Metamorphic rocks of the Murmansk domain (Kola Peninsula) as compared with the oldest rock associations of the northeastern Baltic shield,Canada, and Greenland

Rock associations characterized by heterogeneous sets of petrogeochemical parameters were compared by quantifying the degree of their similarity-dissimilarity and searching for discrimination trends between them. Using procedures specially developed for this purpose, it was demonstrated for the first time that the lithotectonic complexes of the Murmansk domain are fundamentally different from those of typical granulite-gneiss terrains and resemble the granite-greenstone terrains of the Baltic shield, Greenland, and Canada. Based on the whole data set, the Murmansk domain can be considered as a deeply eroded Archean granite-greenstone terrain retaining only the tonalite-trondhjemite-gneiss basement with abundant supracrustal enclaves. A trend of the compositional difference between the older and younger rock associations is similar to that between the tholeiitic and boninitic volcanic series. It was suggested that the petrogeochemical “age” trend reflects the initial stage of the compositional evolution of the metamagmatic rocks of the region from metamorphic rocks similar to tholeiites at the early stages to the Paleoproterozoic boninite-like rocks, which are believed to be linked to the unique PGE-bearing province of the northeastern Baltic shield. This implies that the specific metallogenic features of the region emerged already in the Archean, which supported the suggestion on the long duration of geological processes in the Early Precambrian.     

Chrome-spinels in serpentinites and talc carbonates of the El Ideid-El Sodmein District, central Eastern Desert, Egypt: their metamorphism and petrogenetic implications

Serpentinites and talc-carbonate rocks of El Ideid-El Sodmein District (ISD), central Eastern Desert, Egypt, contain variably altered chrome-spinels. Back-scattered electron images and electron microprobe analyses of chrome-spinels and associated silicates are made to evaluate their textural and compositional variations with metamorphism. In most cases the chrome-spinel crystals are concentrically zoned with unaltered cores through transitional zone of ferritchromit to Cr-magnetite toward the rims. In talc-carbonate rocks chrome-spinels are extensively altered to Cr-magnetite. Compared to cores, the metamorphic rims are enriched in Cr# (0.83–1.0 vs. 0.58–0.63 for rims and cores, respectively) and impoverished in Mg# (0.05–0.29 vs. 0.57–0.63), due to Mg–Fe and Al(Cr)–Fe³⁺ exchange with the surrounding silicates during regional metamorphism rather than serpentinization process. Textural and compositional features of the chrome-spinels suggest transitional greenschist-amphibolite up to lower amphibolite facies metamorphism (at 500–600 °C), which is isofacial with the country rocks. The common preservation of unaltered chrome-spinel cores in the serpentinites, contrary to talc-carbonate rocks, implies that full equilibration has not been attained due to small metamorphic fluid–rock ratio. Microprobe analyses profile across a concentrically zoned grain confirms the presence of two compositional (miscibility?) gaps; one between chrome-spinel core and ferritchromit zone; and another one between ferritchromit zone and Cr-magnetite outer rim.Chrome-spinel cores do not appear to have re-equilibrated completely with the metamorphic spinel rims and surrounding silicates, indicating relic magmatic composition not affected by metamorphism. Core compositions suggest an ophiolitic origin and derivation by high degrees of melting of reduced, depleted harzburgite to dunite mantle peridotites in an oceanic supra-subduction zone (marginal-basin) tectonic environment.     

Development and morphometry of sinkholes in coastal plains of Apulia, southern Italy. Preliminary sinkhole susceptibility assessment

Evolution of coastlines in karst areas may be strongly controlled by dissolution processes which favour the development of surface and subsurface landforms. The generation of caves in these environments is commonly favoured by the mixing between fresh and brackish waters. The sinkholes resulting from the upward propagation of the caves may interfere with the anthropogenic environment and cause damage to human elements (property and activities). To highlight the often underestimated importance of karst phenomena in coastal areas, we have analyzed a coastal stretch of Apulia, in southern Italy. The study area, covering an extension of about 6 km², is situated in the Ionian coast, and presents several interesting karst landforms that are generally connected to caves. Tens of sinkholes were mapped through field surveys, multi-year aerial-photographs (dating back to the 1940s) and archival research. We have performed a morphometric analysis of the sinkholes. The analysis describes the main parameters of the sinkholes (area, length, width, and depth), and the control exerted by the main discontinuity systems in the area. The detrimental effects derived from interaction between human environment and these karst landforms is also under consideration. A sinkhole susceptibility map, which may provide useful information for planners, developers and the insurance industry has eventually been produced through application of a decision tree model.     

