The distribution of manganese and iron between ilmenite and granitic magma in the Ôsumi Peninsula,Japan

Manganoan ilmenite with a variable manganese content occurs as an early accessory constituent of granitic rocks in the Ôsumi Peninsula, southern Kyushu. Electron probe micro-analysis of a grain containing highest manganese gives the structural formula (Fe _1.23 ²⁺ Mn _0.81 ²⁺ ) (Ti_1.97) O₆, if all of the manganese and iron are in the divalent state. The manganese content of manganoan ilmenite increases with an increase of the differentiation index of host rocks, however, the amount of ilmenite tends to decrease with the increase of the same index. The mode of occurrence of the ilmenite suggests that it is the first mafic mineral to precipitate from the magma. The average value of the distribution coefficient of manganese and ferrous iron between ilmenite and granitic magma is 5.5, if the Mn/Fe ratio of the granitic rocks represents that of granitic magma. The variation in the FeO and MnO contents against the differentiation index for granitic rocks of the Ôsumi Peninsula, and the value of the distribution coefficient, show that high manganoan ilmenite is stable in the most differentiated granitic rock of the Ôsumi Peninsula.     

Dispersed iron and manganese in Pacific Ocean sediments

The article considers the areal distribution of dispersed iron and manganese on the bottom of the Pacific Ocean. -Author.     

Sinks of iron and manganese in underground coal mine workings

The sources and sinks of manganese in underground coal mine workings are poorly understood compared to those of iron. The geochemical system in the secondary egress drift of Caphouse Colliery near Horbury, UK, is an ideal system for studying these processes. Five locations along the drift and four secondary inflows to the drift were sampled 24 times through the year commencing May 2005. During the sampling period, the pH in the main channel varied from 6.73 to 7.93 and increased along the flow path. The secondary inflows to the drift from the strata were of higher alkalinity (mean = 385 mg/L as CaCO₃) than the main flow (mean = 330 mg/L as CaCO₃); the affects of mixing between the less alkaline main channel and the more alkaline secondary inflows and of carbon dioxide exsolution are evident in the form of carbonate and hydroxide precipitates. SEM and XRD analysis of precipitates collected from the drift confirm the presence of calcium and manganese carbonates and ferric hydroxide. PHREEQC speciation and solubility modelling confirms supersaturation of the water in the main channel with respect to ferric oxy-hydroxides; iron, manganese, magnesium and calcium carbonates; and manganese oxides. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Elements of the iron and manganese cycles in Lake Baikal

Using data obtained in recent years, we considered the external mass balance and characteristics of internal iron and manganese cycles in Lake Baikal (biological uptake, remineralization, sedimentary and diffusive fluxes, accumulation in sediments, time of renewal, etc.). Some previous results and common concepts were critically reevaluated.     

The control of cathodoluminescence in dolomite by iron and manganese

Variations in the cathodoluminescent properties of carbonates are usually attributed to differing proportions of manganese (Mn²⁺) as the most important activator, and iron (Fe²⁺) as the main inhibitor of luminescence. Interactions between manganese and iron concentrations and the luminescent properties of dolomite are demonstrated by petrographic and chemical analyses of 86 samples of dolomite representing a range of depositional environments and ages (Cambrian to Cretaceous) and a wide geographical distribution (North America and Europe). Iron and manganese are positively correlated in the dolomites, with the former showing a greater range of variation. Very small amounts of manganese are sufficient to activate the luminescence and as little as 100 ppm Mn²⁺ is present in highly luminescing samples. The intensity of luminescence is not proportional to the manganese concentration. Iron begins to quench luminescence as its concentration reaches 10,000 ppm. Above that level, luminescence is rapidly lost and total extinction occurs among samples containing more than 15,000 ppm Fe²⁺, regardless of the manganese concentration.     

On the distribution of iron and manganese at the sediment/water interface: thermodynamic versus kinetic control

Iron and manganese solubility at the sediment/water interface has been studied at a water depth of 20 m in Kiel Bight, Western Baltic. By means of an in situ bell jar system enclosing 3.14 m² sediment surface and 2094 l water a complete redox turn-over in the bottom water was simulated in an experiment lasting 99 days. The concentration of dissolved Fe in the bell jar water never exceeded 0.041 μmol · dm^?3during the first 50 days of the experiment and then rose abruptly as the Eh fell from +600 to ?200 mV. The concentration of dissolved Fe under oxic and anoxic conditions seems to be limited by equilibria with solid Fe-phases (hydroxides and amorphous sulphide, respectively). In contrast to Fe, manganese was released continuously from the bottom during the first 50 days of the experiment leading to exponentially increasing manganese concentrations in the bell jar water. During this time dissolved O₂ had become ready depleted and pH had dropped from 8.3 to 7.5. Contrary to iron, manganese being solubilized in reduced sediment layers can penetrate oxic strata in metastable form due to slow oxidation kinetics; when the redoxcline moves upwards Mn²⁺ is enriched in bottom waters. The maximum concentration of dissolved Mn under anoxic conditions is controlled by a solid phase with solubility properties similar to MnCO₃ (rhodochrosite). Bottom water enrichment in dissolved Mn²⁺ could be traced to originate from excess solid manganese within the top 3 cm of the sediment.     

