Iodine-rich waters involved in supergene enrichment of the Mantos de la Luna argentiferous copper deposit,Atacama Desert,Chile

Recent studies have suggested the involvement of highly saline deep formation waters that modified preexisting Cu assemblages to form atacamite during supergene oxidation of Cu deposits in the Atacama region. In this report, we document the occurrence of (Ag–I) inclusions hosted by supergene chalcocite from Mantos de la Luna, an argentiferous Upper Jurassic stratabound Cu deposit in the Coastal Range of northern Chile. The presence of this unusual mineral assemblage indicates that iodargyrite precipitated from reducing iodine-rich waters, suggesting that the fluids involved in supergene enrichment of Cu deposits in the Coastal Range were more complex than previously thought. This suggests the prevalence of hyperarid conditions during the latest stages of supergene enrichment of the Mantos de la Luna Cu deposit in the Atacama region, supporting the notion that supergene enrichment processes in hyperarid areas are dynamic in nature and do not exclusively require the presence of meteoric water.     

Atacamite formation by deep saline waters in copper deposits from the Atacama Desert,Chile: evidence from fluid inclusions,groundwater geochemistry,TEM, and <Superscript>36</Superscript>Cl data

The presence of large amounts of atacamite in oxide zones from ore deposits in the Atacama Desert of northern Chile requires saline solutions for its formation and hyperarid climate conditions for its preservation. We investigated the nature and origin of atacamite-forming solutions by means of coupling groundwater geochemical analyses with fluid inclusion data, high-resolution mineralogical observations, and chlorine-36 (³⁶Cl) data in atacamite from the Mantos Blancos and Spence Cu deposits. In both deposits, the salinities of fluid inclusions in atacamite are comparable to those measured in saline groundwaters sampled from drill holes. The average salinity of fluid inclusions in atacamite for the Mantos Blancos and Spence deposits (~7–9 and 2–3 wt.% NaCl_eq, respectively) are strongly correlated to the salinities at which gypsum supersaturates from groundwaters in both deposits (total dissolved solids ~5–9 and 1–3 wt.% NaCl_eq, respectively). This correlation is confirmed by transmission electron microscopy observations of atacamite-bearing samples, revealing an intimate association between atacamite and gypsum that can be traced down to the nanometer scale. ³⁶Cl data in atacamite provide new lines of evidence concerning the origin and age of the saline waters that formed atacamite in various stratabound and porphyry Cu deposits from the Atacama Desert. All atacamite samples show very low ³⁶Cl-to-Cl ratios (11 × 10⁻¹⁵ to 28 × 10⁻¹⁵ at at⁻¹), comparable to previously reported ³⁶Cl-to-Cl ratios of deep formation waters and old groundwaters. In addition, ³⁶Cl-to-Cl ratios in atacamite correlate with U and Th concentration in the host rocks but are independent from distance to the ocean. This trend supports an interpretation of the low ³⁶Cl-to-Cl ratios in atacamite as representing subsurface production of fissiogenic ³⁶Cl in secular equilibrium with the solutions involved in atacamite formation. Therefore, ³⁶Cl in atacamite strongly suggest that the chlorine in saline waters related to atacamite formation is old (>1.5 Ma) but that atacamite formation occurred more recently (<1.5 Ma) than suggested in previous interpretations. Our data provide new constraints on the origin of atacamite in Cu deposits from the Atacama Desert and support the recent notion that the formation of atacamite in hyperarid climates such as the Atacama Desert is an ongoing process that has occurred intermittently since the onset of hyperaridity.     

Atacamite in the oxide zone of copper deposits in northern Chile: involvement of deep formation waters?

Atacamite, a copper hydroxychloride, is an important constituent of supergene oxide zones of copper deposits in northern Chile, whereas in similar deposits elsewhere, it is rare. In Chile, it has generally been assumed to be a primary constituent of the supergene zones. There are two difficulties with this supposition. The first is that atacamite requires saline water for its formation, whereas supergene oxidation was caused by percolating, oxygenated meteoric water, mainly rainwater. The second is that atacamite dissolves rapidly or undergoes phase change when exposed to fresh water. Supergene enrichment of copper deposits in northern Chile extended over a long period, 44 to 9 Ma, being terminated by the onset of hyperaridity. During this period, there was at least intermittent rainfall, exposing previously formed atacamite to dissolution or phase change. Furthermore, atacamite-bearing oxide zones in several deposits are directly overlain by thick Miocene alluvial gravels; the stream waters that transported these gravels would have permeated the oxide zones. In some deposits, atacamite-bearing assemblages occur both in the oxide zones and in contiguous gravels. We suggest that atacamite-bearing oxide assemblages are more likely to have been a replacement of preexisting oxide phases after the onset of hyperaridity at about 9 Ma. A hyperarid climate made possible evaporation and concentration of chloride in meteoric waters. In this paper, we discuss another source of saline waters to modify oxide zones. Dewatering of the Domeyko Basin expelled brines along faults, some of which had earlier guided the location of porphyry deposits. At the Spence porphyry copper deposit, saline waters, which δD vs δ ¹⁸O isotope analyses identify as basinal brines, are presently rising through the deposit, then flowing away along the base of the covering gravels. Compositions of these waters lie within the stability fields of atacamite and brochantite, the two minerals that comprise the oxide zone. Evidence is presented for other porphyry deposits, Radomiro Tomic and Gaby Sur, that basinal brines may have been involved in the late formation of atacamite.     

