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Frontiers of Materials Science

ISSN 2095-025X

ISSN 2095-0268(Online)

CN 11-5985/TB

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Front Mater Sci    0, Vol. Issue () : 97-115    https://doi.org/10.1007/s11706-012-0164-6
REVIEW ARTICLE
From nanoparticles via microtemplates and milliparticles to deep-sea nodules: biogenically driven mineral formation
Xiao-Hong WANG1(), Ute SCHLO?MACHER2, Shun-Feng WANG1, Heinz C. SCHR?DER2, Matthias WIENS2, Renato BATEL3, Werner E. G. MüLLER2()
1. National Research Center for Geoanalysis, Chinese Academy of Geological Sciences, 26 Baiwanzhuang Dajie, Beijing 100037, China; 2. ERC Advanced Grant Research Group at the Institute for Physiological Chemistry, University Medical Center of the Johannes Gutenberg University Mainz, Duesbergweg 6, D-55128 Mainz, Germany; 3. Ru?er Bo?kovi? Institute, Center for Marine Research, Giordano Paliaga 5, HR-52210 Rovinj, Croatia
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Abstract

Deep-sea minerals in polymetallic nodules and seamount Co-rich crusts are not only formed by mineralization but also by biologically driven processes involving microorganisms (biomineralization). Within the polymetallic nodules, free-living and biofilm-forming bacteria provide the matrix for manganese deposition, and in seamount Co-rich crusts, coccolithophores represent the dominant organisms that act as bio-seeds for an initial manganese deposition. These (bio)minerals are economically important: manganese is an important alloying component and cobalt forms part of special steels in addition to being used, along with other rare metals, in plasma screens, hard-disk magnets and hybrid car motors. Recent progress in our understanding of the participation of the organic matrices in the enrichment of these metals might provide the basis for feasibility studies of biotechnological applications.