Size distribution of quartz in mudrocks

Sixteen penecontemporaneously deposited mudrock-sandstone pairs ranging in age from Devonian to Cretaceous were treated chemically to isolate the quartz and chert fraction from the other constituents of the rocks. The amount of crystalline silica was determined from the chemical treatments; its size distribution was determined using a combination of normal and Micro Mesh sieving and settling tube analysis; the crystalline silica coarser than 10 μu was examined petrographically to determine the amount of chert. Percentages of crystalline silica in the mudrocks range from 6·7 to 46·7 % and average 27·6 (σ= 10·7). Mean grain size ranges from 4·4 φ to 7·3 φ and averages 6·1 φ. The crystalline silica fraction is a poorly sorted medium to fine silt consisting of one-eighth sand, six-eighths silt, and one-eighth clay size sediment. Percentage of crystalline silica and mean size of crystalline silica in the thirty-two mudrocks and sandstones are positively correlated; r= 0·685, which is significant at the 99 % level. The best fit linear regression line is: Y= 102·7–11·3X. Extrapolation of the regression line indicates that, on the average, crystalline silica is lacking in mudrocks in grain sizes finer than 9·1 φ (1·μm), a result consistent with observations by clay mineralogists. The crystalline silica fraction of both the mudrocks and associated sandstones averages 4% chert in the >10 μm portion. There is no correlation between the mean grain size of the crystalline silica and the percentage of chert in it.     

The contrasting biogeochemistry of iron and manganese in the Pacific Ocean

Vertical and horizontal distributions of dissolved and suspended particulate Fe and Mn, and vertical fluxes of these metals (obtained with sediment traps) were determined throughout the Pacific Ocean. In general, dissolved Fe is low in surface and deep waters (0.1 to 0.7 nmol/kg), with maxima associated with the intermediate depth oxygen minimum zone (2.0 to 6.6 nmol/kg). Vertical distributions of dissolved Mn are similar to previous reports, exhibiting a surface maximum, a subsurface minimum, a Mn maximum layer coincident with the oxygen minimum zone, and lowest values in deep waters.Near-shore removal processes are more intense for dissolved Fe than for dissolved Mn. Dissolved Mn in the surface mixed layer remains elevated much farther offshore than dissolved Fe. Elevated near-surface dissolved Mn concentrations occur in the North Pacific Equatorial Current, suggesting transport from the eastern boundary. Near-surface mixed-layer dissolved Mn concentrations are higher in the North Pacific gyre reflecting enhanced northern hemisphere aeolian sources.Residence time estimates for the settling of refractory paniculate Fe and Mn from the upper water column are 62–220 days (Fe), and 105–235 days (Mn). In contrast, residence times for the scavenging of dissolved Fe and Mn are 2–13 years (Fe) and 3–74 years (Mn). Scavenging residence times for dissolved Mn based on horizontal mixing in the surface mixed layer of the northeast Pacific are 0.4 years (nearshore) to 19 years (1000 km offshore).There is no evidence for in situ Fe redox dissolution within sub-oxic waters in the eastern tropical North Pacific. Dissolved Fe appeared to be controlled by dissolution from sub-oxic sediments, with oxidative scavenging in the water column or upper sediment layers. However, in situ Mn dissolution within the oxygen minimum zone was evident.     

Ion exchange properties of manganese and iron minerals in oceanic micronodules

The results of experimental studies of ion exchange properties of manganese and iron minerals in micronodules (MN) from diverse bioproductive zones of the World Ocean are considered. It was found that the sorption behavior of these minerals is similar to that of ore minerals from ferromanganese nodules (FMN) and low-temperature hydrothermal crusts. The exchange complex of minerals in the MN includes the major (Na⁺, K⁺, Ca²⁺, Mg²⁺, and Mn²⁺) and the subordinate (Ni²⁺, Cu²⁺, Co²⁺, Pb²⁺, and others) cations. Reactivity of theses cations increases from Pb²⁺ and Co²⁺ to Na⁺ and Ca²⁺. Exchange capacity of MN minerals increases from the alkali to heavy metal cations. Capacity of iron and manganese minerals in the oceanic MN increases in the following series: goethite < goethite + birnessite < todorokite + asbolane-buserite + birnessite < asbolane-buserite + birnessite < birnessite + asbolane-buserite < birnessite + vernadite Fe-vernadite + Mn-feroxyhyte. The data obtained supplement the available information on the ion exchange properties of oceanic ferromanganese sediments and refine the role of sorption processes in the redistribution of metal cations at the bottom (ooze) water-sediment interface during the MN formation and growth.     

