Stable isotope (C, O, S) systematics of the mercury mineralization at Idrija, Slovenia: constraints on fluid source and alteration processes

The world-class Idrija mercury deposit (western Slovenia) is hosted by highly deformed Permocarboniferous to Middle Triassic sedimentary rocks within a complex tectonic structure at the transition between the External Dinarides and the Southern Alps. Concordant and discordant mineralization formed concomitant with Middle Triassic bimodal volcanism in an aborted rift. A multiple isotopic (C, O, S) investigation of host rocks and ore minerals was performed to put constraints on the source and composition of the fluid, and the hydrothermal alteration. The distributions of the δ13C and δ18O values of host and gangue carbonates are indicative of a fracture-controlled hydrothermal system, with locally high fluid-rock ratios. Quantitative modeling of the δ13C and δ18O covariation for host carbonates during temperature dependent fluid-rock interaction, and concomitant precipitation of void-filling dolomites points to a slightly acidic hydrothermal fluid (δ13C≈−4‰ and δ18O≈+10‰), which most likely evolved during isotopic exchange with carbonates under low fluid/rock ratios. The δ34S values of hydrothermal and sedimentary sulfur minerals were used to re-evaluate the previously proposed magmatic and evaporitic sulfur sources for the mineralization, and to assess the importance of other possible sulfur sources such as the contemporaneous seawater sulfate, sedimentary pyrite, and organic sulfur compounds. The δ34S values of the sulfides show a large variation at deposit down to hand-specimen scale. They range for cinnabar and pyrite from −19.1 to +22.8‰, and from −22.4 to +59.6‰, respectively, suggesting mixing of sulfur from different sources. The peak of δ34S values of cinnabar and pyrite close to 0‰ is compatible with ore sulfur derived dominantly from a magmatic fluid and/or from hydrothermal leaching of basement rocks. The similar stratigraphic trends of the δ34S values of both cinnabar and pyrite suggest a minor contribution of sedimentary sulfur (pyrite and organic sulfur) to the ore formation. Some of the positive δ34S values are probably derived from thermochemical reduction of evaporitic and contemporaneous seawater sulfate

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

The Mississippi Valley-type (MVT) Pb-Zn ore district at Mežica 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 Mežica covers an area of 64km2 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 δ 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 δ 34 S values are negative within a broad range, with δ 34 S pyrite <δ 34 S sphalerite <δ 34 S galena for both conformable and discordant orebodies, indicating isotopically heterogeneous H2S 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 34S-enriched H2S to the ore fluid. The variations of δ 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 δ 34 S values with time along the different sphalerite generations are consistent with mixing of different H2S sources, with a decreasing contribution of H2S from regional TSR, and an increase from a local H2S 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 δ 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 H2S 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 H2S-rich pore waters during late burial diagenesis, while the discordant orebodies formed by mobilization of the earlier conformable mineralizatio

Fluid flow through the sedimentary cover in northern Switzerland recorded by calcite-celestite veins (Oftringen borehole, Olten)

Abundant veins filled by calcite, celestite and pyrite were found in the core of a 719m deep borehole drilled in Oftringen near Olten, located in the north-western Molasse basin, close to the thrust of the Folded Jura. Host rocks are calcareous marl, argillaceous limestone and limestone of the Dogger and Malm. The δ18O values of vein calcite are lower than in host rock carbonate and, together with microthermometric data from fluid inclusions in vein calcite, indicate precipitation from a seawater-dominated fluid at average temperatures of 56-68°C. Such temperatures were reached at the time of maximum burial of the sedimentary pile in the late Miocene. The depth profile of δ13C and 87Sr/86Sr values and Sr content of both whole-rock carbonate and vein calcite show marked trends towards negative δ13C, high 87Sr/86Sr, and low Sr content in the uppermost 50-150m of the Jurassic profile (upper Oxfordian). The 87Sr/86Sr of vein minerals is generally higher than that of host rock carbonate, up to very high values corresponding to Burdigalian seawater (Upper Marine Molasse, Miocene), which represents the last marine incursion in the region. No evidence for internally derived radiogenic Sr (clay minerals) has been found and so an external source is required. S and O isotope composition of vein celestite and pyrite can be explained by bacterial reduction of Miocene seawater sulphate. The available data set suggests the vein mineralization precipitated from descending Burdigalian seawater and not from a fluid originating in the underlying Triassic evaporite

