(Table 1, page 661) Average composition of fossil nodules from three localities studied in the Transdanubian Central Mountains of Hungary

Fossil manganese nodules and encrustations from seamount' and basin' localities in the Transdanubian Central Mountains of Hungary are lithologically, mineralogically and chemically similar to some modern marine ferromanganese oxide deposits, and show no evidence of postdepositional changes other than cementation. Five groups of deposits were encountered: Fe/Mn nodules, encrusted shells, pavements, stains, and Fe oxide encrusted intraclasts, the first three of which are specific to the 'seamount' environment and the last to the basins'. Optical and electron microprobe investigation of the samples shows them to exhibit many similarities with modern ferromanganese oxide deposits, and that many of the nodules are surrounded by a halo of dispersed ferromanganese oxides, strongly suggesting that they continued to accrete metals through the pore waters of unlithified sediments for a period after burial. By contrast, pavements which appear to have grown on hardgrounds at the sea floor show little or no evidence of derivation of metals from underlying sediments. Geochemical investigations on the deposits show the seamount' varieties to be closer in composition to most modern nodules and crusts than the basin' varieties, and that the latter are essentially manganese and trace-element-poor ferruginous deposits. Nevertheless, all can be more or less compositionally equated with modern ferromanganese oxide deposits forming in marginal Atlantic environments, which would be in accord with the proposed depositional environment of the Transdanubian Central Mountains based on other evidence.

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.

Description and chemical composition of manganese nodules during R/V "Tyro" cruise APNAP 1 to the Madeira Abyssal Plain in 1986

The porewater and sediment composition of two boxcores and of a small gravity core, taken on a manganese-nodule-covered hill and in the Madeira Abyssal Plain proper respectively, are compared. The pore-water study of the two boxcores indicates that oxic conditions prevail in both cores. In addition, it indicates that no detectable fluxes of Mn or Fe occur from the porewater to the ocean bottom water. Variations in the geochemical composition of the sediments can be explained by fluctuations in the amount of carbonate, which acts as a diluting agent. A clear carbonate minimum is observed at 20-22 cm depth in the two cores. This minimum is likely to be associated with the last glacial period (10-20 kyr B.P.). This association is supported by the sediment accumulation rate of 15 mm/kyr as found by extrapolation from the rate for pelagic sediments in the Madeira Abyssal Plain. The bulk composition of the manganese nodules recovered from the submarine hill is chemically almost identical to the average composition of Atlantic nodules. The trace metal and Rare Earth Elements composition indicate a hydrogenous origin for the manganese nodules of this study. On the basis of the chemical composition, and that of nodules relative to that of the adjacent sediments, an average nodule accretian rate of 2.8-3.3 mm/myr has been calculated. Although the analyses of the entire ferromanganese nodules that have been studied seem to indicate a homogenous composition, internal structures of the nodules reveal great inhomogeneity, both visually and chemically. These fluctuations may be related to variations in the fluxes of Mn and Fe, which in turn could be climate-related.

Composition of pore water and diagenetic carbonates of ODP Site 123-765

Degradation of organic matter in slightly organic-rich (1 wt% organic carbon) Neogene calcareous turbidites of the Argo Basin at Site 765 by sulfate reduction results in pore-water phosphate, ammonium, manganese, and carbonate alkalinity maxima. Pore-water calcium and magnesium decrease in the uppermost 100 meters below seafloor (mbsf) in response to the precipitation of calcian dolomite with an average composition of Ca1.15Mg0.83Fe0.02(CO3)2. Clear, euhedral dolomite rhombs range from <1 to 40 µm in diameter and occur in trace to minor amounts (<1-2 wt%) in Pleistocene to Pliocene sediment (62-210 mbsf) The abundance of dolomite increases markedly (2-10 wt%) in Miocene sediment (210-440 mbsf). The dolomite is associated with diagenetic sepiolite and palygorskite, as well as redeposited biogenic low-Mg calcite and aragonitic benthic foraminifers. Currently, dolomite is precipitating at depth within the pore spaces of the sediment, largely as a result of aragonite dissolution. The rate of aragonite dissolution, calculated from the pore-water strontium profile, is sufficient to explain the amount of dolomite observed at Site 765. A foraminiferal aragonite precursor is further supported by the carbon and oxygen isotopic compositions of the dolomite, which are fairly close to the range of isotopic compositions observed for Miocene benthic foraminifers. Dolomite precipitation is promoted by the degradation of organic matter by sulfate-reducing bacteria because the lower pore-water sulfate concentration reduces the effect of sulfate inhibition on the dolomite reaction and because the higher carbonate alkalinity increases the degree of saturation of the pore waters with dolomite. Organic matter degradation also results in the precipitation of pyrite and trace amounts of apatite (francolite), and the release of iron and manganese to the pore water by reduction of Fe and Mn oxides. Spherical, silt-sized aggregates of microcrystalline calcian rhodochrosite occur in trace to minor amounts in Lower Cretaceous sediment from 740 to 900 mbsf at Site 765. A negative carbon isotopic composition suggests that the rhodochrosite formed early in the sulfate reduction zone, but a depleted oxygen isotopic composition suggests that the rhodochrosite may have recrystallized at deeper burial depths.