Keywords polymetallic nodule      biomineralization      bacteria      sustainable exploitation     
Corresponding Author(s): WANG Xiao-Hong,Email:wxh0408@hotmail.com (X.H.W.); MüLLER Werner E. G.,Email:wmueller@uni-mainz.de (W.E.G.M.)   
Issue Date: 05 June 2012
 Cite this article:   
Xiao-Hong WANG,Ute SCHLO?MACHER,Shun-Feng WANG, et al. From nanoparticles via microtemplates and milliparticles to deep-sea nodules: biogenically driven mineral formation[J]. Front Mater Sci, 0, (): 97-115.
 URL:  
https://academic.hep.com.cn/foms/EN/10.1007/s11706-012-0164-6
https://academic.hep.com.cn/foms/EN/Y0/V/I/97
Fig.1  Polymetallic nodules; first description from the monograph of Murray [] based on the collection during the Challenger Expedition (1872 until 1876) [(A), (C), (E) and (G)] and - in comparison - samples dredged within the Clarion-Clipperton Zone (Eastern Pacific Ocean basin) [(B), (D), (F) and (H)].
A polymetallic nodules, collected in 1891 in the Coral Sea close to New Guinea. Outer appearance of a polymetallic nodule, with its smooth surface texture. Section through the center of a nodule originating from the South Pacific. Polished sections through a nodule. This nodule comprises at least four macrolamellae (la-1 to la-4), indicative for different histories during which the lamellae formed hydrogenetically. Broken nodule from the South Pacific with a [; white shark] tooth (t). A recently found nodule with a shark tooth (t). Small magnetic sherules (micronodules [mn]) within a nodule collected in the South Pacific. The smooth to lobated surfaces of the micronodules (mn) reflect efficiently light, while the interstitial material (im) remains less luminous.
Fig.2  Proposed non-enzymatic, biogenic deposition of minerals onto bacteria, from which the growth of nodules originate (scheme).
Abundantly iron and manganese biogenic deposits are seen in the hot springs, as shown here in the mountain region between Lake Baikal (Siberia) and the Khovsgol Lake in near the village Tunka. It is proposed that the S-layer (surface layer) particles, existing at the surface of the bacteria, promote the Mn deposition and hence the immobilization of the ions from the Mn soluble “precursor” ions. Via redox reactions, or oxidation-reduction reactions, controlled deposition/release processes are processed.
Fig.3  NANOSCALE ANALYSIS: Non-enzymatic Mn deposition onto S-layers, existing on the surface of bacteria. Those biogenic structures are assumed to act as bio-seeds.
S-layers, crystalline structures, onto the surfaces of the cone-like bacteria. Each individual cone-like structure (operationally abbreviated here with: b; standing for bacteria) with dimensions of 800 nm × 300 nm is decorated at its outward directed surface, with 20 to 25 pillar-shaped protrusions (p) [representing S-layers] measuring a size of 75 nm × 45 nm. Horizontal view onto a subsurface layer within a nodule, comprising cone-like structures (b). Cone-like structures (b) on a plane area within nodules. The phalanx of cones is arranged in parallel lines on the surface of the plane structure, representing a previous biofilm (bf). The individual cones have a size of 0.8 to 1.0 μm and are regularly arranged in a pattern with an interspacing of 1.0 to 1.5 μm. Element distribution within the nodule, as analyzed by EPMA. The (relative) concentration changes for the following two elements are shown here for manganese (D) and for iron (E). (Scale) The relative concentrations increase with a change in color from dark/blue to yellow to red.
Fig.4  MICROSCALE ANALYSIS: Microorganisms, cocci [from (A) to (C)] and rod-like microorganisms [from (E) to (G)] present in micronodules; SEM analysis.
Within the nodules, both cocci (co) and rods (ro) are seen; surface (su) of the micronodule. Cocci arranged in bead-like chains, known from the genus . An individual coccus revealing small-sized platelets on its surface. In some regions within the nodule rod-like microorganisms (ro) are dominant of cocci (co). One rod-chain (ro) composed of microorganisms. Two division septa (s) within the linearly oriented rods rod-chain (ro(c)) are shown. Solid shell (sh) disclosing an internal hollow space. The shell is made of a Coccolithophore.
Fig.5  MILLISCALE ANALYSIS: Nodule morphology; light optical analysis [(A) and (B)]; SEM [from (C) to (F)].
Nodules were collected from the Clarion-Clipperton Zone in the Pacific Ocean. A cross breakage of a nodule displays the lamellar structure with a pale-gray submetallic luster. The outer lamella (la) is dark brown to black, suggesting a composition of birnessite (bi). The individual lamellae are separated by a zone that comprises a dendritic, ornamentous pattern. This pattern is assembled and composed of single blackish drops, termed here micronodules (mn). Those micronodules are dominant in the surface lamella. Between the darkmetallic micronodules, an interstitial, whitish material (im) can be distinguished. The micronodules (mn) become well distinguishable after breaking the nodules. Frequently, the micronodules (mn) are clustered together and embedded in a nest. At the site of fracture, the micronodules (mn) appear as convex protuberances. Between the micronodules, an interstitial material (im) with a different texture without protuberances exists.
Fig.6  Schematic illustration of the formation of polymetallic nodules from micronodules. Initially, a bio-seed is formed when bacteria adhere to a substrate formed of minute clay/sand aggregates. This bio-seed (magenta) functions as a template and allows the progression of mineralization through abiogenic processes, which lead to the formation of micronodules (brown) that are further assembled into nests (blue) and, finally, into a nodule (red) formed of many nests. Nodules are formed under (rotating) movements caused by, for example, water currents on the sea floor, and additional inorganic abiogenic material is incorporated.
Fig.7  Schematic illustration of the enzymatically caused Mn deposition and release, mediated by a Mn(II)-oxidizing Bacillus strain that co-exist with the demosponge .
Sequence structure of the mnxG gene (termed mnxG-SubDo-03), identified in the -related strain, isolated from . The schematic representation of the mnx region with the central gene MnxG-SubDo-03 is attributed to the MCO [multicopper oxidase] enzyme. The locations of the putative Cu-binding regions within MnxG-SubDo-03, the regions E to F, have been indicated. The primers to identify the MCO from the sponge-associated bacteria (BAC-SubDo-03) span the regions C to B; the respective locations are indicated using the numbering of the gene isolated from the bacterial strain SG-1. The consensus Cu-binding sequence motifs (C/D and A/B) found in all MCOs are marked. In contrast to the controls (left) the bacteria that had incubated in Mn-containing K-medium become decorated with a manganese shell (right). Schematic representation of the proposed role of the BAC-SubDo-03 Bacillus strain, associated with , as an agent in Mn storage. It is outlined that under high Mn concentrations the bacteria take up Mn(II) from the environment through the MCO and deposit the ions as insoluble Mn(IV) on their cell wall. If Mn exists in the environment only at low concentrations the MCO allows the enrichment of the element to physiological levels. Intracellularly, in the sponge body, Mn is solubilized by reduction from Mn(IV) to Mn(II), released from the cell wall and becomes available as co-factor in a series of essential enzymes involved in detoxification of reactive oxygen species.
Fig.8  Protein with binding affinity to polymetallic nodules.
Screening system by phage display expression, identifying the sequence of the oligopeptide with binding affinity to polymetallic nodules. Based on this sequence and the EST database of a (putative) metal-binding protein had been identified. Sequence alignment of the putative metal-binding protein (MBD_SUBDO) with the mouse ribosome biogenesis protein [C16orf42 homolog isoform 1] (C16orf42_MUS; accession number NP_080952). Gaps are indicated with dashes (-). The consensus amino acids are given above the two polypeptides. The two domains identified () the Fer4-like domain in RNase L inhibitor, RLI (+RLI+) and () the domain of unknown function (DUF367) (-DUF367-) are marked in red and blue, respectively.
Fig.9  Functionalized MnO nanoparticles.
Schematic illustration of those MnO nanoparticles, functionalized using a multifunctional polymeric ligand through suitable anchor groups and carrying amine moieties. Protoporphyrin is bound to PEG800 shell via an amide bond. The protoporphyrin IX tagged MnO nanoparticles are used as photodynamic therapeutic agents to induce localized and intracellularly induced apoptosis in Caki-1 cells. Light microscopic images of human kidney cancer cells (Caki-1). MnO-DA-PEG-PP nanoparticles exhibit red fluorescence under a fluorescence microscope that can be co-localized to cell cores stained with DAPI. Caki-1 incubated with MnO-PP, and labeling of Caki-1 incubated with MnO-DA-PEG-PP and Annexin-V. These cells were not irradiated and, therefore, show no signs of apoptosis. Caki-1 cells incubated with MnO-DA-PEG-PP and irradiated with light of a wavelength of 630 nm. Fluorescence of the nanoparticles within the cells, Annexin-V fluorescence of apoptotic cells, and overlay of (d) and (e).
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