Continuidades y rupturas en las relaciones laborales de Argentina tras la crisis del neoliberalismo

Durante la década del 90 se han desarrollado profundas transformaciones en las relaciones laborales que han tendido a la flexibilización de las condiciones de trabajo, cuya base fueron las políticas económicas del neo liberalismo. A partir de 2003, se desarrollan una serie de transformaciones en el mercado de trabajo, en el régimen de acumulación y en el rol del Estado que estarían trayendo cambios en los procesos de flexibilización. En este marco, el objetivo del presente artículo es establecer los cambios y continuidades en las relaciones laborales en torno a los procesos de flexibilización laboral en argentina entre los periodos 1990-2002 y 2003-2011. Para el estudio comparativo, se analizan los procesos desarrollados en el nivel “Macro”; y por medio de los contenidos de los Convenios Colectivos de Trabajo surgidos de la negociación colectiva en el sector automotriz y la distribución de energía eléctrica, aquellos vinculados al nivel “Micro”.Fil: Delfini, Marcelo Fabián. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Medina Freyer Spangenberg, Jorge Enrique. Universidad de Buenos Aires. Facultad de Cs.sociales. Carrera de Relaciones del Trabajo; ArgentinaFil: Drolas, María Ana. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Saavedra 15. Centro de Estudios E Investigaciones Laborales; Argentin

Evidence linking calcium to increased organo-mineral association in soils

Geochemical indicators are emerging as important predictors of soil organic carbon (SOC) dynamics, but evidence concerning the role of calcium (Ca) is scarce. This study investigates the role of Ca prevalence in SOC accumulation by comparing otherwise similar sites with (CaCO$_{3}$-bearing) or without carbonates (CaCO$_{3}$-free). We measured the SOC content and indicators of organic matter quality (C stable isotope composition, expressed as δ$^{13}$C values, and thermal stability) in bulk soil samples. We then used sequential sonication and density fractionation (DF) to separate two occluded pools from free and mineral-associated SOC. The SOC content, mass, and δ$^{13}$C values were determined in all the fractions. X-ray photoelectron spectroscopy was used to investigate the surface chemistry of selected fractions. Our hypothesis was that occlusion would be more prevalent at the CaCO$_{3}$-bearing site due to the influence of Ca on aggregation, inhibiting oxidative transformation, and preserving lower δ$^{13}$C values. Bulk SOC content was twice as high in the CaCO$_{3}$-bearing profiles, which also had lower bulk δ$^{13}$C values, and more occluded SOC. Yet, contrary to our hypothesis, occlusion only accounted for a small proportion of total SOC (< 10%). Instead, it was the heavy fraction (HF), containing mineral-associated organic C, which accounted for the majority of total SOC and for the lower bulk δ$^{13}$C values. Overall, an increased Ca prevalence was associated with a near-doubling of mineral-associated SOC content. Future investigations should now aim to isolate Ca-mediated complexation processes that increase organo-mineral association and preserve organic matter with lower δ$^{13}$C values

Stable Carbon Isotope Composition of c 9, t 11-Conjugated Linoleic Acid in Cow's Milk as Related to Dietary Fatty Acids

This study explores the potential use of stable carbon isotope ratios (δ13C) of single fatty acids (FA) as tracers for the transformation of FA from diet to milk, with focus on the metabolic origin of c9,t11-18:2. For this purpose, dairy cows were fed diets based exclusively on C3 and C4 plants. The FA in milk and feed were fractionated by silver-ion thin-layer chromatography and analyzed for their δ13C values. Mean δ13C values of FA from C3 milk were lower compared to those from C4 milk (−30.1‰ vs. −24.9‰, respectively). In both groups the most negative δ13C values of all FA analyzed were measured for c9,t11-18:2 (C3 milk=−37.0±2.7‰; C4 milk −31.4±1.4‰). Compared to the dietary precursors 18:2n-6 and 18:3n-3, no significant 13C-depletion was measured in t11-18:1. This suggests that the δ13C-change in c9,t11-18:2 did not originate from the microbial biohydrogenation in the rumen, but most probably from endogenous desaturation of t11-18:1. It appears that the natural δ13C differences in some dietary FA are at least partly preserved in milk FA. Therefore, carbon isotope analyses of individual FA could be useful for studying metabolic transformation processes in ruminant

Chicxulub impact spherules in the North Atlantic and Caribbean: age constraints and Cretaceous-Tertiary boundary hiatus