Chemical composition of the soluble fraction of oxidate portions of Lakes Shebadnowan ferromanganese concretions

Shebandowan Lakes, Ontario, are the site of at least 49 shallow (2-12 m) ferromanganese concretion deposits, widely distributed throughout the 48 km of the watercourse. X-ray diffraction and Mossbauer methods have revealed the presence of goethite in some of the concretions. Chemical analyses of the acid soluble portions of 72 samples gave an average composition of 43.1% Fe and 5.65% Mn with a low content of trace elements. The Shebandowan concretions are among the richest in iron of lake concretions reported, possibly because only the acid soluble portion was analysed. Their low content of trace elements suggests rapid growth rates and a relatively young age. A positive correlation was found between Mn and K, Ca, Mg, Cu, Ni, and Co and the relationship between the last three and Mn was deemed significant. Zn was independent of association with either Mn and Fe, probably due to the presence locally of zinc sulphide deposits. Analyses of lake bottom and influent waters suggested that frequent resampling of the sites would be required throughout the year to permit meaningful interpretation of the effect of water composition of concretions. Analyses of sediment cores from 20 concretion sites indicated an upward increase in Fe and Mn and in the Mn/Fe ratio, consistent with the model of upward migration of the elements, where Mn is more mobile than Fe. This study concludes that a considerable proportion of the elements have been supplied to the Shebandowan concretions via the diagenetic process; generally a minor fraction of the elements has been abstracted directly from the superjacent water.

Cu2ZnSnS4 absorber layers obtained through sulphurization of metallic precursors: Graphite box versus sulphur flux

In this work we employed a hybrid method, combining RF-magnetron sputtering with evaporation, for the deposition of tailor made metallic precursors, with varying number of Zn/Sn/Cu (ZTC) periods and compared two approaches to sulphurization. Two series of samples with 1×, 2× and 4× ZTC periods have been prepared. One series of precursors was sulphurized in a tubular furnace directly exposed to a sulphur vapour and N2+5% H2 flux at a pressure of 5.0×10+4 Pa. A second series of identical precursors was sulphurized in the same furnace but inside a graphite box where sulphur pellets have been evaporated again in the presence of N2+5% H2 and at the same pressure as for the sulphur flux experiments. The morphological and chemical analyses revealed a small grain structure but good average composition for all three films sulphurized in the graphite box. As for the three films sulphurized in sulphur flux grain growth was seen with the increase of the number of ZTC periods whilst, in terms of composition, they were slightly Zn poor. The films' crystal structure showed that Cu2ZnSnS4 is the dominant phase. However, in the case of the sulphur flux films SnS2 was also detected. Photoluminescence spectroscopy studies showed an asymmetric broad band emission whichoccurs in the range of 1–1.5 eV. Clearly the radiative recombination efficiency is higher in the series of samples sulphurized in sulphur flux. We have found that sulphurization in sulphur flux leads to better film morphology than when the process is carried out in a graphite box in similar thermodynamic conditions. Solar cells have been prepared and characterized showing a correlation between improved film morphology and cell performance. The best cells achieved an efficiency of 2.4%.

Organic acids in the rhizosphere and phytoavailability of sewage sludge-borne trace elements

The aim of this work was to quantify low molecular weight organic acids in the rhizosphere of plants grown in a sewage sludge-treated media, and to assess the correlation between the release of the acids and the concentrations of trace-elements in the shoots of the plants. The species utilized in the experiment were cultivated in sand and sewage sludge-treated sand. The acetic, citric, lactic, and oxalic acids, were identified and quantified by high performance liquid chromatography in samples collected from a hydroponics system. Averages obtained from each treatment, concentration of trace elements in shoots and concentration of organic acids in the rhizosphere, were compared by Tukey test, at 5% of probability. Linear correlation analysis was applied to verify an association between the concentrations of organic acids and of trace elements. The average composition of organic acids for all plants was: 43.2, 31.1, 20.4 and 5.3% for acetic, citric, lactic, and oxalic acids, respectively. All organic acids evaluated, except for the citric acid, showed a close statistical agreement with the concentrations of Cd, Cu, Ni, and Zn found in the shoots. There is a positive relationship between organic acids present in the rhizosphere and trace element phytoavailability.