The effect of chlorite interlayering on <Superscript>40</Superscript>Ar–<Superscript>39</Superscript>Ar biotite dating: an <Superscript>40</Superscript>Ar–<Superscript>39</Superscript>Ar laser-probe and TEM investigations of variably chloritised biotites

Biotite is one of the most common minerals dated by the ⁴⁰Ar–³⁹Ar method. It frequently shows K contents below the expected stoichiometric value, suggesting the presence of low-K impurities. The most common low-K alteration product of biotite is chlorite. Therefore, it is important to understand the effects of chlorite interlayering on ⁴⁰Ar–³⁹Ar ages in order to correctly interpret ⁴⁰Ar–³⁹Ar data. This study examines the outcome of ⁴⁰Ar–³⁹Ar dating analyses on variably chloritised biotites from Ordovician intrusive rocks. The infrared (IR) laser-probe technique and different gas extraction methods were adopted. Incremental laser-heating data on bulk samples yielded hump-shaped age profiles with meaningless young and old age steps. Both the extent of anomalous old age steps and the degree of discordance of the age spectra were much more pronounced in the more chloritised biotite samples. In contrast, in situ data on rock chips and total-fusion ages on single biotite flakes yielded ages concordant with, or younger than, the inferred emplacement ages. Transmission electron microscopy (TEM) was used to texturally characterise biotite samples at the nanometre scale. It was also used to document the complex decomposition-transformation process affecting interlayered biotite–chlorite during in-vacuo IR-laser heating to temperatures ranging from ~600 to >1,000 °C. TEM results suggest that hump-shaped age profiles result from an interplay between ³⁹Ar_K redistribution by recoil during sample irradiation and differential release of argon isotopes hosted in three main reservoirs. These reservoirs are (from least to most retentive): extended defects, chlorite and biotite. The final descending age segment is attributed to the progressive release of argon with increasing temperature from large biotite domains for which ³⁹Ar_K recoil loss was less important. ⁴⁰Ar–³⁹Ar data support previous findings, which suggest that ⁴⁰Ar–³⁹Ar ages when recoil effects are minimised, provide minimum estimates that approach the true biotite age, when the pristine domains are analysed. The most effective approach for obtaining meaningful ⁴⁰Ar–³⁹Ar ages was using individual total-fusion analyses on carefully selected, single flakes previously split along the basal cleavage by wet-grinding and corresponding to a sample mass of a few micrograms.Editorial responsibility: I Parsons     

Biotite and muscovite <Superscript>40</Superscript>Ar–<Superscript>39</Superscript>Ar geochronological constraints on the post-Svecofennian tectonothermal evolution,Forsmark site,central Sweden

In order to characterize the post-Svecofennian tectonothermal evolution of the Fennoscandian Shield, ⁴⁰Ar–³⁹Ar biotite and some ⁴⁰Ar–³⁹Ar muscovite geochronological data are reported from a total of 30 surface outcrop and 1,000 m long borehole samples at Forsmark, central Sweden. The 13 surface samples were collected across 3 branches of a major WNW to NW trending system of deformation zones, whereas the boreholes were drilled within a tectonic lens, in between two of these zones. The ⁴⁰Ar–³⁹Ar biotite ages indicate that the present erosion surface, in central Sweden, cooled below c. 300°C at 1.73–1.66 Ga, and that the rocks could have accommodated strain in a brittle manner between 1.8 and 1.7 Ga. The variation in surface ages is suggested to be due to fault along the large WNW to NW trending deformation zones, following the establishment of a sub-Cambrian peneplain. The minor variation of ages within a single crustal block may be due to disturbance along ENE to NNE trending fracture zones. Possible cooling paths, derived from ⁴⁰Ar–³⁹Ar hornblende, muscovite and biotite ages, were calculated for the time interval from 1.80 to 1.67 Ga, when the area cooled from c. 500 to 300°C. Cooling rates of 1.9–4°C/m.y. have been attained. Between 1.68 and 1.64 Ga, uplift rates of c. 22 m/m.y. were calculated from borehole ⁴⁰Ar–³⁹Ar biotite data. Tectonothermal histories, inferred from the combined cooling and uplift rates, are related to simple cooling after the Svecofennian orogeny, to crustal movement in response to far-field effects of c. 1.7 Ga orogenic activities further to the west or to a combination of these possibilities.     