Particulate iron and manganese in the Santa Barbara Basin,California

Particulate Fe and Mn may be important trace metal scavengers in the water column as well as being probable indicators of biologically mediated redox processes. A study has been made of suspended particulate composition in the Santa Barbara Basin, a shallow near-shore basin off southern California with sub-oxic conditions below sill depth. Observations have revealed several interesting phenomena relating to the geochemistry of Fe and Mn. Most striking is a profound enrichment of particulate Fe in samples from the bottom two hundred meters. These particulates have a constant Fe/P mole ratio of about three and may originate at the sediment-water interface or may be transported to the basin from local marshes. For particulate Mn, enrichments are observed both in the sub-sill waters and near the base of the euphotic zone. A consideration of particle removal rates suggests that the sub-photic zone enrichment has a biogenic origin. In the sub-sill waters, enrichment in Mn is apparently due to the precipitation of dissolved Mn diffusing from the anoxic basin sediments. A simple mass balance suggests that most of the Mn lost from the sediments is transported from the Santa Barbara Basin in dissolved form.     

Vanadium,manganese and iron in the carbonate rocks of the Rohtas formation

The environmental conditions that prevailed during the formation of the Rohtas carbonates have been delineated on the basis of the Eh-pH diagrams for V, Mn, Fe⁺² and Fe⁺³ compounds. The high content of vanadium in the insoluble residue is indicative of the prevalence of reducing environment. During early-diagenesis manganese seems to have been mobilised from the soft sediments. Higher manganese content in the carbonates is a result of late-diagenesis. Prior to late diagenesis, ferric iron appears to have been precipitated from the waters while manganese remained in solution, and this process accounts for the low iron content of the carbonates.     

The behaviour of dissolved organic material,iron and manganese in estuarine mixing

Fractionation by ultra-filtration of the dissolved organic material (DOM) in the River Beaulieu, with typical concentrations of dissolved organic carbon (DOC) of 7–8 mg C/l, showed it to be mainly in the nominal molecular weight range of 10³–10⁵, with 16–23% of the total DOC in the fraction > 10⁵. The molecular weight distribution of DOM in the more alkaline River Test (average DOC, 2 mg C/l) was similar. In the River Beaulieu water, containing 136–314 βg Fe/l in ‘dissolved’ forms, 90% or more of this Fe was in the nominal molecular weight fraction > 10⁵. Experiments showed that DOM of nominal molecular weight <10⁵ could stabilize Fe(III) in ‘dissolved’ forms. The concentrations of ‘dissolved’ Fe in the river water probably reflect the presence of colloidal Fe stabilized by organic material and this process may influence the apparent molecular weight of the DOM. Dissolved. Mn (100–136 βg/l) in the River Beaulieu was mainly in true solution, probably as Mn(II), with some 30% in forms of molecular weight greater than ca 10⁴.During mi xing in the Beaulieu Estuary, DOC and dissolved Mn behave essentially conservatively. This contrasts with the removal of a large fraction of the dissolved Fe (Holliday and LISS, 1976, Est. Coastal Mar. Sci. 4, 349–353). Concentrations of lattice-held Fe and Mn in suspended particulate material were essentially uniform in the estuary, at 3.2 and 0.012%, respectively, whereas the non-lattice held fractions decreased markedly with increase in salinity. For Mn the decrease was linear and could be most simply accounted for by the physical mixing of riverborne and marine participates, although the possibility that some desorption occurs is not excluded. The non-linear decrease in the concentration of non-lattice held Fe in particulates reflected the more complex situation in which physical mixing is accompanied by removal of material from the ‘dissolved’ fraction.     

The distribution of U and Th in growth zones of manganese nodules

Growth zones and individual sublayers from one manganese nodule and three manganese crusts from an area south of Hawaii were analysed for U and Th by the delayed-neutron counting technique.The concentrations of uranium and thorium in the manganese nodule are highest in the outermost zone on top of the nodule, being the surface last exposed to sea water. In this zone U varies from 6.3 to a maximum of 8.3 ppm in different sublayers, decreasing to 5.0 ppm in the inner zones and 3.4 ppm in the outer zone last exposed to the sediment. Ferromanganese material scraped from the zone last exposed to the sediment which has low concentrations of Fe, relative to the zone last exposed to sea water, has also low U contents (2.7 ppm).Th concentrations are higher in the outermost zone on top of the nodule (40 to a maximum of 130 ppm) than in the zone last exposed to the sediment (about 20 ppm Th).Manganese crusts contain up to 9 ppm U in the outermost zones last exposed to the sea water. They also have higher concentrations of Th (up to 64 ppm) relative to the inner zones of the crust growing on altered andesitic rock, which contains about 8 ppm U and about 26 ppm Th as an average.     

