Geochemistry and descriptions of manganese nodules and crusts retrieved from the open ocean

The book is a compilation of all available data at the time of publication (1965) on the subject of marine minerals together with the author's original ideas regarding their exploitation. It is one of the most significant publications on ocean resources. It is particularly focused on manganese deposits, their description, sedimentary setting, formation and geochemistry.

(Tables 1-3) Silicon dioxide, Corg and trace element concentrations in sediments of the outer Eckernfoerder Bay, Western Baltic Sea

The main question, posed in the work scheme before laboratory analysis was started, was expressed as follows: Do marked seasonal fluctuations occur in trace element content of the sediment surface, and what are the probable influences of factors such as changing hydrographical parameters, plankton sequence etc. ? Special attention was paid to elements known as pollutants, for example mercury. Within this framework samples have been analysed for their contents of manganese, iron, zinc, lead, and mercury. The amounts of silica and organically-bound carbon serve in most cases as reference values for the trace element content. On sand temporary conditions of increased C org content raise the concentrations of all determined elements. Especially the values reached for mercury in July are worth nothing. It is concluded that Zn, Pb, and Hg tend to enrich with respect to C org as the decomposition of organic matter progresses. On mud-sand flocculation and precipitation of Mn/Fe-hydroxides probably represent an additional concentrating factor for the other elements as the relationship of the results for zinc and manganese shows. Manganese may indicate a seasonally related concentrating cycle at the sediment surface.

(Table 3, page 264), Composition of a manganese micronodule found in a fossil red clay bed from Western Timor

Chemical analyses are presented for two Cretaceous clays from Noil Tobee, Timor. Mineralogical examination has shown that they consist principally of quartz, feldspar, illite and chlorite, together with minor amounts of montmorillonite. Both chemically and mineralogically the clays are very similar to the recent argillaceous deep-sea sediments of the Pacific and Indian Oceans, which confirms Molengraaff's theory (1921) that they are of deep-sea origin. Further confirmation of this theory is provided by comparison of the composition of micromanganese nodules, separated from one of these clays, with that of manganese nodules from the Pacific Ocean.

(Table 2, page 1182) Partial composition of manganese encrustations from Gulf of Aden

Manganese encrustations from two adjacent sampling sites in the Gulf of Aden display markedly different compositional characteristics. The enrichment of manganese, and consequent depletion of iron and a series of trace elements, in the manganiferous crusts from Sta. 6243 is attributed to the diagenetic remobilisation of manganese within the sediment column and the resultant enrichment of this element in the encrustations from this station. Molybdenum, and possibly nickel, appear to show similar migration characteristics. Submarine vulcanism does not appear to play any significant role in controlling nodule composition within the area.

Annotated record and chemical analyses of a polygenetic manganese nodule (slab) from the Scott Plateau, Indian Ocean (core VA-16-13KD)

A large manganese nodule (manganese slab) was dredged from 2100 m on the Scott Plateau by R.V. Valdivia in 1977. It is an irregular ellipsoid, with a maximum dimension of 28 cm, parallel to the sea floor. Chemical analyses show that Mn and Fe proportions are comparable, and total Ni + Cu + Co content averages 0.7%. The nodule has a complex growth history which started with radial upward growth leading to coalescing into a continuous crust. The crust was coated with horizontal layers. After fracturing and infilling of cracks with calcareous sediment, further layers encased the nodule.

(Table 1, page 376), Composition of manganese deposits from the Gulf of Aden and the Carlsberg Ridge

Iron-manganese nodules from the ocean floor have been extensively studied. But, because of the fine grain size of the particles of the nodules, structural identification by X-ray and electron diffraction techniques is difficult and the mineralogy of the iron oxide phase has not been well characterized. The observation of the Mössbauer spectrum-in which each nucleus absorbs gamma-rays independently-is not limited by particle size in the same way as is the observation of Bragg peaks in diffraction measurements, in which radiation must be scattered coherently from a large number of atoms. The magnetic hyperfine splitting in the Mössbauer spectrum of magnetic materials is affected, however, when the particles are so small that they become superparamagnetic. We describe here an investigation using the 57Fe Mössbauer effect of two iron-manganese nodules in which the iron oxide phase could not be detected by X-ray or electron diffraction.

