@phdthesis{Stoltnow2023,
  author    = {Stoltnow, Malte},
  title     = {Magmatic-hydrothermal processes along the porphyry to epithermal transition},
  doi       = {10.25932/publishup-61140},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-611402},
  school      = {Universit{\"a}t Potsdam},
  pages     = {xxviii, 132},
  year      = {2023},
  abstract  = {Magmatic-hydrothermal systems form a variety of ore deposits at different proximities to upper-crustal hydrous magma chambers, ranging from greisenization in the roof zone of the intrusion, porphyry mineralization at intermediate depths to epithermal vein deposits near the surface. The physical transport processes and chemical precipitation mechanisms vary between deposit types and are often still debated. The majority of magmatic-hydrothermal ore deposits are located along the Pacific Ring of Fire, whose eastern part is characterized by the Mesozoic to Cenozoic orogenic belts of the western North and South Americas, namely the American Cordillera. Major magmatic-hydrothermal ore deposits along the American Cordillera include (i) porphyry Cu(-Mo-Au) deposits (along the western cordilleras of Mexico, the western U.S., Canada, Chile, Peru, and Argentina); (ii) Climax- (and sub-) type Mo deposits (Colorado Mineral Belt and northern New Mexico); and (iii) porphyry and IS-type epithermal Sn(-W-Ag) deposits of the Central Andean Tin Belt (Bolivia, Peru and northern Argentina). The individual studies presented in this thesis primarily focus on the formation of different styles of mineralization located at different proximities to the intrusion in magmatic-hydrothermal systems along the American Cordillera. This includes (i) two individual geochemical studies on the Sweet Home Mine in the Colorado Mineral Belt (potential endmember of peripheral Climax-type mineralization); (ii) one numerical modeling study setup in a generic porphyry Cu-environment; and (iii) a numerical modeling study on the Central Andean Tin Belt-type Pirquitas Mine in NW Argentina. Microthermometric data of fluid inclusions trapped in greisen quartz and fluorite from the Sweet Home Mine (Detroit City Portal) suggest that the early-stage mineralization precipitated from low- to medium-salinity (1.5-11.5 wt.\% equiv. NaCl), CO2-bearing fluids at temperatures between 360 and 415°C and at depths of at least 3.5 km. Stable isotope and noble gas isotope data indicate that greisen formation and base metal mineralization at the Sweet Home Mine was related to fluids of different origins. Early magmatic fluids were the principal source for mantle-derived volatiles (CO2, H2S/SO2, noble gases), which subsequently mixed with significant amounts of heated meteoric water. Mixing of magmatic fluids with meteoric water is constrained by δ2Hw-δ18Ow relationships of fluid inclusions. The deep hydrothermal mineralization at the Sweet Home Mine shows features similar to deep hydrothermal vein mineralization at Climax-type Mo deposits or on their periphery. This suggests that fluid migration and the deposition of ore and gangue minerals in the Sweet Home Mine was triggered by a deep-seated magmatic intrusion. The second study on the Sweet Home Mine presents Re-Os molybdenite ages of 65.86±0.30 Ma from a Mo-mineralized major normal fault, namely the Contact Structure, and multimineral Rb-Sr isochron ages of 26.26±0.38 Ma and 25.3±3.0 Ma from gangue minerals in greisen assemblages. The age data imply that mineralization at the Sweet Home Mine formed in two separate events: Late Cretaceous (Laramide-related) and Oligocene (Rio Grande Rift-related). Thus, the age of Mo mineralization at the Sweet Home Mine clearly predates that of the Oligocene Climax-type deposits elsewhere in the Colorado Mineral Belt. The Re-Os and Rb-Sr ages also constrain the age of the latest deformation along the Contact Structure to between 62.77±0.50 Ma and 26.26±0.38 Ma, which was employed and/or crosscut by Late Cretaceous and Oligocene fluids. Along the Contact Structure Late Cretaceous molybdenite is spatially associated with Oligocene minerals in the same vein system, a feature that precludes molybdenite recrystallization or reprecipitation by Oligocene ore fluids. Ore precipitation in porphyry copper systems is generally characterized by metal zoning (Cu-Mo to Zn-Pb-Ag), which is suggested to be variably related to