Analysis of Mn-nodules from Breitgrund, Baltic Sea

The usually high concentrations of Zn, Pb, Cd, and Cu in the most recently accreted portions of ferromanganese nodules from the western Baltic Sea are thought to reflect increased metal input due to anthropogenic mobilization. If so, the point of increase represents a time horizon within the structure of the nodule. Similar trace metal distributions of radiometrically dated sediments from the same area suggest that the ferromanganese nodules have grown in thickness between 0.02 and 0.16 mm yr-1. From this growth rate anthropogenic Zn flux to the nodule surface was calculated to be 80 mg m-2 yr-1.

Annotated record and spectrochemical analyses of Mn nodules from Georgia Strait, British Columbia obtained during CNAV Laymore in 1970

A study of the distribution, dispersal and composition of surficial sediments in the Strait of Georgia, B.C., has resulted in the understanding of basic sedimentologic conditions within this area. The Strait of Georgia is: a long, narrow, semi-enclosed basin with a restricted circulation and a single, main, sediment source. The Fraser. River supplies practically all the sediment now being deposited in the Strait of Georgia, the bulk of it during the spring and summer freshet. This river is building a delta into the Strait from the east side near the south end. Ridges of Pleistocene deposits within the Strait and Pleistocene material around the margins, like bedrock exposures, provide local sources of sediment of only minor importance. Rivers and streams other than the Fraser contribute insignificant quantities of sediment to the Strait. Sandy sediments are concentrated in the vicinity of the delta, and in the area to the south and southeast. Mean grain size decreases from the delta toward the northwest along the axis of the Strait, and basinwards from the margins. Silts and clays are deposited in deep water west and north of the delta front, and in deep basins northwest of the delta. Poorly sorted sediments containing a gravel component are located near tidal passes, on the Vancouver Island shelf area, on ridge tops within the Strait, and with sandy sediments at the southeastern end of the study area. The Pleistocene ridges are areas of non-deposition, having at most a thin veneer of modern mud on their crests and upper flanks. The southeastern end of the study area contains a thick wedge of shandy sediment which appears to be part of an earlier delta of the Fraser River. Evidence suggests that it is now a site of active submarine erosion. Sediments throughout the Strait are compositionally extremely similar, with-Pleistocene deposits of the Fraser River drainage basin providing the principal, heterogeneous source. Gravels and coarse sands are composed primarily of lithic fragments, dominantly of dioritic to granodloritlc composition. Sand fractions exhibit increasing simplicity of mineralogy with decreasing grain-size. Quartz, felspar, amphibole and fine-grained lithic fragments are the dominant constituents of the finer sand grades. Coarse and medium silt fractions have compositions similar to the fine sands. Fine silts show an increase in abundance of phyllosilicate material, a feature even more evident in the clay-size fractions on Montmorillonite, illite, chlorite, quartz and feldspar are the main minerals in the coarse clay fraction, with minor mixed-layer clays and kaolinite. The fine clay fraction is dominated by montmorillonite, with lesser amounts of illite and chlorite. The sediments have high base-exchange capacities, related to a considerable content of montmorillonite. Magnesium is present in exchange positions in greater quantity in Georgia Strait sediments than in sediments from the Fraser River, indicating a preferential uptake of this element in the marine environment. Manganese nodules collected from two localities in the Strait imply slow sediment accumulation rates at these sites. Sedimentation rates on and close to the delta, and in the deep basins to the northwest, are high.

Analysis of Mn-nodules from Slupsk Furrow

Rare earth element concentrations in ferromanganese concretions sampled from Slupsk Furrow in the Polish Exclusive Economic Zone are similar to those of concretions from the Gulf of Bothnia. The lack of positive Ce anomalies in the concretions from Slupsk Furrow indicates that they are formed under less oxidizing conditions than spheroidal concretions from the Gulf of Bothnia. Mossbauer studies indicate that poorly crystalline lepidocrosite is the principal iron oxyhydroxide mineral present in these concretions.

Analysis of Mn nodules from cruise GH72-2

The GH72-2 shipborne survey was carried out in the northwest Pacific during 31 days under the 'Basic investigations for exploration of deep sea mineral resources' program. The sediments encountered could be classified as follows: 1) Most of the brown clays occur on the abyssal plain of the basins at depth over 4500m. 2) Calcareous oozes are predominant at the top, slope and foot of seamounts and guyots. 3) Terrigeneous sediments are distributed near islands. The concentrated zone of ferromanganese nodules was located in the Magellan seamounts area. However, the metal contents in Mn, Cu, Ni and Co for these nodules are relatively poor, and these ferromanganese deposits occur at a depth over 5000m. It is interesting to note that the shape of the nodules is sometimes nearly spherical, and that the chemical composition of the nodules is characterized by the low ratio Mn/Fe and Co/Ni.