Re–Os and <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar ages of the Jiguanshan porphyry Mo deposit,Xilamulun metallogenic belt,NE China,and constraints on mineralization events

The large Jiguanshan porphyry Mo deposit, with more than 100 Mt of ore and grades ranging from 0.08% to 0.11%, is located in the newly identified Xilamulun metallogenic belt along the northern margin of the North China Craton. The Mo mineralization is predominantly disseminated in the host granite porphyry, but locally occurs as stockworks in lithic tuff and rhyolitic rocks. ⁴⁰Ar/³⁹Ar dates of samples from groundmass material in the host granite porphyry, post-ore diabase, and quartz porphyry dikes show plateau ages of 155.1 ± 1.9, 149.4 ± 0.9, and 147.6 ± 0.9 Ma, with inverse isochron ages of 156.0 ± 1.8, 149.3 ± 1.3, and 148.3 ± 1.2 Ma, respectively. Seven samples of disseminated molybdenite yielded a weighted average ¹⁸⁷Re-¹⁸⁷Os age of 155.3 ± 0.9 Ma, whereas six veinlet-type molybdenite samples yielded a weighted average ¹⁸⁷Re-¹⁸⁷Os age of 153.0 ± 0.9 Ma, providing direct timing constraints for the Mo mineralization at 153–155 Ma. The regional geological setting together with the emplacement of post-ore diabase and quartz porphyry dikes in the Jiguanshan deposit, are indicative of an extensional regime in Late Jurassic, which was probably linked to lithospheric extension in northeast China.     

<Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar age of gold mineralization of the Malomyr deposit (eastern part of the Mongolian–Okhotsk foldbelt)

Reliable age estimation was obtained originally in this study for gold mineralization of the Malomyr deposit (the eastern part of the Mongolian–Okhotsk foldbelt), which is one of the most well-known deposits in the Russian Far East. The data obtained show that the age of hydrothermal process that resulted in the formation of the Malomyr deposit may be estimated as ～133–132 Ma. Data on magmatism of the same age within the considered region are absent. In the opinion of the authors, mobilization, redistribution of the ore material, and the formation of the Malomyr deposit were mostly controlled by dislocation processes accompanied by hydrothermal activity, which is supported by the results of structural studies.     

Single-crystal EPR and DFT study of a <Superscript>VI</Superscript>Al–O<Superscript>−</Superscript>–<Superscript>VI</Superscript>Al center in jeremejevite: electronic structure and <Superscript>27</Superscript>Al hyperfine constants

Single-crystal electron paramagnetic resonance (EPR) spectra of a gem-quality jeremejevite, Al₆B₅O₁₅(F, OH)₃, from Cape Cross, Namibia, reveal an S = 1/2 hole center characterized by an ²⁷Al hyperfine structure arising from interaction with two equivalent Al nuclei. Spin-Hamiltonian parameters obtained from single-crystal EPR spectra at 295 K are as follows: g ₁ = 2.02899(1), g ₂ = 2.02011(2), g ₃ = 2.00595(1); A ₁/g _e β _e  = −0.881(1) mT, A ₂/g _e β _e  = −0.951(1) mT, and A ₃/g _e β _e  = −0.972(2) mT, with the orientations of the g ₃- and A ₃-axes almost coaxial and perpendicular to the Al–O–Al plane; and those of the g ₁- and A ₁-axes approximately along the Al–Al and Al–OH directions, respectively. These results suggest that this aluminum-associated hole center represents hole trapping on a hydroxyl oxygen atom linked to two equivalent octahedral Al³⁺ ions, after the removal of the proton (i.e., a ^VIAl–O⁻–^VIAl center). Periodic ab initio UHF and DFT calculations confirmed the experimental ²⁷Al hyperfine coupling constants and directions, supporting the proposed structural model. The ^VIAl–O⁻–^VIAl center in jeremejevite undergoes the onset of thermal decay at 300 °C and is completely bleached at 525 °C. These data obtained from the ^VIAl–O⁻–^VIAl center in jeremejevite provide new insights into analogous centers that have been documented in several other minerals.     