solubility decreases during fluid cooling, fluid-rock interactions, partitioning during fluid phase separation and mixing with external fluids. The numerical modeling study setup in a generic porphyry Cu-environment presents new advances of a numerical process model by considering published constraints on the temperature- and salinity-dependent solubility of Cu, Pb and Zn in the ore fluid. This study investigates the roles of vapor-brine separation, halite saturation, initial metal contents, fluid mixing, and remobilization as first-order controls of the physical hydrology on ore formation. The results show that the magmatic vapor and brine phases ascend with different residence times but as miscible fluid mixtures, with salinity increases generating metal-undersaturated bulk fluids. The release rates of magmatic fluids affect the location of the thermohaline fronts, leading to contrasting mechanisms for ore precipitation: higher rates result in halite saturation without significant metal zoning, lower rates produce zoned ore shells due to mixing with meteoric water. Varying metal contents can affect the order of the final metal precipitation sequence. Redissolution of precipitated metals results in zoned ore shell patterns in more peripheral locations and also decouples halite saturation from ore precipitation. The epithermal Pirquitas Sn-Ag-Pb-Zn mine in NW Argentina is hosted in a domain of metamorphosed sediments without geological evidence for volcanic activity within a distance of about 10 km from the deposit. However, recent geochemical studies of ore-stage fluid inclusions indicate a significant contribution of magmatic volatiles. This study tested different formation models by applying an existing numerical process model for porphyry-epithermal systems with a magmatic intrusion located either at a distance of about 10 km underneath the nearest active volcano or hidden underneath the deposit. The results show that the migration of the ore fluid over a 10-km distance results in metal precipitation by cooling before the deposit site is reached. In contrast, simulations with a hidden magmatic intrusion beneath the Pirquitas deposit are in line with field observations, which include mineralized hydrothermal breccias in the deposit area.},
  language  = {en}
}
@article{DesanoisLuedersNiedermannetal.2018,
  author    = {Desanois, Louis and L{\"u}ders, Volker and Niedermann, Samuel and Trumbull, Robert B.},
  title     = {Formation of epithermal Sn-Ag-(Zn) vein-type mineralization at the Pirquitas deposit, NW Argentina},
  series = {Chemical geology : official journal of the European Association for Geochemistry},
  volume    = {508},
  journal   = {Chemical geology : official journal of the European Association for Geochemistry},
  publisher = {Elsevier},
  address   = {Amsterdam},
  issn      = {0009-2541},
  doi       = {10.1016/j.chemgeo.2018.04.024},
  pages     = {78 -- 91},
  year      = {2018},
  abstract  = {The Pirquitas Sn-Ag-(Zn) deposit in northwestern Argentina is thought to be an analogue to the Miocene polymetallic epithermal Sn-Ag deposits of the southern Bolivian Tin Belt, but little is known in detail about the origin and evolution of ore-forming fluids at Pirquitas. This paper reports on a microthermometric study of fluid inclusions in quartz, sphalerite, Ag-Sn sulfides, and Ag-rich sulfosalts using transmitted near infrared and visible light, combined with noble gas isotope analyses of fluids released from mineral separates. The study focused on the vein-hosted mineralization, which formed during two major mineralization events, whereby the first event I comprises two stages (I-1 and I-2). All studied minerals exclusively contain aqueous two-phase inclusions, indicating that the ore-forming fluids did not undergo two-phase phase separation (boiling). Salinity of fluid inclusions in I-1 quartz that precipitated along with pyrite and pyrrhotite ranges between 0 and 7.5 wt\% NaCl equiv. and homogenization temperatures (Th) are between 233 and 370 degrees C. Stage I-2 is characterized by abundant Sn-Ag-Pb-Zn-sulfides and a variety of Ag-rich sulfosalts. Fluid inclusions in stage I-2 Ag-Sn sulfides have salinities up to 10.6 wt\% NaCl equiv. and Th between 213 and 274 degrees C. The deposition of stage I-2 ore is likely related to a new pulse of saline magmatic fluids to the hydrothermal