Sulfur isotope variations from orebody to hand-specimen scale at the Mezica lead-zinc deposit, Slovenia: a predominantly biogenic pattern

The Mississippi Valley-type (MVT) Pb-Zn ore district at Mezica is hosted by Middle to Upper Triassic platform carbonate rocks in the Northern Karavanke/Drau Range geotectonic units of the Eastern Alps, northeastern Slovenia. The mineralization at Mezica covers an area of 64 km(2) with more than 350 orebodies and numerous galena and sphalerite occurrences, which formed epigenetically, both conformable and discordant to bedding. While knowledge on the style of mineralization has grown considerably, the origin of discordant mineralization is still debated. Sulfur stable isotope analyses of 149 sulfide samples from the different types of orebodies provide new insights on the genesis of these mineralizations and their relationship. Over the whole mining district, sphalerite and galena have delta(34)S values in the range of -24.7 to -1.5% VCDT (-13.5 +/- 5.0%) and -24.7 to -1.4% (-10.7 +/- 5.9%), respectively. These values are in the range of the main MVT deposits of the Drau Range. All sulfide delta(34)S values are negative within a broad range, with delta(34)S(pyrite) < delta(34)S(sphalerite) < delta(34)S(galena) for both conformable and discordant orebodies, indicating isotopically heterogeneous H(2)S in the ore-forming fluids and precipitation of the sulfides at thermodynamic disequilibrium. This clearly supports that the main sulfide sulfur originates from bacterially mediated reduction (BSR) of Middle to Upper Triassic seawater sulfate or evaporite sulfate. Thermochemical sulfate reduction (TSR) by organic compounds contributed a minor amount of (34)S-enriched H(2)S to the ore fluid. The variations of delta(34)S values of galena and coarse-grained sphalerite at orefield scale are generally larger than the differences observed in single hand specimens. The progressively more negative delta(34)S values with time along the different sphalerite generations are consistent with mixing of different H(2)S sources, with a decreasing contribution of H(2)S from regional TSR, and an increase from a local H(2)S reservoir produced by BSR (i.e., sedimentary biogenic pyrite, organo-sulfur compounds). Galena in discordant ore (-11.9 to -1.7%; -7.0 +/- 2.7%, n=12) tends to be depleted in (34)S compared with conformable ore (-24.7 to -2.8%, -11.7 +/- 6.2%, n=39). A similar trend is observed from fine-crystalline sphalerite I to coarse open-space filling sphalerite II. Some variation of the sulfide delta(34)S values is attributed to the inherent variability of bacterial sulfate reduction, including metabolic recycling in a locally partially closed system and contribution of H(2)S from hydrolysis of biogenic pyrite and thermal cracking of organo-sulfur compounds. The results suggest that the conformable orebodies originated by mixing of hydrothermal saline metal-rich fluid with H(2)S-rich pore waters during late burial diagenesis, while the discordant orebodies formed by mobilization of the earlier conformable mineralization

New data on the Vrancea Nappe (Moldavidian Basin, Outer Carpathian Domain, Romania): paleogeographic and geodynamic reconstructions

A study has been performed on the Cretaceous to Early Miocene succession of the Vrancea Nappe (Outer Carpathians, Romania), based on field reconstruction of the stratigraphic record, mineralogical-petrographic and geochemical analyses. Extra-basinal clastic supply and intra-basinal autochthonous deposits have been differentiated, appearing laterally inter-fingered and/or interbedded. The main clastic petrofacies consist of calcarenites, sub-litharenites, quartzarenites, sub-arkoses, and polygenic conglomerates derived from extra-basinal margins. An alternate internal and external provenance of the different supplies is the result of the paleogeographic re-organization of the basin/margins system due to tectonic activation and exhumation of rising areas. The intra-basinal deposits consist of black shales and siliceous sediments (silexites and cherty beds), evidencing major environmental changes in the Moldavidian Basin. Organic-matter-rich black shales were deposited during anoxic episodes related to sediment starvation and high nutrient influx due to paleogeographic isolation of the basin caused by plate drifting. The black shales display relatively high contents in sub-mature to mature, Type II lipidic organic matter (good oil and gas-prone source rocks) constituting a potentially active petroleum system. The intra-basinal siliceous sediments are related to oxic pelagic or hemipelagic environments under tectonic quiescence conditions although its increase in the Oligocene part of the succession can be correlated with volcanic supplies. The integration of all the data in the “progressive reorientation of convergence direction” Carpathian model, and their consideration in the framework of a foreland basin, led to propose some constrains on the paleogeographic-geodynamic evolutionary model of the Moldavidian Basin from the Late Cretaceous to the Burdigalian.This research was supported by Urbino University grant (responsible F. Guerrera), Italy; CGL2009-09249 and CGL2011-30153-CO2-02 research projects (Spanish Ministry of Education and Science), Research Groups and projects of the Generalitat Valenciana and from Alicante University (CTMA-IGA Spain); Research Contr. IDEI 436/01.10.2007 (CNCSIS-Romania)