Pleistocene recycling of copper at a porphyry system,Atacama Desert,Chile: Cu isotope evidence

We present Cu isotope data of hypogene and supergene minerals from the Late Paleocene Spence Cu-Mo porphyry in the Atacama Desert of northern Chile. Chalcopyrite displays a restricted range of δ⁶⁵Cu values within the values reported for primary porphyry Cu sulfides (+ 0.28‰ to + 0.34‰, n = 6). Supergene chalcocite samples show heavier and remarkably homogeneous δ⁶⁵Cu values, between + 3.91‰ and + 3.95‰ (n = 6), consistent with previous models of Cu leaching and enrichment in porphyry systems. Secondary Cu minerals from the oxide zone show a wider range of composition, varying from + 1.28‰ and + 1.37‰ for chrysocolla (n = 6) to very light Cu isotope signatures reported for atacamite between -5.72‰ to -6.77‰ (n = 17). These data suggest redox cycling of Cu during supergene enrichment of the Spence Cu deposit, characterized by a first stage of supergene chalcocite formation from acidic, isotopically-heavy leach fluids of meteoric origin down-flowing in a semi-arid climate (44 to ~ 15-9 Ma). Reworking of the initial supergene copper assemblage, during the Pleistocene, by rising neutral and chlorine-rich deep formation waters under well-established hyper-arid climate conditions lead to the formation of atacamite with extremely fractionated Cu compositions. Essentially coeval chrysocolla formed by dissolution of atacamite during short episodes of wetter climatic conditions occurring in the latest Pleistocene.     

Iodine budget in surface waters from Atacama: Natural and anthropogenic iodine sources revealed by halogen geochemistry and iodine-129 isotopes

Iodine enrichment in the Atacama Desert of northern Chile is widespread and varies significantly between reservoirs, including nitrate-rich “caliche” soils, supergene Cu deposits and marine sedimentary rocks. Recent studies have suggested that groundwater has played a key role in the remobilization, transport and deposition of iodine in Atacama over scales of millions-of-years. However, and considering that natural waters are also anomalously enriched in iodine in the region, the relative source contributions of iodine in the waters and its extent of mixing remain unconstrained. In this study we provide new halogen data and isotopic ratios of iodine (¹²⁹I/I) in shallow seawater, rivers, salt lakes, cold and thermal spring water, rainwater and groundwater that help to constrain the relative influence of meteoric, marine and crustal sources in the Atacama waters. Iodine concentrations in surface and ground waters range between 0.35 μM and 26 μM in the Tarapacá region and between 0.25 μM and 48 μM in the Antofagasta region, and show strong enrichment when compared with seawater concentrations (I = ∼0.4 μM). In contrast, no bromine enrichment is detected (1.3–45.7 μM for Tarapacá and 1.7–87.4 μM for Antofagasta) relative to seawater (Br = ∼600 μM). These data, coupled to the high I/Cl and low Br/Cl ratios are indicative of an organic-rich sedimentary source (related with an “initial” fluid) that interacted with meteoric water to produce a mixed fluid, and preclude an exclusively seawater origin for iodine in Atacama natural waters. Iodine isotopic ratios (¹²⁹I/I) are consistent with halogen chemistry and confirm that most of the iodine present in natural waters derives from a deep initial fluid source (i.e., groundwater which has interacted with Jurassic marine basement), with variable influence of at least one atmospheric or meteoric source. Samples with the lowest isotopic ratios (¹²⁹I/I from ∼215 to ∼1000 × 10⁻¹⁵) strongly suggest mixing between the groundwater and iodine storage in organic-rich rocks (with variable influence of volcanic fluids) and pre-anthropogenic meteoric water, while samples with higher values (∼2000–93,700 × 10⁻¹⁵) indicate the input of anthropogenic meteoric fluid. Taking into account the geological, hydrologic and climatic features of the Atacama region, we propose that the mean contribution of anthropogenic ¹²⁹I is associated with ¹²⁹I releases during nuclear weapon tests carried out in the central Pacific Ocean until the mid 1990's (¹²⁹I/I = ∼12,000 × 10⁻¹⁵). This source reflects rapid redistribution of this radioisotope on a global scale. Our results support the notion of a long-lived continental iodine cycle in the hyperarid margin of western South America, which is driven by local hydrological and climate conditions, and confirm that groundwater was a key agent for iodine remobilization and formation of the extensive iodine-rich soils of Atacama.     

