New 40Ar/39Ar alunite ages from the Colquijirca district, Peru: evidence of a long period of magmatic SO2 degassing during formation of epithermal Au-Ag and Cordilleran polymetallic ores

We present 40Ar/39Ar data acquired by infra-red (CO2) laser step-heating of alunite crystals from the large Miocene Colquijirca district in central Peru. Combined with previously published data, our results show that a long (at least 1.3 My) and complex period of magmatic-hydrothermal activity associated with epithermal Au-(Ag) mineralization and base metal, Cordilleran ores took place at Colquijirca. The new data indicate that incursion of magmatic SO2-bearing vapor into the Colquijirca epithermal system began at least as early as ∼11.9Ma and lasted until ∼10.6Ma. Four alunite samples associated with high-sulfidation epithermal Au-(Ag) ore gave 40Ar/39Ar plateau ages between ∼11.9 and ∼11.1Ma (compared to the previously documented ∼11.6 to ∼11.3Ma). By combining individually these new ages with crosscutting relationships, the duration of the Au-(Ag) deposition period can be estimated to at least 0.4My. Three new 40Ar/39Ar plateau ages on alunite associated with the base-metal Cordilleran ores are consistent with previously obtained ages, all of them between 10.83 ± 0.06 and 10.56 ± 0.06Ma, suggesting that most of the sulfide-rich polymetallic deposits of Smelter and Colquijirca formed during this short period. The recognition of consecutive alunite-bearing and alunite-free mineral assemblages within both the Au-(Ag) and the base-metal Cordilleran ores may suggest that SO2-bearing magmatic vapor entered the epithermal environment as multiple discontinuous pulses, a number of which was not necessarily associated in time with ore fluids. It is likely that a period of SO2-bearing vapor degassing longer than 11.9 to 10.6Ma may be recognized with further more detailed wor

Numerical Modelling of Radiogenic Ingrowth and Diffusion of Pb in Apatite Inclusions with Variable Shape and U-Th Zonation

The fundamental premise of apatite U-Th-Pb thermochronology is that radiogenic Pb is redistributed by volume diffusion. In practice, it is often additionally assumed that crystals (1) lose radiogenic Pb to an infinite reservoir, (2) have a simple geometry and (3) are chemically homogeneous. Here we explore the significance of the latter three assumptions by numerical modelling of Pb radiogenic ingrowth and diffusion in apatite inclusions within other minerals. Our results indicate that the host minerals are likely to hamper diffusive Pb loss from the apatite inclusions by limiting the Pb flux across their boundaries, and thus the thermal histories that are reconstructed assuming a fully open boundary may be significantly inaccurate, precluding a meaningful interpretation. We also find that when apatite boundaries are flux-limited, heterogeneities in U and Th concertation within apatite have subordinate effect on bulk-grain U-Th-Pb dates and can cause intra-grain U-Th-Pb dates to increase towards the boundaries. Finally, we show that it is important to correctly account for crystal geometry when modelling intra-grain U-Th-Pb dates. We suggest that the effect of surrounding minerals on diffusive Pb loss from apatite (and loss of other radiogenic isotopes from other minerals) should be examined more closely in future research

