Zhang T, et al. This petroleum-associated Pb accumulated originally in the organic-matter-rich and metal-rich Alum Shale during sedimentation and early diagenesis. Thus, in such brines, the minor complexation capability of organic acid anions (e.g., carboxylates) for Pb and Zn dismissed the possibility that organic acids play a role in the transport of Pb and Zn3. Most hydrothermal ore deposits will be epigenetic. Besides the established role of such organic compounds in the production of reduced sulphur for mineralization, their possible contribution to the metal pool for sulphide mineralization has only been conceptualized and tested experimentally11,12. PMC legacy view 
Isotope composition of Phanerozoic ore leads from the Swedish Segment of the Fennoscandian Shield. Romer R. Sandstone-hosted Pb-Zn mineral deposits and their relation to the tectonic mobilization of the Baltic Shield during the Caledonian orogeny, a reinterpretation. Hein, U.F. Vapor-saturated halite solubility in part of the system NaCl-CaCl2-H2O, with application to fluid inclusions from oceanic hydrothermal systems. Cerny, I. The .gov means its official. Transport of metals by hydrocarbons in MVT deposits. Goldhaber MB, et al. 1b). https://www.britannica.com/science/metasomatic-replacement. Base metal sulphide mineralization mainly takes place when the metal-bearing fluids mix with reduced fluids rich in sulphur species3,4. Manning DAC. Palogeographie der Ober-Trias Karbonatplattform in den Nrdlichen Kalkalpen. Sphalerite and galena appear in three forms: (1) interstitially between partly dissolved quartz grains (mainly in the Upper Sandstone Orebody), (2) replacing barite cement (mainly in the Lower Sandstone Orebody), or (3) replacing ore-stage pyrite in both orebodies16. The fact that not all leachates fall on the regression line including vein Pb may be due to two reasons: (i) leachates are not corrected for time-integrated decay since the formation of the vein mineralization (this would variably shift isotopic compositions of leachates to the left along isochrons corresponding to 400600Ma ages, depending on their U/Pb ratios); Fig. advised N.J.S. Fluorine Anomalies Accompanying the Alpine Pb-Zn Deposits Compared to the Geochemistry of Their Fluorites. Sptl, C.; Wennemann, T.W. All dried down Pb elutions (EOMs, HCl-HNO3 leachates, HF-HNO3 residues, galena aliquots) were re-dissolved using 5mL 2% HNO3. 1b), the analysed Pb-Zn sulphides at Laisvall define a trend (Laisvall line) that is distinct from the isotopic composition of the Pb-Zn sulphides from the basement-hosted veins (vein line). Vanko, D.A. 1Department of Earth Sciences, University of Geneva, Rue des Marachers 13, 1205 Geneva, Switzerland, 5Present Address: Institute of Geochemistry and Petrology, Department of Earth Sciences, ETH Zrich, Clausiusstrasse 25, 8092 Zrich, Switzerland, 2Institute of Earth Surface Dynamics, University of Lausanne, Building Geopolis, 1015 Lausanne, Switzerland, 3Formerly Geological Survey of Sweden (SGU), Box 670 SE-751 28, Uppsala, Sweden, 4Division of Geosciences, Lule University of Technology, SE-971 87 Lule, Sweden. Todt, W., Cliff, W. A., Hanser, A. Additional lead aliquots were obtained from sphalerite samples at the Laisvall deposit (n=6) during Rb-Sr-Pb column chemistry15. The EOM from the shale hydrocarbon source rocks (15-ASF-1 to 15-ASF-5) and mineralized sandstone samples (15-US-01 & -02, 15-LS-01 & -02) was processed in the following way. Horita, J. Seewald JS. 1b). Measurements of Pb isotopic composition were carried out on a Neptune Plus MC-ICPMS at the Section of Earth Sciences, University of Geneva, Switzerland, by adding Tl to the sample solution and using the 203Tl/205Tl ratio (0.418922) to correct for internal mass fractionation. ; Sun, S.S. This research was financially supported by the Swiss National Science Foundation (SNSF, Switzerland, FN 146 353), Boliden AB (Sweden), and the Geological Survey of Sweden. The bitumen fraction of the fourth mineralized sandstone sample has a Pb isotopic composition that is similar to the isotopic composition of Pb-Zn sulphides at Laisvall and therefore falls on the Laisvall mixing line. Estimation of the contribution in lead from the two end-members identified in the present study: (1) basement-derived lead and (2) organic lead. McLennan, S.M. The hydrocarbon fraction mainly consisted of n-alkane, methyl-alkanes, and acyclic isoprenoids16. Bharati S, Patience RL, Larter SR, Standen G, Poplett IJF. ; Frantz, J.D. Dunkl, I.; Farics, .; Jzsa, S.; Lukcs, R.; Haas, J.; Budai, T. Traces of Carnian volcanic activity in the Transdanubian Range, Hungary. are exhaled during lithification. The five Alum Shale bitumen fractions have a lead isotopic composition that falls on the Laisvall mixing line on the low-radiogenic side (end-member 2 in Fig. Petroleum also contributed H2S for mineralization via thermochemical sulphate reduction (modified after ref.16). 1a; 64 Mt at 4% Pb, 0.6% Zn, 9g/t Ag) in northern Sweden was mined for 40 years and was the largest Pb producer in Europe. Publishers note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. Bacterial and thermochemical sulfate reduction in diagenetic settings old and new insights. Samples, weighing 1 to 4kg each, were collected from drill cores at the core archive of Boliden Mineral AB, Sweden or from outcrops in a 5-km radius around the Laisvall mine: (i) shale hydrocarbon source rocks from the Alum Shale Formation (n=5), (ii) mineralized sandstone samples (n=47), (iii) basement granite samples (n=6). Careers. 