Source,transport, and fate of rhenium,selenium, molybdenum,arsenic, and copper in groundwater associated with porphyry–Cu deposits,Atacama Desert,Chile

We collected groundwaters in and around a large (313 Mt at 1.08% Cu and 0.3% cutoff) undisturbed porphyry copper deposit (Spence) in the hyperarid Atacama Desert of northern Chile, which is buried beneath 30–180 m of Miocene piedmont gravels. Groundwaters within and down-flow of the Spence deposit have elevated Se (up to 800 μg/l), Re (up to 31 μg/l), Mo (up to 475 μg/l) and As (up to 278 μg/l) concentrations compared to up-flow waters (interpreted to represent regional groundwater flow). In contrast, Cu is only elevated (up to 2036 μg/l) in groundwaters recovered from within the deposit; Cu concentrations are low down gradient of the deposit. The differential behavior of the metals/metalloids occurs because the former group dissolves as anions, enhancing their mobility, whereas the base metals dissolve as cations and are lost from solution most likely through adsorption to clay surface exchange sites and through formation of secondary copper chlorides, carbonates, and oxides. Most groundwaters within and down-flow of the deposit have Eh–pH values around the Fe^II/Fe^III phase boundary, limiting the impact of Fe-oxyhydroxides on oxyanions mobility. Se, Re, Mo, and As are all mobile (with filtered/unfiltered samples ～ 1) to the limit of sampling 2 km down gradient from the deposit. The increase in ore-related metals, metalloids, and sulfate and decrease in sulfate–S isotope ratios (from values similar to regional salars, + 4 to + 8‰ δ³⁴S_CDT to lower values closer to hypogene sulfides, + 1 to + 4‰ δ³⁴S_CDT) is consistent with active water–rock reactions between saline groundwaters and the Spence deposit. It is likely that hypogene and/or supergene sulfides are being oxidized under the present groundwater conditions and mineral saturation calculations suggest that secondary copper minerals (antlerite, atacamite, malachite) may also be actively forming, suggesting that supergene and exotic copper mineralization is possible even under the present hyperarid climate of the Atacama Desert.     

Controls on supergene enrichment of porphyry copper deposits in the Central Andes: A review and discussion

The Central Andes host some of the world’s largest porphyry copper deposits. The economic viability of these deposits is dependent on the size and quality of their supergene enrichment blanket. Published models that have strongly influenced exploration policy suggest that supergene enrichment ceased at 14 Ma due to an increase in aridity. Here we discuss these models using published geochronological, geomorphological and geological data. Geochronological data indicate that supergene oxidation and enrichment has been active between 17 and 27°S across the forearc of northern Chile and southern Peru from 44 to 6 Ma, and on the Bolivian Altiplano and Eastern Cordillera of Argentina from 11 Ma to present. There is evidence for cessation at 20, 14 and 6 Ma. However, a major problem is that as more geochronological data become available the age ranges and periods of enrichment increase. This suggests that the full spectrum of enrichment ages may not have been sampled. The relationship between supergene enrichment and the age of regional pediplain surface development is not well constrained. Only in two areas have surfaces related to enrichment been directly dated (southern Peru and south of 26°S in Chile) and suggest formation post 14 Ma. Sedimentological data indicate that a fluctuating arid/semi-arid climate prevailed across the Atacama Desert until between 4 and 3 Ma, climatic conditions that are thought to be favourable for supergene enrichment. The balance between uplift, erosion, burial and sufficient water supply to promote enrichment is complex. This suggests that a simple model for controlling supergene enrichment is unlikely to be widely applicable in northern Chile. General models that involve climatic desiccation at 14 Ma related to rainshadow development and/or the presence of an ancestral cold-upwelling Humboldt Current are not supported by the available geological evidence. The integration of disparate sedimentological, geomorphological and supergene age data will be required to fully understand the controls on and distribution of supergene oxidation and enrichment in the Central Andes.     

“Invisible” silver and gold in supergene digenite (Cu1.8S)