Facile synthesis of copper-manganese spinel anodes with high capacity and cycling performance for lithium-ion batteries

Copper-manganese spinel containing anodes were synthesized by a facile sol-gel method and evaluated in lithium-ion battery applications for the first time. The synergistic effects between copper-manganese and the aqueous binder (sodium carboxymethyl cellulose) provided a high specific capacity and excellent cycling performance. It was found that the specific capacity of the copper-manganese spinel remained at 608 mAh g⁻¹ after 100 cycles at a current density of 200 mA g⁻¹. Furthermore, a relatively high reversible capacity of 278 mAh g⁻¹ could be obtained at a current density of 2000 mA g⁻¹, indicating a good rate capability. These studies suggest that copper-manganese spinel is a promising material for lithium-ion battery applications due to a combination of good electrochemical performance and low cost.

Maize inbreds from different heterotic groups as favorable sources for increased potential bioavailability of magnesium, iron, manganese and zinc

Malnutrition, as a global problem, is mainly caused by low level of mineral elements in staple food (deficient soil). Biofortification is based on selection of genotypes with enhanced concentration of mineral elements in grain, as well as decreased concentration of substances which interfere bioavailability of mineral elements in gut (like phytic acid), and increased content of substances that increase availability (such as β-carotene). The experiment with 51 maize ( Zea mays L.) inbred lines with different heterotic background was set up in order to evaluate chemical composition of grain and to determine the relations between phytic acid (PA), β-carotene, and mineral elements: Mg, Fe, Mn, and Zn. The highest average phytate, β-carotene, Fe, and Mn content was found in grain of inbreds from Lancaster heterotic group. The highest content of Mg was in grain of Independent source and Zn in grain of BSSS group. Increased level of Fe and Mn in Lancaster lines could be partially affected by higher PA content in grain, while increased β-carotene content could improve Mn and Zn availability from grain of BSSS genotypes and Mg availability from Lancaster inbreds. It is important to underline that PA reduction is followed by Zn content increase in grain of Lancaster heterotic group, as well as that variations in Mg, Fe, and Mn contents are independent on PA status in inbreds from Independent source, indicating that the genotypes with higher Mg, Fe and Mn status from this group could serve as favorable source for improved Mg, Fe, and Mn absorption.

Functionalised zinc oxide nanowire gas sensors : enhanced NO2 gas sensor response by chemical modification of nanowire surfaces

Surface coating with an organic self-assembled monolayer (SAM) can enhance surface reactions or the absorption of specific gases and hence improve the response of a metal oxide (MOx) sensor toward particular target gases in the environment. In this study the effect of an adsorbed organic layer on the dynamic response of zinc oxide nanowire gas sensors was investigated. The effect of ZnO surface functionalisation by two different organic molecules, tris(hydroxymethyl)aminomethane (THMA) and dodecanethiol (DT), was studied. The response towards ammonia, nitrous oxide and nitrogen dioxide was investigated for three sensor configurations, namely pure ZnO nanowires, organic-coated ZnO nanowires and ZnO nanowires covered with a sparse layer of organic-coated ZnO nanoparticles. Exposure of the nanowire sensors to the oxidising gas NO2 produced a significant and reproducible response. ZnO and THMA-coated ZnO nanowire sensors both readily detected NO2 down to a concentration in the very low ppm range. Notably, the THMA-coated nanowires consistently displayed a small, enhanced response to NO2 compared to uncoated ZnO nanowire sensors. At the lower concentration levels tested, ZnO nanowire sensors that were coated with THMA-capped ZnO nanoparticles were found to exhibit the greatest enhanced response. ΔR/R was two times greater than that for the as-prepared ZnO nanowire sensors. It is proposed that the ΔR/R enhancement in this case originates from the changes induced in the depletion-layer width of the ZnO nanoparticles that bridge ZnO nanowires resulting from THMA ligand binding to the surface of the particle coating. The heightened response and selectivity to the NO2 target are positive results arising from the coating of these ZnO nanowire sensors with organic-SAM-functionalised ZnO nanoparticles.

Vibrational spectroscopic characterization of the phosphate mineral phosphophyllite – Zn2Fe(PO4)2·4H2O, from Hagendorf Süd, Germany and in comparison with other zinc phosphates

This research was undertaken on phosphophyllite sample from the Hagendorf Süd pegmatite, Bavaria, Germany. Chemical analysis was carried out by Scanning Electron Microscope in the EDS mode and indicates a zinc and iron phosphate with partial substitution of manganese, which partially replaced iron. The calculated chemical formula of the studied sample was determined to be: Zn2(Fe0.65, Mn0.35)P1.00(PO4)2- �4(H2O). The intense Raman peak at 995 cm�1 is assigned to the m1 PO3� 4 symmetric stretching mode and the two Raman bands at 1073 and 1135 cm�1 to the m3 PO3� 4 antisymmetric stretching modes. The m4 PO3� 4 bending modes are observed at 505, 571, 592 and 653 cm�1 and the m2 PO3� 4 bending mode at 415 cm�1. The sharp Raman band at 3567 cm�1 attributed to the stretching vibration of OH units brings into question the actual formula of phosphophyllite. Vibrational spectroscopy enables an assessment of the molecular structure of phosphophyllite to be assessed.