Prediction of the equilibrium structures and photomagnetic properties of the Prussian blue analogue RbMn[Fe(CN)6] by density functional theory

A periodic density functional theory method using the B3LYP hybrid exchange-correlation potential is applied to the Prussian blue analogue RbMn[Fe(CN)6] to evaluate the suitability of the method for studying, and predicting, the photomagnetic behavior of Prussian blue analogues and related materials. The method allows correct description of the equilibrium structures of the different electronic configurations with regard to the cell parameters and bond distances. In agreement with the experimental data, the calculations have shown that the low-temperature phase (LT; Fe(2+)(t(6)2g, S = 0)-CN-Mn(3+)(t(3)2g e(1)g, S = 2)) is the stable phase at low temperature instead of the high-temperature phase (HT; Fe(3+)(t(5)2g, S = 1/2)-CN-Mn(2+)(t(3)2g e(2)g, S = 5/2)). Additionally, the method gives an estimation for the enthalpy difference (HT LT) with a value of 143 J mol(-1) K(-1). The comparison of our calculations with experimental data from the literature and from our calorimetric and X-ray photoelectron spectroscopy measurements on the Rb0.97Mn[Fe(CN)6]0.98 x 1.03 H2O compound is analyzed, and in general, a satisfactory agreement is obtained. The method also predicts the metastable nature of the electronic configuration of the high-temperature phase, a necessary condition to photoinduce that phase at low temperatures. It gives a photoactivation energy of 2.36 eV, which is in agreement with photoinduced demagnetization produced by a green laser.

Origin of the ESR spectrum in the Prussian Blue analogue RbMn[Fe(CN)6]*H2O

We present an ESR study at excitation frequencies of 9.4 GHz and 222.4 GHz of powders and single crystals of a Prussian Blue analogue (PBA), RbMn[Fe(CN)6]*H2O in which Fe and Mn undergoes a charge transfer transition between 175 and 300 K. The ESR of PBA powders, also reported by Pregelj et al. (JMMM, 316, E680 (2007)) is assigned to cubic magnetic clusters of Mn2+ ions surrounding Fe(CN)6 vacancies. The clusters are well isolated from the bulk and are superparamagnetic below 50 K. In single crystals various defects with lower symmetry are also observed. Spin-lattice relaxation broadens the bulk ESR beyond observability. This strong spin relaxation is unexpected above the charge transfer transition and is attributed to a mixing of the Mn3+ - Fe2+ state into the prevalent Mn2+ - Fe3+ state.

Annotated record of the detailed examination of Mn micronodules from stations over George Bank, Atlantic Ocean

Ferromanganese micronodules have been found on Georges Bank, off the U.S. northeast coast, distributed throughout the surficial sediments within an area about 125 km long and at least 12 km wide. These coarse, sand-sized concretions have precipitated from metal-rich interstitial waters and contain many of the textural and structural features common to other neritic nodules. Most of the nodules have accreted around detrital grains, and X-ray powder diffraction analyses indicate the presence of geothite and vernadite ( delta -MnO sub(2)) in the ferromanganese layers. Chemical analyses of the micronodules, when compared with similar data on deep-sea manganese nodules, reveal lower Mn/Fe ratios, significantly higher concentrations of V and As, comparable values of Mo, and an order of magnitude less of Co, Ni, Ce and most other, metals.

Annotated record of the detailed examination of Mn deposits from the QUEBRADA (1969) and SIQUEIROS (1974) expeditions around the East Pacific Rise

Basalt samples obtained from the Siqueiros transform fault/fracture zone and the adjacent East Pacific Rise are mostly very fresh oceanic tholeiite and fractionated oceanic tholeiite with Fe+3/ Fe+2 ? 0.25; however, alkali basalts occur in the area as well. The rocks of the tholeiitic suite are ol + pl phyric and ol + pl + cpx phyric basalts, while the alkali basalts are ol and ol + pl phyric. Microprobe analyses of the tholeiitic suite phenocrysts indicate that they are Fo68-Fo86, An58-An75, and augite (Ca34Mg50Fe16). The range of olivine and plagioclase compositions represents the chemical variation of the phenocryst compositions with fractionation. The phenocyrsts in the alkali basalts are Fo81 and An69. The suite of tholeiites comprises a fractionation series characterized by relative enrichment of Fe, Ti, Mn, V, Na, K, and P and depletion of Ca, Al, Mg, Ni, and Cr. The fractionated tholeiites occur on the median ridge (which is a sliver of normal oceanic crust) of the double Siqueiros transform fault, on the western Siqueiros fracture zone, and on the adjoining East Pacific Rise, while the two transform fault troughs contain mostly unfractionated or only slightly fractionated tholeiite. We suggest that the fractionated tholeiites are produced by fractional crystallization of more 'primitive' tholeiitic liquid in a crustal magma chamber below the crest of the East Pacific Rise. This magma chamber may be disrupted by the transform fault troughs, thus explaining the paucity of fractionated tholeiites in the troughs. The alkali basalts are found only on the flanks of a topographic high near the intersection of the northern transform trough with the East Pacific Rise.