Chemical and isotopic investigations (δ<Superscript>18</Superscript>O, δ<Superscript>2</Superscript>H, <Superscript>3</Superscript>H, <Superscript>87</Superscript>Sr/<Superscript>86</Superscript>Sr) to define groundwater processes occurring in a deep-seated landslide in flysch

Deep-seated landslides are complex systems. In many cases, multidisciplinary studies are necessary to unravel the key hydrological features that can influence their evolution in space and time. The deep-seated Berceto landslide, in the northern Apennines of Italy, has been investigated in order to define the origin and geochemical evolution of groundwater (GW), to identify the slope system hydrological boundary, and to highlight the GW flow paths, transit time and transfer modalities inside the landslide body. This research is based on a multidisciplinary approach that involves monitoring GW levels, obtaining analyses of water chemistry and stable and unstable isotopes (δ¹⁸O-δ²H, ³H, ⁸⁷Sr/⁸⁶Sr), performing soil leaching tests, geochemical modelling (PHREEQC), and principal component analysis (PCA). The results of δ¹⁸O-δ²H and ⁸⁷Sr/⁸⁶Sr analyses show that the source of GW recharge in the Berceto landslide is local rainwater, and external contributions from a local stream can be excluded. In the landslide body, two GW hydrotypes (Ca-HCO₃ and Na-HCO₃) are identified, and the results of PHREEQC and PCA confirm that the chemical features of the GW depend on water–rock interaction processes occurring inside the landslide. The ³H content suggests a recent origin for GW and appears to highlight mixing between shallow and deep GW aliquots. The ³H content and GW levels data confirm that shallow GW is mainly controlled by a mass transfer mechanism. The ³H analyses with GW levels also indicate that only deep GW is controlled by a pressure transfer mechanism, and this mechanism is likely the main influence on the landslide kinematics.     

Origin and evolution of oilfield brines from Tertiary strata in western Qaidam Basin: Constraints from <Superscript>87</Superscript>Sr/<Superscript>86</Superscript>Sr, δD, δ<Superscript>18</Superscript>O, δ<Superscript>34</Superscript>S and water chemistry

Chemistry of major and minor elements, ⁸⁷Sr/⁸⁶Sr, δD, δ¹⁸O and δ³⁴S of brines were measured from Tertiary strata and Quaternary salt lakes in the western Qaidam Basin. The water chemistry data show that all oilfield brines are CaCl₂ type. They were enriched in Ca²⁺, B³⁺, Li⁺, Sr²⁺, Br⁻, and were depleted in Mg²⁺, SO₄ ²⁻, which indicated that these brines had the characteristics of deeply circulated water. The relationship between δD and δ¹⁸O shows that all data of these brines decline towards the Global Meteoric Water Line (GWL) and Qaidam Meteoric Water Line (QWL), and that the intersection between oilfield brines and Meteoric Water Lines was close to the local spring and fresh water in the piedmont in the western Qaidam Basin. The results suggest that oilfield brines has initially originated from meteoric water, and then might be affected by water-rock metamorphose, because most oilfield brines distribute in the range of metamorphosing water. The ⁸⁷Sr/⁸⁶Sr values of most oilfield brines range from 0.71121 to 0.71194, and was less than that in salt lake water (>0.712), but close to that of halite in the study area. These imply that salt dissolution occurred in the process of migration. In addition, all oilfield brines have obviously much positive δ³⁴S values (ranging from 26.46‰ to 54.57‰) than that of salt lake brines, which was caused by bacterial sulfate reduction resulting in positive shift of δ³⁴S value and depleteed SO₄ ²⁻ in oilfield brines. Combined with water chemical data and δD, δ¹⁸O, ⁸⁷Sr/⁸⁶Sr, δ³⁴S values, we concluded that oilfield brines mainly originate from the deeply circulated meteoric waters, and then are affected by salt dissolution, water-rock metamorphose, sulfate reduction and dolomitization during the process of migration. These processes alter the chemical compositions of oilfield brines and accumulate rich elements (such as B, Li, Sr, Br, K and so on) for sustainable utilization of salt lake resources in the Qaidam Basin.     