The Chicxulub impact is commonly believed to have caused the Cretaceous-Tertiary boundary mass extinction and a thin impact spherule layer in the North Atlantic and Caribbean is frequently cited as proof. We evaluated this claim in the seven best North Atlantic and Caribbean Cretaceous-Tertiary boundary sequences based on high-resolution biostratigraphy, quantitative faunal analyses and stable isotopes. Results reveal a major Cretaceous-Tertiary boundary unconformity spanning most of Danian subzone P1a(1) and Maastrichtian zones CF1-CF2 (~400 ka) in the NW Atlantic Bass River core, ODP Sites 1049A, 1049C and 1050C. In the Caribbean ODP Sites 999B and 1001B the unconformity spans from the early Danian zone P1a(1) through to zones CF1-CF4 (~3 Ma). Only in the Demerara Rise ODP Site 1259B is erosion relatively minor and restricted to the earliest Danian zone P0 and most of subzone P1a(1) (~150 ka). In all sites examined, Chicxulub impact spherules are reworked into the early Danian subzone P1a(1) about 150-200 ka after the mass extinction. A similar pattern of erosion and redeposition of impact spherules in Danian sediments has previously been documented from Cuba, Haiti, Belize, Guatemala, south and central Mexico. This pattern can be explained by intensified Gulf stream circulation at times of climate cooling and sea level changes. The age of the Chicxulub impact cannot be determined from these reworked impact spherule layers, but can be evaluated based on the stratigraphically oldest spherule layer in NE Mexico and Texas, which indicates that this impact predates the Cretaceous-Tertiary boundary by about 130-150 k

Permian–polysulphide-siderite–barite–haematite deposit Rude in Samoborska Gora Mts., Zagorje–Transdanubian zone of the Inner Dinarides

Samoborska Gora Mts. is situated within westernmost part of the Zagorje&ndash;Mid&ndash;Transdanubian zone of the Inner Dinarides. The Samoborska Gora Mts. consists dominantly of Permian unmetamorphosed siliciclastic sediments and evaporites, overlain by Lower Triassic sediments. Rude mineralization is hosted by Permian siliciclastic sediments, beneath gypsum and anhydrite strata. Central part of the deposit consists of 1.5 km long stratabound mineralization, grading laterally into ferruginous sandstone and protruding vertically into a gypsum&ndash;anhydrite layer. Siderite&ndash;polysulfide&ndash;barite&ndash;quartz veins are located underneath the stratabound mineralization. Late stage galena&ndash;barite veins overprints the formerly formed mineralization types. The Rude ore deposit was generated by NaCl&plusmn;CaCl2&ndash;H2O solutions. Stratabound mineralization was precipitated from solutions with salinities between 7 and 11 wt. % NaCl equ., homogenizing between 150&deg;C to 230&deg;C. Vein type mineralization derived from solutions with salinities between 4 and 20 wt. % NaCl equ., homogenizing between 80&deg;C and 160&deg;C, while late stage galena&ndash;barite veins were precipitated from solutions with salinities between 11 and 16 wt. % NaCl equ., homogenizing between 100&deg;C to 140&deg;C. Fluid inclusions bulk leachate chemistry recorded Na+&gt;Mg2+&gt;K+&gt;Ca2+&gt;Li+ and Cl&ndash;&gt;SO42&ndash; ions. Sulfur isotope composition of barites and overlying gypsum steams from the Permian seawater sulfate, supported by increased Br&ndash; content, which follows successively the seawater evaporation line. The sulfur isotopic composition of sulfides varies between &ndash;0.2 and +12.5 &permil;, as a result of thermal reduction of Permian marine sulfate. Ore&ndash;forming fluids were produced by hydrothermal convective cells (reflux brine model) and derived primarily from Permian seawater,- modified by evaporation and interaction with the Permian sedimentary rocks. Rude deposits in Samoborska Gora Mts. may be declared as a prototype of the Permian siderite&ndash;polysulfide&ndash;barite deposits, products of the rifting along the passive Gondwana margin, in the Inner Dinarides, and their equivalents in extension northeastward into Zagorje&ndash;Transdanubian Zone and Gemerides, and southeastward to Hellenide&ndash;Albanides.Samoborska Gora Mts. is situated within the westernmost part of the Zagorje–Mid–Transdanubian zone of the Inner Dinarides. The Samoborska Gora Mts. predominantly consists of Permian unmetamorphosed siliciclastic sediments and evaporites, overlain by Lower Triassic sediments. Rude mineralization is hosted by Permian siliciclastic sediments, below gypsum and anhydrite strata. The central part of the deposit consists of a 1.5 km long stratabound mineralization, grading laterally into ferruginous sandstone and protruding vertically into a gypsum–anhydrite layer. Siderite–polysulphide–barite–quartz veins are located below the stratabound mineralization. The stratiform part of the deposit is situated above the stratabound and consists of haematite lajer with barite concretions and veinlets. Late stage galena–barite veins overprint earlier types of mineralization. The Rude ore deposit was generated by predominantly NaCl ±} CaCl2–H2O solutions. Detrital quartz from stratiform mineralization was precipitated from solutions with salinities between 7 and 11 wt. % NaCl equ., homogenizing between 150 °C to 230 °C. Stratabound/siderite–polysulphide–barite–quartz vein type mineralization was derived from solutions with salinities between 5 and 19 wt. % NaCl equ., homogenizing between 80 °C and 160 °C, while late stage galena–barite veins were precipitated from solutions with salinities between 11 and 16 wt. % NaCl equ., homogenizing between 100 °C to 140 °C. Fluid inclusion bulk leachate chemistry recorded Na+>Mg2+>K+>Ca2+>Li+ and Cl–>SO4 2–ions. Sulphur isotope composition of barites and overlying gypsum stems from Permian seawater sulphate, supported by increased Br– content, which follows successively the seawater evaporation line. The sulphur isotopic composition of sulphides varies between –0.2 and +12.5 ‰, as a result of thermal reduction of Permian marine sulphate. Ore–forming fluids were produced by hydrothermal convective cells (reflux brine model), and were derived primarily from Permian seawater, modified by evaporation and interaction with Permian sedimentary rocks. Rude deposits in SamoborskaGora Mts. may be declared as a precursor? of the Permian siderite–polysulphide–barite deposits (products of rifting along the passive Gondwana margin), in the Inner Dinarides, and their equivalents extending northeastward into the Zagorje–Transdanubian Zone and the Gemerides, and southeastward to the Hellenide–Albanides