Annotated record and chemical composition of Mn deposits from R/V Mahi Cruise Abyssal Hills 69 stations

A University of Hawaii oceanographic cruise, Abyssal Hills 69, with the R/V Mahi, was carried out to study the association of manganese nodules with an abyssal hill. Manganese nodules from three dredge hauls on an abyssal hill located at 36°W and 157°W exhibited differences in morphology and composition between stations only three miles apart. The morphology of the nodules suggests that nodules from a single site have similar morphologies because they began growth at the same time, probably because of a volcanic event. Differences in morphology between stations indicate a local supply of elements. Atomic absorption analysis for manganese, iron, cobalt, nickel, and copper revealed that nodules nearest to a probable fault line and source of volcanism have a, lower manganese to iron ratio than nodules farther removed. This finding supports the theory that volcanism contributes to the formation of some nodules. Additional evidence showing association with volcanism consists of volcanic nuclei in nodules, crusts formed on layers of volcanic ash, and basalt encrusted to various degrees. The variation in cobalt, nickel, and copper contents Gt the nodules from a single dredge is two-to threefold, but iron content is more uniiorm. Four of the six cores from the area increased in manganese concentration with depth, suggesting that diffusion is concentrating manganese in the upper zone of the sediments or in nodules. The author concludes that volcanism is contributing to the formation of nodules by supplying nuclei and transition elements, but is not necessary for the formation of manganese nodules.

Annotated record of the detailed examination of Mn deposits from R/V Xiang Yang Hong 16 stations (1983) in the Pacific Ocean

Electron microprobe and X-ray diffraction data for north Pacific manganese nodules reveal that the transition metal distributions are controlled by the mineralogy. Microlayers rich in 10Å-manganates generally have high Mn/Fe ratios and positive correlations between Ni, Cu and Mn, and between Co and Fe. Microlayers rich in vernadite, on the other hand, show low Mn/Fe ratios, and Co, Ni and Cu all show positive correlations with Mn. The 10Å-manganates form mainly in porewaters with high Mn/Fe ratios. The Ni2+ and Cu2+ ions are post-depositionally incorporated into the interlayers of the manganates, whereas Co3+ is substituted for Fe3+ in ferric oxyhydroxides. In seawater with a low Mn/Fe ratio, on the other hand, the adsorption of positively charged ferric oxyhydroxides on negatively charged [MnO6] octahedral layers suppresses the growth of 10Å-manganates, enhancing the formation of vernadite. Positively charged hydroxides of Co3+, Ni2+ and Cu2+ are also adsorbed on the [MnO6] layers. These mechanisms of mineral formation and metal uptake are corroborated by data for other oceanic non-hydrothermal manganese nodules and crusts.

Annotated record and chemical analysis of manganese nodules from R/V Moana Wave Cruise Mn-74-01 and Mn-74-02 stations

Cruise Mn-74-02 of the R/V MOANA WAVE was the second part of the field work of the NSF/IDOE Inter-University Ferromanganese Research Program in 1974, and we gratefully acknowledge the support of the office for the International Decade of Ocean Exploration and the Office of Oceanographic Facilities and Support. This program was designed to investigate the origin, growth, and distribution of copper/nickel-rich manganese nodules in the Pacific Ocean. The field effort was designed to satisfy sample requirements of the fifteen principal investigators, while increasing general knowledge of the copper/nickel-rich nodule deposits of the equatorial Pacific. This report is the second of a series of cruise reports designed to assist sample requests for documented nodules, sediment, and water samples so that laboratory results can be realistically compared and related to the environment of nodule growth. Nodule samples and bathymetric and navigational data are archived at the Hawaii Institute of Geophysics, University of Hawaii. Bulk chemical analyses of nodules and reduction of survey data were carried out at Hawaii. Sediment cores were stored at the University of Hawaii and at Scripps Institution of Oceanography. The SIO analytical facility provided stratigraphic data on sediment chemistry.