Despite its potential economic and environmental importance, the study of trace metals in supergene (secondary) Cu-sulfides has been seriously overlooked in the past decades. In this study, the concentration and mineralogical form of “invisible” precious metals (Ag, Au) and metalloids (As, Sb, Se, Te) in supergene digenite (Cu_1.8S) from various Cu deposits in the Atacama Desert of northern Chile, the world’s premier Cu province, were determined in detail using a combination of microanalytical techniques. Secondary ion mass spectrometry (SIMS) and electron microprobe analyzer (EMPA) measurements reveal that, apart from hosting up to ∼11,000 ppm Ag, supergene digenite can incorporate up to part-per-million contents of Au (∼6 ppm) and associated metalloids such as As (∼300 ppm), Sb (∼60 ppm), Se (∼96 ppm) and Te (∼18 ppm). SIMS analyses of trace metals show that Ag and Au concentrations strongly correlate with As in supergene digenite, defining wedge-shaped zones in Ag-As and Au-As log-log spaces. SIMS depth profiling and high-resolution transmission electron microscopy (HRTEM) observations reveal that samples with anomalously high Ag/As (>∼30) and Au/As (>∼0.03) ratios plot above the wedge zones and contain nanoparticles of metallic Ag and Au, while samples with lower ratios contain Ag and Au that is structurally bound to the Cu-sulfide matrix. The Ag-Au-As relations reported in this study strongly suggest that the incorporation of precious metals in Cu-sulfides formed under supergene, low-temperature conditions respond to the incorporation of a minor component, in this case As. Therefore, As might play a significant role by increasing the solubility of Ag and Au in supergene digenite and controlling the formation and occurrence of Ag and Au nanoparticles. Considering the fact that processes of supergene enrichment in Cu deposits can be active from tens of millions of years (e.g. Atacama Desert), we conclude that supergene digenite may play a previously unforeseen role in scavenging precious metals from undersaturated (or locally slightly supersaturated) solutions in near-surface environments.     

The El Galeno and Michiquillay porphyry Cu–Au–Mo deposits: geological descriptions and comparison of Miocene porphyry systems in the Cajamarca district, northern Peru

El Galeno and Michiquillay are early to middle Miocene Cu–Au–Mo porphyry-related deposits located in the auriferous Cajamarca district of northern Peru. The El Galeno deposit (486 Mt at 0.57% Cu, 0.14 g/t Au and 150 ppm Mo) is associated with multiple dioritic intrusions hosted within Lower Cretaceous quartzites and shales. Emplacement of the porphyry stocks (17.5–16.5 Ma) in a hanging wall anticline was structurally controlled by oblique faults superimposed on early WNW-trending fold-thrust structures. Early K-feldspar–biotite–magnetite (potassic) alteration was associated with pyrite and chalcopyrite mineralisation. A quartz–magnetite assemblage that occurs at depth has completely replaced potassically altered rocks. Late- and post-mineralisation stocks are spatially and temporally related to weak quartz–muscovite (phyllic) alteration. High Au grades are associated with early intrusive phases located near the centre of the deposit. Highest Cu grades (~0.9% Cu) are mostly associated with a supergene enrichment blanket, whilst high Mo grades are restricted to contacts with the metasedimentary rocks. The Michiquillay Cu–Au–Mo deposit (631 Mt at 0.69% Cu, 0.15 g/t Au, 100–200 ppm Mo) is associated with a Miocene (20.0–19.8 Ma) dioritic complex that was emplaced within the hanging wall of a back thrust fault. The intrusive complex is hosted in quartzites and limestones. The NE-trending deposit is crosscut by NNW-trending prospect-scale faults that influenced both alteration and metal distribution. In the SW and NE of the deposit, potassic alteration zones contain moderate hypogene grades (0.14 g/t Au and 0.8% Cu) and are characterised by chalcopyrite and pyrite mineralisation. The core of the deposit is defined by a lower grade (0.08 g/t Au and 0.57% Cu) phyllic alteration that overprinted early potassic alteration. Michiquillay contains a supergene enrichment blanket of 45–80 m thickness with an average Cu grade of 1.15%, which is overlain by a deep leached cap (up to 150 m). Cu–Au–Mo (El Galeno-Michiquillay) and Au-rich (Minas Conga) deposits in the Cajamarca region are of similar age (early–middle Miocene) and intrusive rock type (dioritic) associations. Despite these geochronological and geochemical similarities, findings from this study suggest variation in metal grade between the hybrid-type and Au-rich deposits result from a combination of physio-chemical factors. These include variations in temperature and oxygen fugacity conditions during hypogene mineralisation resulting in varied sulphide assemblages, host rock type, precipitation of ubiquitous hydrothermal magnetite, and late hydrothermal fluid flow resulting in a well-developed phyllic alteration zone.     

Long term atmospheric deposition as the source of nitrate and other salts in the Atacama Desert, Chile: New evidence from mass-independent oxygen isotopic compositions

Isotopic analysis of nitrate and sulfate minerals from the nitrate ore fields of the Atacama Desert in northern Chile has shown anomalous ¹⁷O enrichments in both minerals. Δ¹⁷O values of 14-21 ‰ in nitrate and 0.4 to 4 ‰ in sulfate are the most positive found in terrestrial minerals to date. Modeling of atmospheric processes indicates that the Δ¹⁷O signatures are the result of photochemical reactions in the troposphere and stratosphere. We conclude that the bulk of the nitrate, sulfate and other soluble salts in some parts of the Atacama Desert must be the result of atmospheric deposition of particles produced by gas to particle conversion, with minor but varying amounts from sea spray and local terrestrial sources. Flux calculations indicate that the major salt deposits could have accumulated from atmospheric deposition in a period of 200,000 to 2.0 M years during hyper-arid conditions similar to those currently found in the Atacama Desert. Correlations between Δ¹⁷O and δ¹⁸O in nitrate salts from the Atacama Desert and Mojave Desert, California, indicate varying fractions of microbial and photochemical end-member sources. The photochemical nitrate isotope signature is well preserved in the driest surficial environments that are almost lifeless, whereas the microbial nitrate isotope signature becomes dominant rapidly with increasing moisture, biologic activity, and nitrogen cycling. These isotopic signatures have important implications for paleoclimate, astrobiology, and N cycling studies.     

