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.     

Triassic Nb-enriched basalts, magnesian andesites, and adakites of the Qiangtang terrane (Central Tibet): evidence for metasomatism by slab-derived melts in the mantle wedge

New chronological, geochemical, and isotopic data are reported for Triassic (219–236 Ma) adakite-magnesian andesite-Nb-enriched basaltic rock associations from the Tuotuohe area, central Qiangtang terrane. The adakites and magnesian andesites are characterized by high Sr/Y (25–45), La/Yb (14–42) and Na₂O/K₂O (12–49) ratios, high Al₂O₃ (15.34–18.28 wt%) and moderate to high Sr concentrations (220–498 ppm) and ε_ND (t) (+0.86 to +1.21) values. Low enrichments of Th, Rb relative to Nb, and subequal normalized Nb and La contents, and enrichments of light rare earth elements combine to distinguish a group of Nb-enriched basaltic rocks (NEBs). They have positive ε_ND (t) (+2.57 to +5.16) values. Positive correlations between Th, La and Nb and an absence of negative Nb anomalies on mantle normalized plots indicate the NEBs are products of a mantle source metasomatized by a slab melt rather than by hydrous fluids. A continuous compositional variation between adakites and magnesian andesites confirms slab melt interaction with mantle peridotite. The spatial association of the NEBs with adakites and magnesian andesites define an “adakitic metasomatic volcanic series” recognized in many demonstrably subduction-related environments (e.g., Mindanao arc, Philippines; Kamchatka arc, Russia; and southern Baja California arc, Mexico). The age of the Touhuohe suite, and its correlation with Triassic NEB to the north indicates that volcanism derived from subduction-modified mantle was abundant prior to 220 Ma in the central Qiangtang terrane.     

The Ca-Eskola component in eclogitic clinopyroxene as a function of pressure, temperature and bulk composition: an experimental study to 15 GPa with possible implications for the formation of oriented SiO2-inclusions in omphacite

Experiments have been conducted in the P-T range 2.5–15 GPa and 850–1,500°C using bulk compositions in the systems SiO₂–TiO₂–Al₂O₃–Fe₂O₃–FeO–MnO–MgO–CaO–Na₂O–K₂O–P₂O₅ and SiO₂–TiO₂–Al₂O₃–MgO–CaO–Na₂O to investigate the Ca-Eskola (CaEs Ca_0.5□_0.5AlSi₂O₆) content of clinopyroxene in eclogitic assemblages containing garnet + clinopyroxene + SiO₂ ± TiO₂ ± kyanite as a function of P, T, and bulk composition. The results show that CaEs_ss in clinopyroxene increases with increasing T and is strongly bulk composition dependent whereby high CaEs-contents are favoured by bulk compositions with high normative anorthite and low diopside contents. In this study, a maximum of 18 mol% CaEs_ss was found at 6 GPa and 1,350°C in a kyanite-eclogite assemblage garnet + clinopyroxene + kyanite + rutile + coesite. By comparison, no significant increase in CaEs_ss with increasing P could be observed. If the formation of oriented SiO₂-rods frequently observed in eclogititc clinopyroxenes is due to the retrogressive breakdown of a CaEs-component then these textures are a cooling rather than a decompression phenomenon and are most likely to be found in kyanite-bearing eclogites cooled from temperatures ≥750°C. The presence of clinopyroxene with approx. 4 mol% CaEs_ss in an experiment conducted at 2.5 GPa/850°C confirms earlier suggestions based on field data that vacancy-rich clinopyroxenes are not necessarily restricted to ultrahigh pressure metamorphic conditions. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Application of precise 142Nd/144Nd analysis of small samples to inclusions in diamonds (Finsch,South Africa) and Hadean Zircons (Jack Hills,Western Australia)