The temporal evolution of the Mitu group, south-east Peru – first U-Pb age data

The Eastern Cordillera of southern Peru formed along a crustal zone that has been active as part of the western Gondwana margin since the middle Paleozoic. The present study investigates the Mitu Group of south-east Peru in the area of Abancay-Cusco-Sicuani-Titicaca. This unit comprises continental clastic sediments deposited in syn-sedimentary basins during an extensional period in Permo-Triassic times and has not benefitted from a thorough geochemical-geochronological investigation so far. One of the main reasons for this lack of data is a complex structure of the graben system, tectonically complicated by compressional inversion of the extensional basins during Andean orogeny. Due to dominating coarse-grained clastics, the Mitu Group is devoid of fossils and its age is only poorly bracketed to be Permo -Triassic based on its stratigraphic relation to the underlying Copacabana and overlying Pucara groups. The upper levels of the Copacabana have been constrained by palynology to the Artinskian (Doubinger and Marocco, 1981). However, a hiatus may be observed between the Copacabana and the Mitu groups in most places, rendering the age estimate of the basal Mitu imprecise. The Pucara Group, regarded by Rosas et al. (2007) as thermal sag after Mitu extension, is attributed to the late Triassic - early Jurassic on the basis of ammonite fossils and U-Pb zircon ages from ash beds (Schaltegger et al., 2008). The aim of this study is to provide more accurate and precise age constraints for the age and duration of the Mitu Group by using U-Pb geochronology of volcanic zircon in rhyolitic lavas, and of detrital zircon in clastic sediments. For andesitic volcanic lithologies, age approximations will be obtained by Ar-Ar techniques applied to amphibole and groundmass samples. Field data were obtained from a long and apparently complete section through the Mitu, situated 120km SE of Cusco near the city of Sicuani. This section consists of typical Mitu deposits; continental red beds, breccias and andesitic lavas. However, a zircon-bearing rhyolitic lava at the bottom gives us the opportunity to date the start of Mitu sedimentation by U-Pb ID-TIMS; this analysis will provide a precise age for the base of the Mitu group for the first time. In the Sicuani area the Mitu unconformably overlies the Ambo group, suggesting that the entire Copacabana is missing. Laser-ablation ICP-MS U-Pb data of detrial zircons from a sandstone just below the unconformity indicate a maximum age of latest Carboniferous (303Ma) for the underlying Ambo group. This maximum age overlaps with the palynological age of the lower Copacabana (Azcuy et al., 2002), raising the question whether the Ambo and Copacabana are truly diachronous or just coeval units of different sedimentary facies associations. In another section, 100km W of Cusco, near the city of Abancay, we found Mitu sediments overlying the Copacabana Group. Here the Copacabana contains well preserved plant fossils of the lycopsids family also found elsewhere in Peru and Bolivia. Lack of acidic volcanism during Mitu extension in this region prevents from dating of lavas using the U-Pb method. The detrital zircon population in a sandstone in the lowermost part of the Mitu was analysed for U-Pb ages, using LA-ICP-MS techniques. The youngest zircons in the population are around 235 Ma hence providing a maximum age for the onset of Mitu group sedimentation. The Artinskian age for the upper Copacabana from Doubinger and Marocco (1981) has also been obtained from the Abancay region, establishing a hiatus of some 50 Myrs between the two units. The Mitu Group is intruded by a 220 Ma granite body (Lipa and Saraiva, 2008) indicating significant burial of the sediments at this time. 500km SE of Cusco, on the Bolivian shores of lake Titicaca, the Ambo Group features plant fossils of the Lycopsids family like those found in the Copacabana near Abancay. Our detrital zircon LA-ICPMS study on a quartz arenite just below the fossils indicates a maximum U-Pb age of 343Ma. However a zircon-bearing ash bed will allow for more precise calibration of the fossil age by ID-TIMS techniques. The zircon U-Pb data will provide a test whether the Copacabana and the Ambo group are indeed diachronous or just lateral variations of a sedimentary system

Constraining the age of the Mitu Group, South-East Peru: U-Pb ages of detrital and igneous zircons

The present study investigates the Mitu Group of south-east Peru (13-16°S), which consists of continental clastic sedimentary rocks and interbedded basaltic to andesitic lavas. There is a paucity of geochemical and geochronological data from the Mitu Group, and the interpretation of its evolution is complicated by i) rapid changes in fault structure along-strike of the graben system, and ii) inversion during Andean orogenesis. Due to dominating coarsegrained clastics, the Mitu Group is devoid of fossils and its age is poorly bracketed to the Permo-Triassic, based on its stratigraphic relationships with the underlying Copacabana and overlying Pucará groups. The upper strata of the Copacabana Group have been constrained by palynology to the Artinskian, while marine fossils at the base of the Pucará Group indicate a Norian age. The Pucará Group is only present in northern Peru, whereas the Mitu Group has an erosional contact with overlying Cretaceous sandstones in the study area. Preliminary data suggest that the lower Mitu Group is middle Triassic, leaving a significant hiatus between the Copacabana and Mitu groups

Inclusions of Amorphous and Crystalline SiO 2 in Minerals from Itrongay (Madagascar) and Other Evidence for the Natural Occurrence of Hydrosilicate Fluids