Supergene manganese ore records 75 Myr-long Campanian to Pleistocene geodynamic evolution and weathering history of the Central African Great Lakes Region – Tectonics drives,climate assists

The southeastern part of the Democratic Republic of the Congo locally hosts Proterozoic manganese deposits. The deposits of Kisenge-Kamata are the most significant, but manganese ores are also known to occur at Kasekelesa (former Katanga Province) and Mwene-Ditu (former Kasai Province). For the present study, cryptomelane-rich samples from these two localities were dated, using the ⁴⁰Ar/³⁹Ar step-heating method with a CO₂ laser probe. The ages obtained are within a range of c. 77 Myr to c. 2 Myr. Cryptomelane formation took place at c. 76.4 Ma, c. 59.6 Ma, c. 45 Ma, c. 35 Ma, c. 23.8 Ma, c. 15.4 Ma, and c. 13.3 Ma at Kasekelesa, and it occurred at c. 35 Ma, c. 22.4 Ma, c. 15 Ma, c. 5.5–7.2 Ma, c. 3.6 Ma, and c. 2.1–2.3 Ma at Mwene-Ditu. The Campanian age (c. 76.4 Ma) recorded at Kasekelesa is the oldest ⁴⁰Ar/³⁹Ar age that has up to now been recorded for Mn ores from Africa. It documents the formation of oxidized ore along a Campanian or older erosion surface, which could be part of the ‘African Erosion Surface’. The complete age record suggests that continent-wide tectonics accounts for most of the recognized supergene ore formation episodes, controlled by vertical lithospheric movements that are ultimately responsible for alternating stages of landscape stability and erosion. Tectonics is thus regarded as the first-order control for secondary ore formation in Central Africa, over the last 80 Myr. Climate is a second-order control, because sufficient water supply is needed for supergene enrichment, whereby climatic conditions are recognized to have been favourable during some relatively cold Late Mesozoic and Paleogene periods, as well as during some humid and warm Neogene stages.     

Geodynamic and climate controls in the formation of Mio–Pliocene world-class oxidized cobalt and manganese ores in the Katanga province, DR Congo

The Katanga province, Democratic Republic of Congo, hosts world-class cobalt deposits accounting for ~50% of the world reserves. They originated from sediment-hosted stratiform copper and cobalt sulfide deposits within Neoproterozoic metasedimentary rocks. Heterogenite, the main oxidized cobalt mineral, is concentrated as “cobalt caps” along the top of silicified dolomite inselbergs. The supergene cobalt enrichment process is part of a regional process of residual ore formation that also forms world-class “manganese cap” deposits in western Katanga, i.e., the “black earths” that are exploited by both industrial and artisanal mining. Here, we provide constraints on the genesis and the timing of these deposits. Ar–Ar analyses of oxidized Mn ore and in situ U–Pb SIMS measurements of heterogenite yield Mio–Pliocene ages. The Ar–Ar ages suggest a multi-phase process, starting in the Late Miocene (10–5 Ma), when the metal-rich substratum was exposed to the action of meteoric fluids, due to major regional uplift. Further oxidation took place in the Pliocene (3.7–2.3 Ma) and formed most of the observed deposits under humid conditions: Co- and Mn-caps on metal-rich substrata, and coeval Fe laterites on barren areas. These deposits formed prior to the regional shift toward more arid conditions in Central Africa. Arid conditions still prevailed during the Quaternary and resulted in erosion and valley incision, which dismantled the metal-bearing caps and led to ore accumulation in valleys and along foot slopes.     

U-series dating of co-seismic gypsum and submarine paleoseismology of active faults in Northern Chile (23°S)