Fast kimberlite ascent rates estimated from hydrogen diffusion profiles in xenolithic mantle olivines from southern Africa

Fourier transform infrared spectrometry (FTIR) analyses of olivines from peridotite xenoliths found in southern African kimberlites indicate 0 to 80 ppm H₂O concentrations. OH absorbance profiles across olivine grains show homogeneous H contents from core to edge for most samples. In one sample the olivines are H-free, while another has olivines characterized by lower H contents at the grain edges compared to the cores, indicating H loss during transport of the xenolith to the surface. Flat or near-flat H profiles place severe constraints on the duration of H loss from olivine grains, with implications for kimberlite magma ascent rates. Diffusion equations were used to estimate times of H loss of about 4 h for the sample with heterogeneous olivine H contents. Resulting kimberlite ascent rates are calculated to be 5-37 m s⁻¹ minimum, although these estimates are highly dependent on volatile contents and degassing behavior of the host kimberlite magma. Xenolithic olivines from alkali basalts generally have lower H contents and more pronounced H diffusion profiles than do those from kimberlites. This difference is likely caused by higher magma temperatures and lower ascent rates of alkali basalts compared to kimberlites.     

Upwelling, species, and depth effects on coral skeletal cadmium-to-calcium ratios (Cd/Ca)

Skeletal cadmium-to-calcium (Cd/Ca) ratios in hermatypic stony corals have been used to reconstruct changes in upwelling over time, yet there has not been a systematic evaluation of this tracer’s natural variability within and among coral species, between depths and across environmental conditions. Here, coral skeletal Cd/Ca ratios were measured in multiple colonies of Pavona clavus, Pavona gigantea and Porites lobata reared at two depths (1 and 7 m) during both upwelling and nonupwelling intervals in the Gulf of Panama (Pacific). Overall, skeletal Cd/Ca ratios were significantly higher during upwelling than during nonupwelling, in shallow than in deep corals, and in both species of Pavona than in P. lobata. P. lobata skeletal Cd/Ca ratios were uniformly low compared to those in the other species, with no significant differences between upwelling and nonupwelling values. Among colonies of the same species, skeletal Cd/Ca ratios were always higher in all shallow P. gigantea colonies during upwelling compared to nonupwelling, though the magnitude of the increase varied among colonies. For P. lobata, P. clavus and deep P. gigantea, changes in skeletal Cd/Ca ratios were not consistent among all colonies, with some colonies having lower ratios during upwelling than during nonupwelling. No statistically significant relationships were found between skeletal Cd/Ca ratios and maximum linear skeletal extension, δ¹³C or δ¹⁸O, suggesting that at seasonal resolution the Cd/Ca signal was decoupled from growth rate, coral metabolism, and ocean temperature and salinity, respectively. These results led to the following conclusions, (1) coral skeletal Cd/Ca ratios are independent of skeletal extension, coral metabolism and ambient temperature/salinity, (2) shallow P. gigantea is the most reliable species for paleoupwelling reconstruction and (3) the average Cd/Ca record of several colonies, rather than of a single coral, is needed to reliably reconstruct paleoupwelling events.     

Experimental investigation of the effects of temperature and ionic strength on Mo isotope fractionation during adsorption to manganese oxides

The Mo stable isotope system is being applied to study changes in ocean redox. Such applications implicitly assume that Mo isotope fractionation in aqueous systems is relatively insensitive to frequently changing environmental variables such as temperature (T) and ionic strength (I). A major driver of fractionation is the adsorption of Mo to Mn oxyhydroxide surfaces [Barling J. and Anbar A. D. (2004) Molybdenum isotope fractionation during adsorption by manganese oxides. Earth Planet. Sci. Lett.217(3-4), 315-329]. Here, we report the results of experiments that determine the extent to which Mo isotope fractionation during adsorption of Mo to the Mn oxyhydroxide mineral birnessite is sensitive to T and I. The results are compared to new predictions from quantum chemical computations. We measured fractionation from 1 to 50 °C at I = 0.1 m and found that Δ^97/95Mo_{dissolved-adsorbed} varies from 1.9‰ to 1.6‰ over this temperature range. Experiments were also performed at 25 °C in synthetic seawater (I = 0.7); fractionation at this condition was the same within analytical error as in low ionic strength experiments. These findings confirm that the Mo isotope fractionation during adsorption to Mn oxyhydroxides is relatively insensitive to variations and T and I over environmentally relevant ranges. To relate these findings to potential mechanisms of Mo isotope fractionation, we also report results for density functional theory computations of the fractionation between and various possible structures of molybdic acid as a function of temperature. Because no plausible species fractionates from with a magnitude matching the experiments, we are left with three possibilities to explain the fractionation: (1) solvation effects on the vibrational frequencies of aqueous species considered thus far are significant, such that our calculations in vacuo yield inaccurate fractionations; (2) a trace aqueous species not yet considered fractionates from and then adsorbs to birnessite; or (3) a surface complex not present in solution forms on birnessite in which Mo is not tetrahedrally coordinated. Our findings help validate assumptions underlying paleoceanographic applications of the Mo isotope system and also lead us closer to understanding the mechanism of isotope fractionation during adsorption of Mo to Mn oxyhydroxides.     