¹⁴⁶Sm–¹⁴²Nd and ¹⁴⁷Sm–¹⁴³Nd systematics were investigated in garnet inclusions in diamonds from Finsch (S. Africa) and Hadean zircons from Jack Hills (W. Australia) to assess the potential of these systems as recorders of early Earth evolution. The study of Finsch inclusions was conducted on a composite sample of 50 peridotitic pyropes with a Nd model age of 3.3 Ga. Analysis of the Jack Hills zircons was performed on 790 grains with ion microprobe ²⁰⁷Pb/²⁰⁶Pb spot ages from 3.95 to 4.19 Ga. Finsch pyropes yield 100 × ?¹⁴²Nd = ? 6 ± 12 ppm, ?¹⁴³Nd = ? 32.5, and ¹⁴⁷Sm/¹⁴⁴Nd = 0.1150. These results do not confirm previous claims for a 30 ppm ¹⁴²Nd excess in South African cratonic mantle. The lack of a ¹⁴²Nd anomaly in these inclusions suggests that isotopic heterogeneities created by early mantle differentiation were remixed at a very fine scale prior to isolation of the South African lithosphere. Alternatively, this result may indicate that only a fraction of the mantle experienced depletion during the first 400 Myr of its history. Analysis of the Jack Hills zircon composite yielded 100 × ?¹⁴²Nd = 8 ± 10 ppm, ?¹⁴³Nd = 45 ± 1, and ¹⁴⁷Sm/¹⁴⁴Nd = 0.5891. Back-calculation of this present-day ?¹⁴³Nd yields an unrealistic estimate for the initial ?¹⁴³Nd of ? 160 ?-units, clearly indicating post-crystallization disturbance of the ¹⁴⁷Sm–¹⁴³Nd system. Examination of ^146,147Sm–^142,143Nd data reveals that the Nd budget of the Jack Hills sample is dominated by non-radiogenic Nd, possibly contained in recrystallized zircon rims or secondary subsurface minerals. This secondary material is characterized by highly discordant U–Pb ages. Although the mass fraction of altered zircon is unlikely to exceed 5–10% of total sample, its high LREE content precludes a reliable evaluation of ¹⁴⁶Sm–¹⁴²Nd systematics in Jack Hills zircons.     

Shale basins,sulfur-deficient ore brines and the formation of exhalative base metal deposits

The massive sulfide deposits of the Iberian Pyrite Belt are interbedded with felsic volcanic rocks and shale, and underlain by several thousand meters of siliciclastic sedimentary rocks known as the PQ Group. Isotope geochemistry and regional geology are both consistent with equilibration of the ore-forming fluids with the PQ Group, prior to ore deposition near the former seafloor. The average Cu:Zn:Pb ratio of the PQ Group rocks (ca. 26:55:19) is similar to the weighted average of all the massive sulfide orebodies combined (ca. 25:52:23).The genetic relationship between massive sulfide deposits and a siliciclastic sedimentary metal source is explained here by a thermodynamic model, proposing that mildly reducing redox conditions imposed by equilibration with the sedimentary rocks are most critical for the formation of an effective ore-forming fluid. Relatively metal-rich but organic-poor pyrite-bearing shale undergoing dewatering of saline pore fluids is an effective source for the generation of sulfur-deficient but relatively iron and base metal-rich brines. Thus, we propose that the giant deposits of the Iberian Pyrite Belt owe their existence not to exceptionally metal-enriched (e.g., magmatic) fluids, but to the existence of a fairly ordinary but large metal source in reactive siliciclastic sediments, combined with an underlying igneous heat source and a particularly efficient mechanism of sulfide precipitation by mixing with H₂S-rich fluids at or near the seafloor.Essentially similar mineral equilibria are imposed when saline fluids are buffered by typical continental basement rocks. Leaching of retrograde minerals and possibly residual salts from their magmatic or metamorphic prehistory is expected to generate similar, variably metal-rich but relatively sulfide-deficient fluids. Thus, the existence of mildly reducing rocks can be the dominant chemical control in the source of fluids generating many volcanogenic, Irish-type or sedex deposits, many of which are known to precipitate their metal load in response to biogenic sulfide addition at the ore deposition site.     

Formation of Zn–Ca phyllomanganate nanoparticles in grass roots

It is now well established that a number of terrestrial and aquatic microorganisms have the capacity to oxidize and precipitate Mn as phyllomanganate. However, this biomineralization has never been shown to occur in plant tissues, nor has the structure of a natural Mn(IV) biooxide been characterized in detail. We show that the graminaceous plant Festuca rubra (red fescue) produces a Zn-rich phyllomanganate with constant Zn:Mn and Ca:Mn atomic ratios (0.46 and 0.38, respectively) when grown on a contaminated sediment. This new phase is so far the Zn-richest manganate known to form in nature (chalcophanite has a Zn:Mn ratio of 0.33) and has no synthetic equivalent. Visual examination of root fragments under a microscope shows black precipitates about ten to several tens of microns in size, and their imaging with backscattered and secondary electrons demonstrates that they are located in the root epidermis. In situ measurements by Mn and Zn K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray diffraction (XRD) with a micro-focused beam can be quantitatively described by a single-phase model consisting of Mn(IV) octahedral layers with 22% vacant sites capped with tetrahedral and octahedral Zn in proportions of 3:1. The layer charge deficit is also partly balanced by interlayer Mn and Ca. Diffracting crystallites have a domain radius of 33 Å in the ab plane and contain only 1.2 layers (8.6 Å) on average. Since this biogenic Mn oxide consists mostly of isolated layers, basal 00l reflections are essentially absent despite its lamellar structure. Individual Mn layers are probably held together in the Mn–Zn precipitates by stabilizing organic molecules. Zinc biomineralization by plants likely is a defense mechanism against toxicity induced by excess concentrations of this metal in the rhizosphere.     

