Geochemistry of iron and manganese in soils and sediments of a mangrove system, Island of Pai Matos (Cananeia - SP, Brazil)

Five zones along a transect of 180 m were selected for study on the Island of Pai Matos (Sao Paulo, Brazil). Four of the zones are colonised by vascular plants (Spartina SP, Laguncularia LG, Avicennia AV and Rhizophora RH) and were denominated soils, and the other zone, which lacks vegetation, was denominated sediment (SD). The geochemical conditions differed significantly in soils and sediment and also at different depths. The soils were oxic (Eh > 350 mV) or suboxic (Eh: 350-100 mV) at the surface and anoxic (Eh < 100 mV) at depth, whereas in the sediment anoxic conditions prevailed at all depths, but with a lower concentration of sulphides in the pore water and pyrite in the solid fraction. Under these geochemical conditions Fe is retained in the soils, while the Mn tends to be mobilized and lost. The most abundant form of iron oxyhydroxide was lepidocrocite (mean concentration for all sites and depths, 45 +/- 19 mu mol g(-1)), followed by goethite (30 19 mu mol g(-1))and ferrihydrite (19 +/- 11 mu mol g(-1)),with significant differences among the mean concentrations. There was a significant decrease with depth in all the types of Fe oxyhydroxides measured, particularly the poorly crystalline forms. The pyrite fraction was an important component of the free Fe pool (non-silicate Fe) in all soils as well as in the sediment, especially below 20 cm depth (mean concentration for all sites and depths, 60 +/- 54 mu mol CI). Furthermore, the mean concentration of Fe-pyrite for all sites and depths was higher than that obtained for any of the three Fe oxyhydroxides measured. The Fe-AVS was a minor fraction, indicating that the high concentrations of dissolved Fe in the soils in the upper area of the transect result from the oxidation of Fe sulphides during low tide. Mossbauer spectroscopy also revealed that most of the Fe (III) was associated with silicates, in this case nontronite. The presence of crystals of pyrite associated with phyllosilicates in samples from the upper layer of the soils may indicate that pyritization of this form of Fe(III) is more rapid than usually reported for ocean bed sediments. The sequential extraction of Mn did not reveal any clearly dominant fraction, with the Mn-carbonate fraction being the most prevalent, followed by exchangeable Mn and oxides of Mn, whereas pyrite-Mn and Mn associated with crystalline Fe-oxides were present at significantly lower concentrations. The high concentration of dissolved Mn found in the soils in the lower part of the transect is consistent with the fact that the solubility is determined by the carbonate fraction. Unlike for Fe, in the soils in the higher zone, which are subject to intense drainage during low tide, there was loss of Mn, as reflected by the concentration of total Mn. (C) 2008 Elsevier B.V. All rights reserved.

Geochemical composition of a representative collection of manganese nodules and slabs collected in the Western Pacific

Chemical analyses were performed on seveteen manganese nodules collected from the Pacific Ocean floor. The results were discussed compared with the previous data on the manganese nodules. Minerals were found to be todorokite, delta-MnO2 and other silicates, montmorillonite, illite, phillipsite and alpha-SiO2. Average composition shows that copper is concentrated on the deep sea nodules more than the shallow ones, and that the todorokite rich nodules contain more copper and nickel than the delta-MnO2 rich ones.

Description and chemical composition of manganese nodules collected in the Pacific Ocean

Chemical and X-ray analyses were performed on the fifteen manganese nodules collected from the Pacific Ocean floor. The results were discussed compared with the previous data on the manganese nodules. Minerals were found to be todorokite, delta-MnO2 and other silicates, montmorillonite, illite, phillipsite and alpha-Si02. Average composition shows that copper is concentrated on the deep sea nodules more than the shallow ones, and that the todorokite rich nodules contain more copper and nickel than the delta-MnO2 rich ones. The analyses of fresh water iron-manganese precipitates by bacterial activity suggest that biological process is one of the important factors on the genesis of the sedimentary iron-manganese deposits, in¬cluding the manganese nodule.

Documentation of manganese nodules form the northwest Indian Ocean

Microscopic and electron probe examination of some manganese nodules show that they consist of segregations of manganese-iron oxides in an interstitial material almost free of manganese but rich in iron and silicates. The segregations are widely spaced in the volcanic cores of the nodules but become more abundant towards their outer crusts where they form the centres of linked polygons of interstitial materials. Most of the minor elements are concentrated in the segregations compared to the interstitial materials. It is suggested that the structures observed result partly from solution and reprecipitation of elements in the original volcanic cores of the nodules and partly from the replacement and coating of these cores by manganese-iron oxides precipitated from sea water.

(Table 1) Chemical composition of Fe-rich layered silicates from the East Korean Rise, Japan Sea

Mineral and chemical compositions of highly ferruginous layered silicates (HLS) of glauconite sands occurred on the East Korean Rise outside volcanic structures and on an unnamed volcano and the Chentsov Volcano have been studied. The use of cluster and discriminant analyses has resulted to more objectively distinguished groups among HLS, and the use of factor analysis - to illustrate correlations between chemical elements in different groups. It has been found that green mineral assemblages of the East Korean Rise are heterogeneous in terms of morphology, composition and origin, and their formation is a complex multistage process including both neoformation and degradation.

Chemical composition of layer silicates from the Sado Ridge, Sea of Japan

Detailed mineralogical investigations of high-Fe layer silicates from loose sediments (glauconite sands) of the Sado Ridge revealed that green aggregates found on submarine rises of the Japan Sea floor have different genesis. It was demonstrated that round dark green grains approximate micas in composition. Primary volcanic rocks presumably have undergone extensive secondary alterations and then were disintegrated. Their disintegration products (protoceladonite) filling pores were redeposited and buried in sediments for a long time. Angular green grains mainly represented by smectite also formed at lower temperatures during disintegration of altered volcanosedimentary rocks. These younger grains had no prolonged exposure. Pseudomorphs of siliceous microplankton consist of both hydromica and smectites. They are presumably authigenic products formed with participation of microorganisms or electrostatic processes (spherical shape), or their combination. The formation mechanism of minerals filling cavities in pyroclastics is not entirely clear.

Description and chemical composition of manganese nodules in a core located in the Nares Abyssal Plain, Atlantic Ocean

Three nodules from a core taken north of Puerto Rico are composed chiefly of an x-ray amorphous, hydrated, iron-manganese oxide, with secondary goethite, and minor detrital silicates incorporated during growth of the nodules. No primary manganese mineral is apparent. The nodules are enriched in iron and depleted in manganese relative to Atlantic Ocean averages. The formation of these nodules appears to have been contemporary with sedimentation and related to volcanic activity.

Synthesis and thermal stability of hydrotalcites containing manganese

The hydrotalcite based upon manganese known as charmarite Mn4Al2(OH)12CO3•3H2O has been synthesised with different Mn/Al ratios from 4:1 to 2:1. Impurities of manganese oxide, rhodochrosite and bayerite at low concentrations were also produced during the synthesis. The thermal stability of charmarite was investigated using thermogravimetry. The manganese hydrotalcite decomposed in stages with mass loss steps at 211, 305 and 793°C. The product of the thermal decomposition was amorphous material mixed with manganese oxide. A comparison is made with the thermal decomposition of the Mg/Al hydrotalcite. It is concluded that the synthetic charmarite is slightly less stable than hydrotalcite.