Trace Element and Sulfur Isotope Signatures of Volcanogenic Massive Sulfide (VMS) Mineralization: A Case Study from the Sunnhordland Area in SW Norway

The Sunnhordland area in SW Norway hosts more than 100 known mineral occurrences, mostly of volcanogenic massive sulfide (VMS) and orogeny Au types. The VMS mineralization is hosted by plutonic, volcanic and sedimentary lithologies of the Lower Ordovician ophiolitic complexes. This study presents new trace element and δ 34S data from VMS deposits hosted by gabbro and basalt of the Lykling Ophiolite Complex and organic-rich sediments of the Langevåg Group. The Alsvågen gabbro-hosted VMS mineralization exhibits a significant Cu content (1.2 to >10 wt.%), with chalcopyrite and cubanite being the main Cu-bearing minerals. The enrichment of pyrite in Co, Se, and Te and the high Se/As and Se/Tl ratios indicate elevated formation temperatures, while the high Se/S ratio indicates a contribution of magmatic volatiles. The δ 34S values of the sulfide phases also support a substantial influx of magmatic sulfur. Chalcopyrite from the Alsvågen VMS mineralization shows significant enrichment in Se, Ag, Zn, Cd and In, while pyrrhotite concentrates Ni and Co. The Lindøya basalt-hosted VMS mineralization consists mainly of pyrite and pyrrhotite. Pyrite is enriched in As, Mn, Pb, Sb, V, and Tl. The δ 34S values of sulfides and the Se/S ratio in pyrite suggest that sulfur was predominantly sourced from the host basalt. The Litlabø sediment-hosted VMS mineralization is also dominated by pyrite and pyrrhotite. Pyrite is enriched in As, Mn, Pb, Sb, V and Tl. The δ 34S values, which range from −19.7 to −15.7 ‰ VCDT, point to the bacterial reduction of marine sulfate as the main source of sulfur. Trace element characteristics of pyrite, especially the Tl, Sb, Se, As, Co and Ni concentrations, together with their mutual ratios, provide a solid basis for distinguishing gabbro-hosted VMS mineralization from basalt- and sediment-hosted types of VMS mineralization in the study area. The distinctive trace element features of pyrite, in conjunction with its sulfur isotope signature, have been identified as a robust tool for the discrimination of gabbro-, basalt- and sediment-hosted VMS mineralization