Experimental studies increasingly often report low-temperature (200−800 °C) and low-pressure (0.05−3 kbar) hydrosilicate fluids with >40 wt.% of SiO2 and >10 wt.% of H2O. Compositionally similar fluids were long suggested to potentially exist in natural systems such as pegmatites and hydrothermal veins. However, they are rarely invoked in recent petrogenetic models, perhaps because of the scarcity of direct evidence for their natural occurrence. Here we review such evidence from previous works and add to this by documenting inclusions of hydrosilicate fluids in quartz and feldspar from Itrongay. The latter comprise opal-A, opal-CT, moganite and quartz inclusions that frequently contain H2O and have negative crystal shapes. They coexist with inclusions of CO2- and H2O-rich fluids and complex polycrystalline inclusions containing chlorides, sulphates, carbonates, arsenates, oxides, hydroxides and silicates, which we interpret as remnants of saline liquids. Collectively, previous studies and our new results indicate that hydrosilicate fluids may be common in the Earth’s crust, although their tendency to transform into quartz upon cooling and exhumation renders them difficult to recognise. These data warrant more comprehensive research into the nature of such hydrosilicate fluids and their distribution across a wide range of pressure and temperature conditions and geological systems

Multi-proxy isotopic tracing of magmatic sources and crustal recycling in the Palaeozoic to Early Jurassic active margin of North-Western Gondwana

We trace source variations of active margin granitoids which crystallised intermittently over ~300 Ma in varying kinematic regimes, by combining zircon Lu-Hf isotopic data from Early Palaeozoic to Early Jurassic igneous and metaigneous rocks in the Mérida Andes, Venezuela and the Santander Massif, Colombia, with new whole rock Rb/Sr and Sm-Nd isotopic data, and quartz O isotopic data. These new data are unique in South America because they were obtained from discrete magmatic and metamorphic zircon populations, providing a high temporal res- olution dataset, and compare several isotopic systems on the same samples. Collectively, these data provide valu- able insight into the evolution of the isotopic structure of the continental crust in long-lived active margins. Phanerozoic active margin-related granitoids in the Mérida Andes and the Santander Massif yield zircon Lu-Hf model ages ranging between 0.77 Ga and 1.57 Ga which clearly define temporal trends that can be correlated with changes in tectonic regimes. The oldest Lu-Hf model ages of N1.3 Ga are restricted to granitoids which formed during Barrovian metamorphism and crustal thickening between ~499 Ma and ~473 Ma. These granitoids yield high initial 87Sr/86Sr ratios, suggesting that evolved, Rb-rich middle to upper crust was the major source of melt. Granitoids and rhyolites which crystallised during subsequent extension between ~472 Ma and ~452 Ma yield younger Lu-Hf model ages of 0.80 Ga–1.3 Ga and low initial 87Sr/86Sr ratios, suggesting that they were de- rived from much more juvenile, Rb-poor sources such as mafic lower crust and mantle-derived melts. The rapid change in magmatic sources at ~472 Ma can be attributed either to reduced crustal assimilation during extension, or a short pulse of crustal growth by addition of juvenile material to the continental crust. Between ~472 Ma and ~196 Ma Lu-Hf model ages remain mostly constant between ~1.0 and ~1.2 Ga. The large scatter and the absence of definite trends in initial 87Sr/86Sr ratios suggest that both mafic, Rb-poor, and evolved Rb-rich sources were im- portant precursors of active margin magmas in Colombia and Venezuela throughout the Palaeozoic to the Early Jurassic. Previous studies have shown that the genesis of arc magmas may be stimulated by heat advection to the crust during the underplating of mantle derived melt, but the absence of permanent younging trends in Lu-Hf model ages from ~472 Ma to ~196 Ma suggests that very little new crust was generated during this period in the studied region. An overwhelming majority of the analysed igneous rocks yield zircon Lu-Hf model ages of N1 Ga which may be accounted for by documented local crustal end members of 1 Ga–1.6 Ga, and do not require contributions from the depleted mantle. Therefore, recycling of ~1 Ga and older crust was a dominant process in the north-western corner of Gondwana between ~472 Ma and ~196 Ma. This study shows that whole rock Sm-Nd and zircon Lu-Hf data can be interpreted similarly regarding the age of the source regions, whereas Rb-Sr and O isotope data from the same rocks yield valuable information regarding the geochemical nature of the source

Data on the arc magmatism developed in the Antarctic Peninsula and Patagonia during the Late Triassic – Jurassic: A compilation of new and previous geochronology, geochemistry and isotopic tracing results