system. The mineralization event II deposited the richest Ag ores at Pirquitas. Colloform sphalerite and pyrargyrite deposited during event II contain two-phase aqueous fluid inclusions with homogenization temperatures between 190 and 252 degrees C and salinities between 0.9 and 4.3 wt\% NaCl equiv. Noble gas concentrations and isotopic compositions of ore-hosted fluid inclusions were determined from crushing hand-picked ore minerals from both mineralization events. With one exception, all samples yielded He-3/He-4 ratios between 1.9 and 4.1 Ra, which is within the range of published data from the volcanic arc and somewhat higher than typical values of meteoric water-derived hot-springs in the region. This demonstrates a significant contribution of magmatic fluids to the Pirquitas mineralization although no intrusive rocks are exposed in the mine region. Taking the noble gas evidence for a magmatic fluid source, we interpret the trends of decreasing Th and salinity values in fluid inclusions from events I and II to represent waning of the magmatic-hydrothermal system and/or increased admixing of meteoric water to the magmatic fluids.},
  language  = {en}
}
@phdthesis{Desanois2019,
  author    = {Desanois, Louis},
  title     = {On the origin of epithermal Sn-Ag-Zn mineralization at the Pirquitas mine, NW Argentina},
  doi       = {10.25932/publishup-43082},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-430822},
  school      = {Universit{\"a}t Potsdam},
  pages     = {104},
  year      = {2019},
  abstract  = {The Central Andes host large reserves of base and precious metals. The region represented, in 2017, an important part of the worldwide mining activity. Three principal types of deposits have been identified and studied: 1) porphyry type deposits extending from central Chile and Argentina to Bolivia, and Northern Peru, 2) iron oxide-copper-gold (IOCG) deposits, extending from central Peru to central Chile, and 3) epithermal tin polymetallic deposits extending from Southern Peru to Northern Argentina, which compose a large part of the deposits of the Bolivian Tin Belt (BTB). Deposits in the BTB can be divided into two major types: (1) tin-tungsten-zinc pluton-related polymetallic deposits, and (2) tin-silver-lead-zinc epithermal polymetallic vein deposits. Mina Pirquitas is a tin-silver-lead-zinc epithermal polymetallic vein deposit, located in north-west Argentina, that used to be one of the most important tin-silver producing mine of the country. It was interpreted to be part of the BTB and it shares similar mineral associations with southern pluton related BTB epithermal deposits. Two major mineralization events related to three pulses of magmatic fluids mixed with meteoric water have been identified. The first event can be divided in two stages: 1) stage I-1 with quartz, pyrite, and cassiterite precipitating from fluids between 233 and 370 °C and salinity between 0 and 7.5 wt\%, corresponding to a first pulse of fluids, and 2) stage I-2 with sphalerite and tin-silver-lead-antimony sulfosalts precipitating from fluids between 213 and 274 °C with salinity up to 10.6 wt\%, corresponding to a new pulse of magmatic fluids in the hydrothermal system. The mineralization event II deposited the richest silver ores at Pirquitas. Event II fluids temperatures and salinities range between 190 and 252 °C and between 0.9 and 4.3 wt\% respectively. This corresponds to the waning supply of magmatic fluids. Noble gas isotopic compositions and concentrations in ore-hosted fluid inclusions demonstrate a significant contribution of magmatic fluids to the Pirquitas mineralization although no intrusive rocks are exposed in the mine area. Lead and sulfur isotopic measurements on ore minerals show that Pirquitas shares a similar signature with southern pluton related polymetallic deposits in the BTB. Furthermore, the major part of the sulfur isotopic values of sulfide and sulfosalt minerals from Pirquitas ranges in the field for sulfur derived from igneous rocks. This suggests that the main contribution of sulfur to the hydrothermal system at Pirquitas is likely to be magma-derived. The precise age of the deposit is still unknown but the results of wolframite dating of 2.9 ± 9.1 Ma and local structural observations suggest that the late mineralization event is younger than 12 Ma.},
  language  = {en}
}