Seasonal patterns of carbon chemistry and isotopes in tufa depositing groundwaters of southwestern Japan

Annually laminated carbonates, known as tufas, commonly develop in limestone areas and typically record seasonal patterns of oxygen- and carbon-isotope compositions. δ¹⁸O values are principally controlled by seasonal changes of water temperature, whereas δ¹³C values are the result of complex reactions among the gaseous, liquid, and solid sources of carbon in the system. We examined the processes that cause the seasonal patterns of δ¹³C in groundwater systems at three tufa-depositing sites in southwestern Japan by applying model calculations to geochemical data. Underground inorganic carbon species are exchanged with gaseous CO₂, which is mainly introduced to the underground hydrological system by natural atmospheric ventilation and by diffusion of soil air. These processes control the seasonal pattern of δ¹³C, which is low in summer and high in winter. Among the three sites we investigated, we identified two extreme cases of the degree of carbon exchange between liquid and gaseous phases. For the case with high radiocarbon composition (Δ¹⁴C) and low pCO₂, there was substantial carbon exchange because of a large contribution of atmospheric CO₂ and a small water mass. For the other extreme case, which was characterized by low Δ¹⁴C and high pCO₂, the contribution of atmospheric CO₂ was small and the water mass was relatively large. Our results suggest that at two of the three sites water residence time within the soil profile was longer than 1 year. Our results also suggested a short residence time (less than 1 year) of water in the soil profile at the site with the smallest water mass, which is consistent with large seasonal amplitude of the springwater temperature variations. The Δ¹⁴C value of tufas is closely related to the hydrological conditions in which they are deposited. If the initial Δ¹⁴C value of a tufa-depositing system is stable, ¹⁴C-chronology can be used to date paleo-tufas.     

Kinetics of Cd sorption, desorption and fixation by calcite: A long-term radiotracer study

Time-dependent sorption and desorption of Cd on calcite was studied over 210 days utilizing ¹⁰⁹Cd as a tracer to distinguish between ‘labile’ and ‘non-labile’ forms of sorbed Cd. Stabilizing the calcite suspensions for 12 months under atmospheric P_CO2 and controlled temperature was necessary to reliably follow Cd dynamics following initial sorption. Results revealed time-dependant Cd sorption and marked desorption hysteresis by calcite under environmentally relevant conditions. Data obtained were fitted to a first-order kinetic model and a concentric shell diffusion model. Both models described the progressive transfer of Cd²⁺ to a less reactive form within calcite and subsequent desorption of Cd subject to different initial contact times. The kinetic model provided a better fit to the combined sorption and desorption data (R² = 0.992). It differentiates between two ‘pools’ of sorbed Cd²⁺ on calcite, ‘labile’ and ‘non-labile’, in which labile sorbed Cd is in immediate equilibrium with the free Cd²⁺ ion activity in solution whereas non-labile Cd is kinetically restricted. For the diffusion model (R² = 0.959), the rate constants describing Cd dynamics in calcite produced a half-life for Cd desorption of ∼175 d, for release to a ‘zero-sink’ solution. Results from this study allow comment on the likely mechanisms occurring at the calcite surface following long-term Cd sorption.     

Cr-spinel/olivine and Cr-spinel/liquid nickel partition coefficients from natural samples

The Nernst partition coefficient of nickel (D^Ni) between Cr-spinel and silicate melt in natural systems has been investigated using mid-ocean ridge basalts (MORB) and other volcanic rocks. The Cr-spinel/olivine D^Ni values in volcanic rocks are between 1.2 and 0.3, indicating that the Cr-spinel/liquid D^Ni values vary from slightly higher to significantly lower than the olivine/liquid D^Ni values in natural systems. The Cr-spinel/liquid D^Ni values from the MORB samples vary between 6 and 11, slightly higher than those from the S-bearing experiments of Satari et al. [Satari P., Brenan J. M., Horn I. and McDonough W. F. (2002) Experimental constraints on the sulfide- and chromite-silicate melt partitioning behavior of rhenium and platinum-group elements. Economic Geology97, 385-398]. The results of the MORB samples and the experiments of Satari et al. (2002) indicate a negative correlation between the Cr-spinel/liquid D^Ni and the X_Cr values in Cr-spinels (Cr cation number on the basis of 3 total cations in the spinel structure). Variations of Cr-spinel/liquid D^Ni values with Cr-spinel compositions can be estimated from an empirical equation based on the results of the MORB samples and the experiments by Satari et al. (2002). The choice of Cr-spinel/liquid D^Ni = 10 for numerical modeling by Righter et al. [Righter K., Leeman W. P. and Hervig R. L. (2006) Partitioning of Ni, Co, and V between spinel-structured oxides and silicate melts: importance of spinel composition. Chemical Geology227, 1-25] is reasonable for basaltic systems. For picritic and komatiitic systems a lower value of ∼5 is more appropriate.