We present the results of U-Pb zircon dating conducted using laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS), isotopic tracing analyses of Hf in zircon and Sr-Nd in whole-rock and whole-rock major oxides, and trace element abundances of 12 plutonic and volcanic rocks present on the Antarctic Peninsula. The dataset is presented in combination with the results of previous studies conducted in both Patagonia and the Antarctic Peninsula. These results were filtered for concordant 206Pb–238U zircon ages and topology of the 40Ar/39Ar age spectra. These results may be useful for researchers studying the geological evolution of southern Gondwana, West Antarctica or Patagonia. The interpretation of this dataset is found in the co-submitted paper by Bastias, et al. (2021a) titled ‘A revised interpretation of the Chon Aike magmatic province: active margin origin and implications for the opening of the Weddell Sea’

Geochronology and geochemistry of the northern Scotia Sea: a revised interpretation of the North and West Scotia ridge junction

Understanding the tectonic evolution of the Scotia Sea is critical to interpreting how ocean gateways developed during the Cenozoic and their influence on ocean circulation patterns and water exchange between the Atlantic and Southern oceans. We examine the geochronology and detrital age history of lithologies from the prominent, submerged Barker Plateau of the North Scotia Ridge. Metasedimentary rocks of the North Scotia Ridge share a strong geological affinity with the Fuegian Andes and South Georgia, indicating a common geological history and no direct affinity to the Antarctic Peninsula. The detrital zircon geochronology indicates that deposition was likely to have taken place during the mid – Late Cretaceous. A tonalite intrusion from the Barker Plateau has been dated at 49.6 ±0.3Ma and indicates that magmatism of the Patagonian–Fuegian batholith continued into the Eocene. This was coincident with the very early stages of Drake Passage opening, the expansion of the proto Scotia Sea and reorganization of the Fuegian Andes. The West Scotia Ridge is an extinct spreading centerthat shaped the Scotia Sea and consists of seven spreading segments separated by prominent transform faults. Spreading was active from 30–6Ma and ceased with activity on the W7 segment at the junction with the North Scotia Ridge. Reinterpretation of the gravity and magnetic anomalies indicate that the architecture of the W7 spreading segment is distinct to the other segments of the West Scotia Ridge. Basaltic lava samples from the eastern flank of the W7 segment have been dated as Early – mid Cretaceous in age (137–93Ma) and have a prominent arc geochemical signature indicating that seafloor spreading did not occur on the W7 segment. Instead the W7 segment is likely to represent a downfaulted block of the North Scotia Ridge of the Fuegian Andes continental margin arc, or is potentially related to the putative Cretaceous Central Scotia Sea

Diffusion vs. fluid alteration in alkali feldspar ⁴⁰Ar/³⁹Ar thermochronology: does cross-correlation of log(r/r₀) and age spectra validate thermal histories?

For six decades geoscientists have been trying to quantitatively understand the nature of radiogenic Ar loss from alkali feldspar. Some researchers suggest that volume diffusion is the dominant mechanism, and they use conventional step-heating ⁴⁰Ar/³⁹Ar data from alkali feldspar to recover the thermal histories of rocks. They argue that a high degree of correlation between log(r/r₀) and ⁴⁰Ar/³⁹Ar age spectra, which is observed in a number of natural examples, justifies this hypothesis. In contrast, other investigators suggest that fluid-mediated recrystallisation and alteration control the radiogenic Ar redistribution, hence rendering alkali feldspar useless as a thermochronometer. By means of numerical modelling, we found that the latter mechanism as well is able to produce samples with highly correlated log(r/r₀) and ⁴⁰Ar/³⁹Ar age spectra. In addition, we show that apparent thermal histories recovered for altered alkali feldspar crystals by interpreting step-heating ⁴⁰Ar/³⁹Ar data may be grossly inaccurate, and yet seemingly fit the prevailing understanding of regional geology. Such inaccurate apparent thermal histories can be obtained even from alkali feldspar crystals that underwent volumetrically low degrees of alteration. Therefore, we conclude that conventional step-heating ⁴⁰Ar/³⁹Ar data are insufficient to support the assumption that radiogenic Ar loss from alkali feldspar occurred solely by volume diffusion and validate the constrained thermal histories, even if upheld by a priori knowledge of regional tectonics. We further suggest that all thermochronological constraints obtained using such data should be supported by detailed petrological characterisation of alkali feldspar