Catalyst engineering for lithium ion batteries: The catalytic role of Ge in enhancing the electrochemical performance of SnO2(GeO2)0.13/G anodes

The catalytic role of germanium (Ge) was investigated to improve the electrochemical performance of tin dioxide grown on graphene (SnO(2)/G) nanocomposites as an anode material of lithium ion batteries (LIBs). Germanium dioxide (GeO(20) and SnO(2) nanoparticles (<10 nm) were uniformly anchored on the graphene sheets via a simple single-step hydrothermal method. The synthesized SnO(2)(GeO(2))0.13/G nanocomposites can deliver a capacity of 1200 mA h g(-1) at a current density of 100 mA g(-1), which is much higher than the traditional theoretical specific capacity of such nanocomposites (∼ 702 mA h g(-1)). More importantly, the SnO(2)(GeO(2))0.13/G nanocomposites exhibited an improved rate, large current capability (885 mA h g(-1) at a discharge current of 2000 mA g(-1)) and excellent long cycling stability (almost 100% retention after 600 cycles). The enhanced electrochemical performance was attributed to the catalytic effect of Ge, which enabled the reversible reaction of metals (Sn and Ge) to metals oxide (SnO(2) and GeO(2)) during the charge/discharge processes. Our demonstrated approach towards nanocomposite catalyst engineering opens new avenues for next-generation high-performance rechargeable Li-ion batteries anode materials.

Mechanism of action of selenious acid in the electrodeposition of manganese

The effect of selenious acid as an addition agent in the electrodeposition of manganese was studied by analysing the current-potential curves for manganese deposition. The mechanism of action of this addition agent was found to be essentially similar to that proposed for sulphur dioxide, namely to affect the manganese deposition indirectly by influencing the hydrogen evolution reaction which is a parallel reaction at the electrode surface.

Synthesis of zinc oxide porous structures by anodization with water as an electrolyte

We report a simple, reliable and one-step method of synthesizing ZnO porous structures at room temperature by anodization of zinc (Zn) sheet with water as an electrolyte and graphite as a counter electrode. We observed that the de-ionized (DI) water used in the experiment is slightly acidic (pH=5.8), which is due to the dissolution of carbon dioxide from the atmosphere forming carbonic acid. Porous ZnO is characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy and photoluminescence (PL) studies. The current-transient measurement is carried out using a Gamry Instruments Reference 3000 and the thickness of the deposited films is measured using a Dektak surface profilometer. The PL, Raman and X-ray photoelectron spectroscopy are used to confirm the presence of ZnO phase. We have demonstrated that the hybrid structures of ZnO and poly (3,4-ethylenedioxythiophene):poly (styrene sulfonate) (PEDOT:PSS) exhibit good rectifying characteristics. The evaluated barrier height and the ideality factor are 0.45 eV and 3.6, respectively.

A broad pore size distribution mesoporous SnO2 as anode for lithium-ion batteries

We demonstrate here that mesoporous tin dioxide (abbreviated M-SnO2) with a broad pore size distribution can be a prospective anode in lithium-ion batteries. M-SnO2 with pore size ranging between 2 and 7.5 nm was synthesized using a hydrothermal procedure involving two different surfactants of slightly different sizes, and characterized. The irreversible capacity loss that occurs during the first discharge and charge cycle is 890 mAh g(-1), which is smaller than the 1,010-mAh g(-1) loss recorded for mesoporous SnO2 (abbreviated S-SnO2) synthesized using a single surfactant. After 50 cycles, the discharge capacity of M-SnO2 (504 mAh g(-1)) is higher than that of S-SnO2 (401 mAh g(-1)) and solid nanoparticles of SnO2 (abbreviated nano-SnO2 < 4 mAh g(-1)) and nano-SnO2. Transmission electron microscopy revealed higher disorder in the pore arrangement in M-SnO2. This, in turn imparts lower stiffness to M-SnO2 (elastic modulus, E (R) a parts per thousand aEuro parts per thousand 14.5 GPa) vis-a-vis S-SnO2 (E (R) a parts per thousand aEuro parts per thousand 20.5 GPa), as obtained using the nanoindentation technique. Thus, the superior battery performance of M-SnO2 is attributed to its intrinsic material mechanical property. The fluidity of the internal microstructure of M-SnO2 resulted in a lower degree of aggregation of Sn particles compared to S-SnO2 and nano-SnO2 structural stabilization and long-term cyclability.