The convergence of the Nazca and South American plates along the subduction margin of the central Andes results in large subduction earthquakes and tectonic activity along major fault systems. Despite its relevance, the paleoseismic record of this region is scarce, hampering our understanding about the relationship between the Andes building and earthquake occurrence. In this study, we used the U-series disequilibrium method to obtain absolute ages of paleoearthquake events associated with normal displacements along the active Mejillones and Salar del Carmen faults in the Coastal Range of the Atacama Desert of northern Chile. The ²³⁰Th–²³⁴U disequilibrium ages in co-seismic gypsum salts sampled along the fault traces together with marine evidences indicate that earthquakes occurred at ca. 29.7 ± 1.7 ka, 11 ± 4 ka and 2.4 ± 0.8 ka. When coupled with paleoseismic marine and radiocarbon (¹⁴C) records in the nearby Mejillones Bay evidencing large dislocations along the Mejillones Fault, the geochronological dataset presented here is consistent with the notion that gypsum salts formed during large earthquakes as a result of co-seismic dilatancy pumping of saline waters along the major faults. Based on maximum observed cumulative vertical offsets in the studied faults, this phenomena could have occurred episodically at a rate in the order of 1:40 to 1:50 with respect to the very large subduction earthquakes during the latest Pleistocene–Holocene period. The results presented here reveal that the U-series disequilibrium method can be successfully applied to date the gypsum salts deposited along faults during seismic events, and therefore directly constrain the age of large paleoearthquakes in hyperarid and seismically active zones.     

Characteristics and genesis of Gangdese porphyry copper deposits in the southern Tibetan Plateau: Preliminary geochemical and geochronological results

Porphyry-type Cu (Mo, Au) deposits have been discovered along the Gangdese magmatic arc in the southern Tibetan Plateau. Extensive field investigations and systematic studies of geochemistry, S–Pb isotopic tracing, together with Re–Os and ⁴⁰Ar/³⁹Ar isotopic dating indicate that the mineralisation of the copper belt is genetically related to emplacement of late orogenic granitic porphyries during the post-collisional crustal relaxation period of the Late Himalayan epoch. These porphyries are petrochemically K-enriched and belong to shoshonitic to high-K calc-alkaline series. They display enrichment of large ion lithophile elements (LILE) Rb, K, U, Th, Sr, Pb and depletion of high field strength elements (HFSE) Nb, Ta, Ti and the heavy rare earth elements (HREE) and Y without Eu anomalies. These characteristics demonstrate that subduction played a dominant role in their petrogenesis and residual garnet was left in the magma sources. Pb isotope data show a linear correlation in the plumbotectonic framework diagram ranging from orogenic Pb in the eastern segment of the copper belt to mantle Pb in the western segment. These constitute a mixing line of the Indian Oceanic MORB with Indian Oceanic sediments and suggest that the porphyry magmas were dominantly derived from partial melting of subducted oceanic crusts mixed with a minor quantity of sediments and mantle wedge components.The Gangdese porphyry copper polymetallic belt has alteration characteristics and zonation typical of porphyry-type copper deposits which include potassic alteration (K-feldspathisation and biotitisation), silicification, sericitisation, and propylitisation. Mineralisation mainly occurs in strongly altered granitic cataclasite at the exo-contact with veinlet-disseminated textures. The porphyries themselves are weakly mineralised with disseminated pyrite and chalcopyrite. The copper deposits contain simple ore mineral associations consisting of chalcopyrite, pyrite, bornite, molybdenite, sphalerite and oxidised minerals of malachite, covellite and molybdite. During supergene oxidation, primary ores underwent secondary enrichment to form economic orebodies with Cu grade ranging from 1% to 5%.Ore sulphides of the copper belt display S and Pb isotopic compositions identical to the ore-bearing porphyries. Their δ³⁴S values vary between − 3.8‰ and + 2.4‰ and are typical of mantle sulphur. The ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb ratios vary in the ranges: 18.106 to 18.752, 15.501 to 15.638, and 37.394 to 39.058, respectively, and yielded radiogenetic lead-enriched signatures. Twelve molybdenite samples from the copper belt yielded isochron ages of 14.76 ± 0.22 Ma and 13.99 ± 0.16 Ma for the Nanmu and Chongjiang deposits and model ages of 13.5 to 13.6 Ma for the Lakang'e deposit. Meanwhile, ⁴⁰Ar/³⁹Ar isotopic dating of two biotite phenocrysts from the Chongjiang and Lakang'e deposits give plateau ages of 13.5 ± 1.0 Ma and 13.42 ±0.10 Ma, respectively. During the geodynamic evolution of the Gangdese collision-orogenic belt, intrusion of the ore-bearing porphyries took place just before the rapid uplift and E–W extension of the southern Plateau. And the ore-forming process may have occurred simultaneously with the uplift and extension (14 ± 0.1 Ma).     

