Koschinsky and Halbach, 1995; Koschinsky and Hein, 2003). Mo is a very interesting element. Mo species that could be adsorbed on the surface of ferrihydrite present a tetrahedrally coordinated outer-sphere complex, while that on Mn oxides was an octahedrally coordinated inner-sphere complex (Kashiwabara et al., 2009, 2011).
4.3.3 Ion exchange
Similar to zeolite minerals, Mn-phase minerals exhibit molecular sieve effects because of their unique interlayer structure and channel structure. In addition to the two surface complexation models of occupant metal cations at the Fe-Mn mineral surfaces, metal cations occupy the interlayer of water molecules in parallel. These species are primarily alkali metals and alkaline earth metals, such as Mg2+, Ca2+, Ba2+, Na+, and K+ (Fig. 13c; Golden et al., 1987; Mellin and Lei, 1993; Feng et al., 1995, 1999). Metal cations, such as Zn2+, Cu2+, and Ni2+, occupy [MnO6] octahedron vacancies (Feng et al., 1999). Many redox-sensitive metals, such as Co and Ce, can participate in redox reactions at the mineral surfaces during uptake onto Fe-Mn oxide/hydroxide minerals. Moffett and Ho (1996) found that Co presents a positive correlation with Mn in seawater. XANES and XPEEM analytical results indicated that Co has a valence of +3 in natural Mn oxides (Manceau et al., 1992; Xue, 2007). XPS results also showed that Co3+ is present in the surface of birnessite, which adsorbs Co2+ (Burns, 1976). The adsorptive Co2+ may be oxidized to Co3+ by Mn3+ in the crystal lattices of Mn minerals (Murray and Dillard, 1979; Manceau and Charlet, 1992; Xue, 2007). Therefore, the adsorption and oxidation reactions of Co may mainly occur on the surfaces of Mn oxide minerals. These reactions are the main mechanisms that take place during the concentration of Co into Mn oxide minerals. However, the ionic radius of the Co3+ (0.63 Å) is very close to that of Mn4+ (0.62 Å), and Co3+ can isomorphously substitute the Mn4+ in the [MnO6] octahedron such that Co3+ can balance the charge and stabilize the resultant structure (Burns, 1976; Fig. 13c). Therefore, ion exchange of Co3+ and Mn4+ is one pathway of uptake onto the Mn mineral phase.
5 Conclusions
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Many interface reactions, such as surface adsorption, redox reaction, and surface ectopic catalytic reaction, occur between Fe-Mn minerals and seawater (Hochella, 1990; Stumm, 1992). The surface reactions of minerals can be further divided into surface adsorption and complexation, ion exchange, surface eutectic, redox reaction, and catalytic reaction. According to the reaction model, Fe-Mn mineral surfaces possess numerous active sites of hydroxyl groups with protons, because of the unique interlayer and nanopore structure of these minerals in the crusts and nodules. Thus, surface adsorption and complexation, as well as redox reactions are the main pathways by which minerals accumulate metal cations. Therefore, the ore-forming elements in the interface of seawater and the Fe-Mn minerals in the submarine ferromanganese crusts and nodules employ the following enrichment mechanisms. First, the metal ion complexes with the surface hydroxyl groups of Fe-Mn minerals to form hydroxyl complexes, which are connected by coordination bonds or stable inner-sphere complexes that exchange protons on the colloid surfaces. Second, the charged surfaces of the minerals and metal cations form outer-sphere complexes, which make up the electrostatic double layer, through electrostatic interaction. Finally, the metal cations isomorphously exchange the Mn and Fe ions of the mineral lattice structure.
Acknowledgements
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The authors thank the Guangzhou Marine Geological Survey for supplying the samples and two anonymous reviewers for their professional comments that improved this manuscript.
Funding
Less
  • The National Natural Science Foundation of China under contract Nos 40473024 and 40343019; the research fund from State Key Laboratory for Mineral Deposits Research in Nanjing University under contract No. 20-15-07; the Investigation and Development of Marine Resources during the 12th Five Year Plan Project under contract No. DY125-13-R-05; the Doctoral Program of Higher Education Research Fund under contract Nos 20040558049 and 20120171130005; the Project of High Level Talents in Colleges of Guangdong Province (2011) and the Fundamental Research Funds for Central Universities under contract Nos 16lgjc11, 12lgjc05 and 09lgpy09.
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Year 2017 volume 36 Issue 6
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Article Info
doi: 10.1007/s13131-017-1004-4
  • Receive Date：2016-02-16
  • Online Date：2026-04-14
  • Published：2017-02-01
Article Data
Affiliations
History
  • Received：2016-02-16
  • Accepted：2016-04-18
Funding
The National Natural Science Foundation of China under contract Nos 40473024 and 40343019; the research fund from State Key Laboratory for Mineral Deposits Research in Nanjing University under contract No. 20-15-07; the Investigation and Development of Marine Resources during the 12th Five Year Plan Project under contract No. DY125-13-R-05; the Doctoral Program of Higher Education Research Fund under contract Nos 20040558049 and 20120171130005; the Project of High Level Talents in Colleges of Guangdong Province (2011) and the Fundamental Research Funds for Central Universities under contract Nos 16lgjc11, 12lgjc05 and 09lgpy09.
Affiliations
    1 School of Marine Sciences, Sun Yat-sen University, Guangzhou 510006, China
    2 Guangdong Provincial Key Laboratory of Marine Resources and Coastal Engineering, Guangzhou 510006, China
    3 School of Earth Sciences and Geological Engineering, Sun Yat-sen University, Guangzhou 510275, China
    4 State Key Laboratory for Mineral Deposits Research, Nanjing University, Nanjing 210046, China

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表12种不同金属材料的力学参数
科
Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
Genus		 种数
Number of
species		 占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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