The composition and crystallinity of the near-surface regions of weathered alkali feldspars

Our ability to identify thin non-stoichiometric and amorphous layers beneath mineral surfaces has been tested by undertaking X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) work on alkali feldspars from pH 1 dissolution experiments. The outcomes of this work were used to help interpret XPS and TEM results from alkali feldspars weathered for <10,000 years in soils overlying the Shap Granite (north-west England). The chemistry of effluent solutions indicates that silica-rich layers a few nanometers in thickness formed during the pH 1 experiments. These layers can be successfully identified by XPS and have lower Al/Si, Na/Si, K/Si and Ca/Si values than the outermost ∼9 nm of unweathered controls. Development of Al-Si non-stoichiometry is coupled with loss of crystal structure to produce amorphous layers that are identifiable by TEM where >∼2.5 nm thick, whereas the crystallinity of albite is retained despite leaching of Na to depths of tens to hundreds on nanometers. Integration of XPS data over the outermost 6-9 nm of naturally weathered Shap feldspars shows that they have stoichiometric Al/Si and K/Si ratios, which is consistent with findings of previous TEM work on the same material that they lack amorphous layers. There is some XPS evidence for loss of K from the outermost couple of nanometers of Shap orthoclase, and the possibility of leaching of Na from albite to greater depths cannot be excluded using the XPS or TEM results. This study demonstrates that the leached layer model, as formulated from laboratory experiments, is inapplicable to the weathering of alkali feldspars within acidic soils, which is an essentially stoichiometric reaction.     

A spectrophotometric study of Nd(III), Sm(III) and Er(III) complexation in sulfate-bearing solutions at elevated temperatures

The speciation of Nd(III), Sm(III), and Er(III) in sulfate-bearing solutions has been determined spectrophotometrically at temperatures from 25 to 250 °C and a pressure of 100 bars. The data obtained earlier on the speciation of Nd in sulfate-bearing solutions (Migdisov et al., 2006) have been re-evaluated and corrected using a more appropriate activity model and are compared with the corresponding data for Sm(III) and Er(III) and new data for Nd(III). Based on this comparison, the dominant species in the solution are interpreted to be and , with the latter complex increasing in importance at higher temperature. Equilibrium constants were calculated for the following reactions:

     

Large and giant hydrocarbon accumulations in the transitional continent-ocean zone

The petroleum resource potential is considered for the Atlantic, West Pacific, and East Pacific types of deepwater continental margins. The most considerable energy resources are concentrated at the Atlantic-type passive margins in the zone transitional to the ocean. The less studied continental slope of backarc seas of the generally active margins of the West Pacific type is currently not so rich in discoveries as the Atlantic-type margin, but is not devoid of certain expectations. In some of their parameters, the margins bounded by continental slopes may be regarded as analogs of classical passive margins. At the margins of the East Pacific type, the petroleum potential is solely confined to transform segments. In the shelf-continental-slope basins of the rift and pull-apart nature, petroleum fields occur largely in the upper fan complex, and to a lesser extent in the lower graben (rift) complex. In light of world experience, the shelf-continental-slope basins of the Arctic and Pacific margins of Russia are evaluated as highly promising.     

Opacitization conditions of hornblende in Bezymyannyi volcano andesites (March 30, 1956 eruption)

The paper is devoted to the conditions under which opacite rims developed around hornblende grains in andesite of the catastrophic eruption (March 30, 1956) of Bezymyannyi volcano, Kamchatka. The opacite rims were produced by a bimetasomatic reaction between hornblende and melt with the development of the following zoning: hornblende → Px + Pl + Ti-Mag → Px + Pl → Px → melt. Biometasomatic reaction was accompanied by the active removal of CaO from the rim, addition of SiO₂, and more complicated behavior of other components. The hornblende also shows reactions of its volumetric decomposition under near-isochemical conditions. The opacite rims developed under isobaric conditions, at a pressure of approximately 6 kbar. The main reason for the instability of the hornblende was the heating of the magma chamber from 890 to 1005°C due to new hot magma portion injection. The time interval between the injection and the start of eruption was estimated from the thickness of the opacite rims and did not exceed 37 days. Hence, the March 30, 1956, eruption was not related to the volcanic activity in November of 1955 but to the injection of a fresh magma portion in February–March of 1956.