The dissolution kinetics of atacamite in the acid range and the stability of atacamite containing soils from Namaqualand,South Africa

The Cu hydroxy mineral, atacamite, is commonly associated with saline environments and is generally thought to dissolve rapidly in the presence of fresh water. A Cu contaminated soil from the arid Namaqualand region, South Africa, shows atacamite as the dominant Cu containing mineral. The stability of the Cu phase in this soil was determined through equilibrium and leaching studies using both deionised water (DI) and a concentrated (0.5 M) NaCl solution. Initially a high concentration of exchangeable Cu was released from the soils leached with NaCl. Continued leaching with NaCl resulted in a substantial decrease in Cu release as atacamite equilibria started to control dissolved Cu. This suggests that an initial spike of Cu laden water will leach from the soils at the onset of a large rainfall event. Further additions of water will result in a lower but sustained release of Cu from the soil. The Cu contaminated soils are exposed to acidic sulphate leachate thus the dissolution kinetics of synthetic atacamite in the acidic range (pH 5.5–4.0) was determined in both NaCl and DI solutions. The kinetic data showed that atacamite dissolution rates are significantly higher in DI than in NaCl but the rates converge at pH 4. In comparison to common acid soluble minerals, atacamite displays a moderate dissolution rate (10^−9.55–10^−7.14 mol m⁻² s⁻¹) within the acid range (pH 5.5–4.0). The atacamite dissolution reaction order with respect to pH is 1.3 and 1.6 in DI and NaCl solutions, respectively, suggesting that dissolution rates of atacamite are highly pH dependent in the acid range. The type of acid used to lower the pH had no effect on the reaction kinetics, with HNO₃ and H₂SO₄ resulting in comparable dissolution rates of atacamite at pH 4.5.     

Transition from arid to hyper-arid environment in the southern Levant deserts as recorded by early Pleistocene cummulic Aridisols

The time at which deserts established their current arid or hyper-arid conditions remains a fundamental question regarding the history of Earth. Cosmogenic isotope exposure ages of desert pavement and welded, calcic–gypsic–salic Reg soils that developed on relatively flat alluvial surfaces ～2 Ma ago in the Negev Desert indicate long geomorphic stability under extremely dry conditions. Over a short interval during their initial stage of development between 1–2 Ma, these cumulative soils are characterized by calcic soils reaching maximum stage III of carbonate morphology. This interval is the only period when calcic soil horizons formed on stable abandoned alluvial surfaces in the southern Negev Desert. Since ～1 Ma pedogenesis changed toward more arid soil environment and the formation of gypsic–salic soil horizons that were later followed by dust accumulation. The dichotomy of only moderately-developed calcic soil (stages II–III) during a relatively long time interval (10⁵–10⁶ years) indicates an arid environment that does not support continuous development but only occasional calcic soil formation. The very low δ¹⁸O and relatively high δ¹³C values of these early pedogenic carbonates support soil formation under arid climatic conditions. Such an environment was probably characterized by rare and relatively longer duration rainstorms which occasionally allowed deeper infiltration of rainwater and longer retention of soil moisture. This, in turn enabled the growth of sparse vegetation that enhanced deposition of pedogenic carbonate. At ～1 Ma these rare events of slightly wetter conditions ceased and less atmospheric moisture reached the southern Negev Desert leading to deposition of soluble salts and dust deposited in the soils. The combination of long-term hyperaridity, scarcity of vegetation and lack of bioturbation, salts cementation, dust accumulation and tight desert pavement cover, has protected the surfaces from erosion forming one of the most remarkably stable landscapes on Earth, a landscape that essentially has not eroded, but accumulated salt and dust for more than 10⁶ yr.     

The Jurassic – Tertiary unconformity: A new exploration target for supergene-enriched iron oxide copper-gold –style mineralization in the Humboldt mafic complex,Nevada, USA

A Late Cretaceous to Early Oligocene episode of paleoweathering and supergene activity has been identified within the Jurassic-age (170 Ma) Humboldt mafic complex (HMC) and associated Boyer Ranch Formation of west-central Nevada, USA. This episode is responsible for significant subaerial weathering, erosion, oxidation and most importantly local supergene metal enrichment which could potentially have a major economic impact upon iron oxide copper-gold (IOCG)-style mineralization within the complex and in the Boyer Ranch Formation. Paleoweathering profiles that developed on the exposed Jurassic surface during this time now mark an angular unconformity (J-T unconformity) with a stratigraphically overlying, Tertiary (Oligocene) rhyolitic volcanic-volcaniclastic sequence.Differential uplift of the Jurassic surface is a direct result of the Middle and/or Late Jurassic Luning-Fencemaker compressional overthrust faulting event during which the entire complex was tectonically transported to its present location. The uplifted Jurassic paleosurface experienced one or more cycles of weathering, erosion, depression of the water table and uninterrupted supergene activity beginning at the end of the Cretaceous and possibly accelerating during the Paleocene-Eocene Thermal Maximum Event (∼56 Ma). Geochemically mature supergene Cu-oxide profiles developed over exhumed mineralized sections in terrains with favorable fault block movements. These paloweathering systems evolved from moderately acidic pH to near-neutral or slightly alkaline pH environments over time. High protolith reactivity and low hypogene pyrite concentrations modified acidity of supergene fluids thus limiting Cu mobility.Profiles that survived erosion were later buried and preserved by the Oligocene-age rhyolitic volcanic-volcaniclastic sequence before the onset of mid-Tertiary Basin and Range normal faulting. Subsequent partial unroofing of overlying Tertiary volcanic cover resulted in further erosion of some profiles. Erosional remnants mapped in the field include all or some components of the original supergene Cu-oxide profiles. Drilling results suggest profiles that remain buried are generally intact.Although this field-oriented study is considered preliminary, it concludes that known Jurassic-age IOCG-style mineral occurrences in the central HMC have been subjected to prolonged subaerial paleoweathering and supergene activity that has not been previously recognized. Where complete or nearly complete profiles are preserved, efficient cumulative Cu-enrichment to potentially ore grades has been documented in well defined oxide zones. These findings can be extrapolated to the entire J-T unconformity along which concealed and enriched deposits may exist. As such, the unconformity is considered a prime exploration target that is highly prospective for new discoveries of economically viable, supergene-enriched IOCG resources.     