8600 Rockville Pike Oppizzi, P.; Camana, G.; Neri, P.; Rossi, C.; Rodeghiero, F.; Bernasconi, E. Le mineralizzazioni a barite e fluorite del Monte San Giorgio (Canton Ticino meridionale). Role of crude oil in the genesis of Mississippi Valley-Type deposits: Evidence from the Cincinnati arch. The high proportion of lead contributed to the Laisvall deposit by petroleum and associated waters opens the possibility to evaluate in a new way the role of hydrocarbons in genetic models for epigenetic sediment-hosted base metal (e.g., Cu, Pb, Zn) ore deposits. Carbonate-bound lead-zinc deposits of the Alpine and extra-Alpine Mesozoic; implications for prospecting and evaluation of their stratigraphy and facies relationships. Hydrocarbon as ore fluids. Metals contained in epigenetic sediment-hosted Zn-Pb sulphide deposits, which are referred as or related to Mississippi Valley-type (MVT) deposits, are thought to be mostly leached from local basement rocks and their detrital erosional rocks, and transported as chloride-metal complexes in oxidized basinal brines14. The five shale hydrocarbon source rock samples and four mineralized sandstone samples were crushed, pulverized (>125m) and c. 200g aliquots were taken for organic geochemistry studies. Inverse correlation between concentration of organic acid anions (e.g., acetate) and metal content was noticed in basinal chloride-dominated and metal-bearing fluids2. Parekh, P.P. This interpretation is in line with the necessity of a physical contact between hydrocarbon and aqueous sulphate for TSR to occur given the fact that sulphate does not react by TSR in the solid state19. This dataset was complemented with published Pb isotope data of galena and sphalerite aliquots from vein occurrences in the Palaeoproterozoic basement31. Lead sources in the epigenetic sandstone-hosted Pb-Zn deposit at Laisvall, Sweden. carried out the computational analysis required to constrain the lead source model ages. ; Mller, P.; Dulski, P. Distribution of trace elements between carbonate and non-carbonate phases of limestone. The exchange does not occur molecule for molecule, but volume for volume; hence, fewer molecules of a less dense mineral will replace those of a more dense mineral. EOM did not contain any non-organic material (e.g., clays, other silicates, carbonates, oxides, phosphates). 200 ppm Zn, but are almost devoid of Th (2 ppm). The authors declare no competing interests. The lead isotopic composition of the bitumen fractions from three mineralized sandstone samples falls in the field of end-member 2 defined by the Alum Shale bitumen fractions. Federal government websites often end in .gov or .mil. We suggest that this lead end-member corresponds to the isotopic composition of Pb leached from basement rocks at the time of vein formation (broadly coeval with the formation of the Laisvall deposit). Schroll, E. Alpine type Pb-Zn-deposits (APT) hosted by Triassic carbonates. The estimation is based on the average lead isotopic composition (206Pb/204Pb and 207Pb/204Pb ratios) of each source, and the isotopic composition of the two extreme sulphide ore samples from the Laisvall mixing line. Synthetic fluid inclusions: VIII. Johansson , Rickard DT. The results show that residues, which represent the common Pb isotope composition, fall on the low-radiogenic continuation of the vein line whereas leachates scatter at variably more radiogenic values around the vein line (Fig. H2O. Wilkinson, J.J. Fluid inclusions in hydrothermal ore deposits. The Alpine sector of the Tethyan shelfexamples of Triassic to Jurassic sedimentation and deformation from the Northern Calcareous Alps. Yuan S, Ellis GS, Chou I-M, Burruss RC. Molnr, F. Characteristics of Variscan and Palaeogene fluid mobilization processes in the Velence Mts., Hungary: A comparative fluid inclusion study. wrote the manuscript and all authors contributed comments and improvements to the manuscript. I am aware that syngenetic is minerals forming at the same time as the rock, and that epigenetic are minerals that have formed after the rock has. Therefore, petroleum compounds produced by the Alum Shale rocks could have potentially supplied lead for sulphide mineralization in sandstone, adding to the established source of radiogenic lead derived from Palaeoproterozoic basement rocks at Laisvall or their detrital erosional products due to leaching by basinal brines2729. Bigi, G.; Castellarin, A.; Coli, M.; Dal Piaz, G.V. Sulphide precipitation mainly occurs when these basinal brines interact with fluids rich in reduced sulphur species produced mostly by thermochemical sulphate reduction (TSR) mediated by hydrocarbons. & Hofmann, A. W. Evaluation of a. Ludwig, K. R. Users manual for Isoplot 3.00: a geochronological toolkit for Microsoft Excel 4 (2003). Oxygen and carbon isotope fractionation in the system dolomite-water-CO. Budai, T.; Haas, J.; Vrs, A.; Molnr, Z. Please refer to the appropriate style manual or other sources if you have any questions. Our results imply that lead originally found in the bitumen of the Alum Shale rocks was transported eastwards during the arc-continent collisional event by liquid petroleum and its associated aqueous phase to the mineralization site in sandstone at Laisvall15,16 (Fig. What would be some good examples of each of them?