Effect of foliar application of Cu, Zn, and Mn on yield and quality indicators of winter wheat grain

Micronutrients are part of many crucial physiological plant processes. The combined application of N and micronutrients helps in obtaining grain yield with beneficial technological and consumer properties. The main micronutrients needed by cereals include Cu, Mn, and Zn. The subject of this study was to determine yield, quality indicators (protein content and composition, gluten content, grain bulk density, Zeleny sedimentation index, and grain hardness), as well as mineral content (Cu, Zn, Mn, Fe) in winter wheat grain ( Triticum aestivum L.) fertilized by foliar micronutrient application. A field experiment was carried out at the Educational and Experimental Station in Tomaszkowo, Poland. The application of mineral fertilizers (NPK) supplemented with Cu increased Cu content (13.0%) and ω, α/β, and γ (18.7%, 4.9%, and 3.4%, respectively) gliadins in wheat grain. Foliar Zn fertilization combined with NPK increased Cu content (14.9%) as well as high (HMW) and low molecular weight (LMW) glutenins (38.8% and 6.7%, respectively). Zinc fertilization significantly reduced monomeric gliadin content and increased polymeric glutenin content in grain, which contributed in reducing the gliadin:glutenin ratio (0.77). Mineral fertilizers supplemented with Mn increased Fe content in wheat grain (14.3%). It also significantly increased protein (3.8%) and gluten (4.4%) content, Zeleny sedimentation index (12.4%), and grain hardness (18.5%). Foliar Mn fertilization increased the content of ω, α/β, and γ gliadin fractions (19.9%, 9.5%, and 2.1%, respectively), as well as HMW and LMW glutenins (18.9% and 4.5%, respectively). Mineral NPK fertilization, combined with micronutrients (Cu + Zn + Mn), increased Cu and Zn content in grain (22.6% and 17.7%, respectively). The content of ω, α/β, and γ gliadins increased (20.3%, 10.5%, and 12.1%, respectively) as well as HMW glutenins (7.9%).

Evaluation Of Fe Uptake And Translocation In Transgenic And Non-transgenic Soybean Plants Using Enriched Stable (57)fe As A Tracer.

A tracer experiment is carried out with transgenic T (variety M 7211 RR) and non-transgenic NT (variety MSOY 8200) soybean plants to evaluate if genetic modification can influence the uptake and translocation of Fe. A chelate of EDTA with enriched stable (57)Fe is applied to the plants cultivated in vermiculite plus substrate and the (57)Fe acts as a tracer. The exposure of plants to enriched (57)Fe causes the dilution of the natural previously existing Fe in the plant compartments and then the changed Fe isotopic ratio ((57)Fe/(56)Fe) is measured using a quadrupole-based inductively coupled plasma mass spectrometer equipped with a dynamic reaction cell (DRC). Mathematical calculations based on the isotope dilution methodology allow distinguishing the natural abundance Fe from the enriched Fe (incorporated during the experiment). The NT soybean plants acquire higher amounts of Fe from natural abundance (originally present in the soil) and from enriched Fe (coming from the (57)Fe-EDTA during the experiment) than T soybean ones, demonstrating that the NT soybean plants probably absorb higher amounts of Fe, independently of the source. The percentage of newly incorporated Fe (coming from the treatment) was approximately 2.0 and 1.1% for NT and T soybean plants, respectively. A higher fraction (90.1%) of enriched Fe is translocated to upper parts, and a slightly lower fraction (3.8%) is accumulated in the stems by NT plants than by T ones (85.1%; 5.1%). Moreover, in both plants, the Fe-EDTA facilitates the transport and translocation of Fe to the leaves. The genetic modification is probably responsible for differences observed between T and NT soybean plants.

Tuning The Surface Anisotropy In Fe-doped Nio Nanoparticles.

Ni(1-x)FexO nanoparticles have been obtained by the co-precipitation chemical route. X-ray diffraction analyses using Rietveld refinement have shown a slight decrease in the microstrain and mean particle size as a function of the Fe content. The zero-field-cooling (ZFC) and field-cooling (FC) magnetization curves show superparamagnetic behavior at high temperatures and a low temperature peak (at T = 11 K), which is enhanced with increasing Fe concentration. Unusual behavior of the coercive field in the low temperature region and an exchange bias behavior were also observed. A decrease in the Fe concentration induces an increase in the exchange bias field. We argue that these behaviors can be linked with the strengthening of surface anisotropy caused by the incorporation of Fe ions.

Comparação da eficiência do processo de ozonização e ozonização catalítica (Mn II e Cu II) na degradação de fenol

This paper discusses the results obtained with homogeneous catalytic ozonation [Mn (II) and Cu (II)] in phenol degradation. The reduction of total phenols and total organic carbon (TOC) and the ozone consumption were evaluated. The efficiency in phenol degradation (total phenol removal) at pH 3, with the catalytic process (Mn (II)), increased from 37% to 55% while the TOC removal increased from 4 to 63% in a seven-minute treatment. The ozonation process efficiency at pH 10 was 43% and 39% for phenol and TOC removal, respectively. The presence of both metallic ions (Mn2+ and Cu+2) in the ozonation process resulted in a positive effect.