Lower and Middle Pleistocene human settlements recorded in fluvial deposits of the middle Loire River Basin,Centre Region,France

This paper records the findings from c. 80 prehistoric sites that have been discovered in the alluvial deposits of the rivers Creuse, Cher, and Loir, tributaries of the middle Loire River, over the period since 1981. These deposits comprise river terrace aggradations formed during successive glacial–interglacial cycles which have recorded climate and environment during Quaternary time. The systematic dating of these river deposits by Electron Spin Resonance (ESR) applied to optically bleached sedimentary quartz has resulted in the establishment of a chronological framework for the evolution of these rivers during Lower and Middle Pleistocene (between 1.7 Ma and 130 ka). Evidence for Early Palaeolithic (Mode 1) industries with an in situ context (workshops, soils) in the highest aggradations indicates that Hominins were present in the study area, near the geographical centre of France (47°N), around 1.1 Ma. Examination of the sites indicates that Human occupations were located along valley bottom sites during temperate episodes. Subsequently, after a gap of several hundred thousand years industries with handaxes appear in the Middle Loire Basin in the interval between 700 and 600 ka, and then continuously from 400 ka. These two phases of settlement produced industrial assemblages with clear differences in their responses to the supplies of raw materials and in the modes of making flakes.     

Formation of weathering-derived magnesite deposits in the New England Orogen, New South Wales, Australia: Implications from mineralogy, geochemistry and genesis of the Attunga magnesite deposit

Nodular, cryptocrystalline, weathering-derived magnesite deposits in the New England Orogen, Australia, provide a significant source of high-purity magnesite. Common textural features and related isotopic fingerprints indicate a close genetic relationship between weathering-derived magnesite deposits hosted by ultramafic rocks at Attunga and by sediments at Kunwarara while silica-carbonate rock alteration and rare hydrothermal magnesite vein deposits reflect contrasting conditions of formation. Localised weathering of carbonates in a soil environment shifts stable isotopic composition towards low δ ¹³C and high δ ¹⁸O typical for weathering-derived magnesites while intrusion-related fluids do not significantly change the isotopic composition of affected carbonates. At Attunga, magnesite consists of irregular, nodular veins and masses filling faults and cracks in the weathered serpentinite host rock as well as soft powdery magnesite in pervasive serpentinite alteration zones. The high-grade magnesite at Attunga can be contaminated by amorphous silica and serpentine relicts but does not contain dolomite or ferroan magnesite as observed for its hydrothermal equivalent, the Piedmont magnesite deposit, or other widespread deposits of silica-carbonate rock in the Great Serpentinite Belt. Heavy δ ¹⁸O values are compatible with a supergene formation from meteoric waters while low δ ¹³C suggests C3-photosynthetic plants as the predominant source of carbon for the Attunga magnesites. We infer that weathering-derived, nodular magnesite deposits hosted in ultramafic rocks like the Attunga magnesite deposit have formed in a two-step process involving the hypogene formation of a pre-cursor magnesite deposit and complete supergene overprinting by meteoric waters that acquired carbon from percolation through soil.     

新疆东天山地区土屋和延东铜矿床斑岩叠加改造成矿作用

土屋和延东铜矿床位于东天山大南湖-头苏泉岛弧带南部,是中亚成矿带的重要组成部分。文章根据脉次穿插关系、蚀变矿物组合及矿物共生关系,将土屋和延东铜矿床均划分为斑岩成矿期、叠加改造期和表生期3个期次。土屋铜矿床的铜矿化形成于斑岩成矿期和叠加改造期,而延东铜矿床的铜矿化主要形成于叠加改造期;土屋和延东铜矿床伴生的钼矿化主要形成于叠加改造期。因此,笔者认为前人获得的辉钼矿Re-Os年龄(326.2~322.7 Ma)代表叠加改造期的成矿年龄,该期矿化与石英钠长斑岩((323.6±2.5)Ma)的侵入相关,而斑岩成矿期的矿化与斜长花岗斑岩(339~332 Ma)相关,成矿年龄为341.2~333.9 Ma。叠加改造期的存在,使得斑岩成矿期的蚀变分带可能受到了叠加和破坏。