碱熔—磷钒钼黄法测定铁、锰矿中的磷

以氢氧化钾熔融分解样品，以热水浸提、铁、铜、钴、镍等干扰物进入沉淀而与磷分离，然后在7％的硝酸介质以钼酸铵铵及偏钒酸铵混合显色剂显色测定磷的含量，该方法简便、稳定、快速、适合于铁、锰矿中磷的测定。     

XANES analysis of the mechanisms of arsenic removal in biological iron and manganese treatment unit

Biological iron and manganese removal utilizing indigenous iron and manganese oxidizing bacteria （IRB hereafter） in groundwater can also be applied to arsenic removal according to our pilot-scale test. The arsenic removal probably occurred through sorption and complexation of arsenic to iron and manganese oxides formed by enzymic action of IRB. We investigated the chemical properties of iron and manganese oxides in IRB floc and the valence state of arsenic sorbed to the floc to clarify the mechanisms of the arsenic [especially As （Ⅲ）] removal. The floc samples were collected from two drinking water plants using IRB （Jyoyo and Yamatokoriyama, Japan）, and our pilot - scale test site where arsenic and iron removal using IRB is under way （Mukoh, Japan）. The Jyoyo and Yamatokoriyama IRB floc samples were subjected to As （Ⅲ） and As（Ⅴ） sorption experiments. The elemental composition of the floc samples was measured. XANES spectra were collected on As, Fe and Mn K-edges at synchrotron radiation facility Spring 8 （Hyogo, Japan）. FT-IR and the X-ray diffraction spectra of the samples were also obtained. The IRB floc contained ca. 35 % Fe, 0.3%-3.5% Mn and 2%-6% P. The samples were highly amorphous and contained ferrihidrites and hydrated iron phosphate. According to XANES analyses of IRB, As associated with IRB was in ＋5 valence state when As （Ⅲ） （or As （Ⅴ）） was added in laboratory sorption test, Fe in ＋3 valence state, and Mn a mixture of＋3 and ＋4 valence states. Small shift was observed in the XANES spectra of IRB on As K-edge as the equilibration time of the sorption experiment was increased. Gradual oxidation of a small amount of As （Ⅲ） associated with IRB or change in arsenic binding with sorption site were the probable mechanism.     

珠江三角洲地区地下水锰的分布特征及其成因

为了解珠江三角洲地区地下水中锰的含量及其成因,笔者采集并分析了352组地下水样和13组地表水样。结果表明:珠江三角洲地区地下水的锰含量在未检出至8.32mg/L之间,平均浓度为0.34mg/L,超标率达49.4%。在该区9个地级市范围都存在地下水锰超标现象。区内地下水的锰含量与总溶解固体(TDS)、化学需氧量(COD)以及HCO3ˉ都呈极显著的正相关关系,而与Eh呈极显著的负相关关系。珠江三角洲地区地下水中锰含量的分布与该地区的工业化程度以及所处的补、径、排条件密切相关。影响该地区地下水锰含量分布的因素主要有氧化还原环境、酸碱条件、地下水的总溶解固体、上覆盖层性质、地下水径流条件以及含水层介质等。     

The distribution of total nitrogen in iron meteorites

Total nitrogen abundances in 123 iron meteorites have been determined by inert carrier-gas fusion extraction-gas chromatography. The median value for the iron meteorites was found to be 18 ppm N. The N contents of Sulfide inclusions are greater, in nine cases out of ten, than the corresponding metallic phase. The N content of the iron meteorites is positively correlated with germanium content. The effects of terrestrial weathering and heat treatment by man are discussed in relation to the N contents measured for certain specimens. A correlation between N and cooling rates was found, with lower cooling rates associated with greater N abundances.     

Size distribution analyses for estimating diamond grade and value

Analysing the size frequency distributions (SFDs) of both micro diamonds and macro diamonds from primary deposits shows that the distributions are continuous across all sizes and that there are two regions of different character with a transition about 1–2 mm. Using log axes, the frequency curve is linear for the smaller sizes allowing slope and intercept parameters to be determined which are less ambiguous than stone counts and ratios of macro to micro populations that are generally reported. Modelling a diamond population that has undergone removal of a uniform thickness of the outer layer transforms a linear frequency curve into a quadratic form, which is also the form of the frequency curve for macro diamonds. Diamonds grown synthetically also display a linear distribution across a smaller fraction of their size distribution curve.