The Meso-Cenozoic thermo-tectonic evolution of the Eastern Pyrenees: an <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar fission track and (U–Th)/He thermochronological study of the Canigou and Mont-Louis massifs

Vertical displacements on the SW–NE Têt fault (Eastern Pyrenees Axial Zone, France), which separates the Variscan Canigou-Carança and Mont-Louis massifs, were constrained using a thermochronologic multi-method approach. ⁴⁰Ar/³⁹Ar data from the granitic Mont-Louis massif record its Variscan cooling history and reveal no ages younger than Early Cretaceous, while the Canigou-Carança gneiss massif records systematically younger ⁴⁰Ar/³⁹Ar ages. These younger ⁴⁰Ar/³⁹Ar ages in the Canigou-Carança gneiss massif are the result of partial to total rejuvenation of argon isotopic systems related to a thermal flow coeval with the Cretaceous HT-BP metamorphism in the North Pyrenean Zone. Only the deepest rocks from the Canigou-Carança suffered this extensive Mid-Cretaceous thermal overprint probably due to differential burial around 4 km at that time. The post Mid-Cretaceous vertical displacements along the Têt fault are recorded by “low” temperature thermochronology using K-feldspar ⁴⁰Ar/³⁹Ar, zircon and apatite fission track and (U–Th)/He datings. The Mont-Louis granite samples experienced a long period of protracted cooling reflecting a lack of thermo-tectonic activity in this area from Late Palaeozoic to Early Cenozoic, followed by cooling from 55–60 Ma to Late Eocene at a mean rate of 15–20°C/Ma in the final stage. This cooling stage corresponds to Têt fault reactivation with a reversed component, promoting exhumation of the Mont-Louis roof zone contemporaneously with the south-vergent Pyrenean thrusting. In the Canigou-Carança massif, the main cooling event occurred from 32 to 18 Ma at a maximum rate of 30°C/Ma during Early Oligocene followed by a more moderate rate of 3°C/Ma from Late Oligocene to Early Burdigalian, coeval with the normal reactivation of the Têt fault in brittle conditions that accommodated the final exhumation of the massif during the opening of the Gulf of Lion.     

Accessory mineral U–Th–Pb ages and <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar eruption chronology,and their bearing on rhyolitic magma evolution in the Pleistocene Coso volcanic field,California

We determined Ar/Ar eruption ages of eight extrusions from the Pleistocene Coso volcanic field, a long-lived series of small volume rhyolitic domes in eastern California. Combined with ion-microprobe dating of crystal ages of zircon and allanite from these lavas and from granophyre geothermal well cuttings, we were able to track the range of magma-production rates over the past 650 ka at Coso. In ≤230 ka rhyolites we find no evidence of protracted magma residence or recycled zircon (or allanite) from Pleistocene predecessors. A significant subset of zircon in the ~85 ka rhyolites yielded ages between ~100 and 200 Ma, requiring that generation of at least some rhyolites involves material from Mesozoic basement. Similar zircon xenocrysts are found in an ~200 ka granophyre. The new age constraints imply that magma evolution at Coso can occur rapidly as demonstrated by significant changes in rhyolite composition over short time intervals (≤10’s to 100’s ka). In conjunction with radioisotopic age constraints from other young silicic volcanic fields, dating of Coso rhyolites highlights the fact that at least some (and often the more voluminous) rhyolites are produced relatively rapidly, but that many small-volume rhyolites likely represent separation from long-lived mushy magma bodies.     

Zircon U–Pb and phlogopite <Superscript>40</Superscript>Ar–<Superscript>39</Superscript>Ar age of the Chengchao and Jinshandian skarn Fe deposits,southeast Hubei Province,Middle–Lower Yangtze River Valley metallogenic belt,China

The Chengchao and Jinshandian deposits in the southeast Hubei Province are the two largest skarn Fe deposits in the Middle–Lower Yangtze River Valley metallogenic belt (MLYRVMB), China. They are characterized by NW-striking orebodies that are developed along the contacts between the Late Mesozoic granitoid and Triassic carbonate and clastic rocks. New sensitive high-resolution ion microprobe and laser ablation inductively coupled plasma mass spectrometry zircon U–Pb dating of the mineralization-related quartz diorite and granite at Chengchao yield ages of 129 ± 2 and 127 ± 2 Ma, respectively, and those at Jinshandian of 127 ± 2 and 133 ± 1 Ma, respectively. These results are interpreted as the crystallization age of these intrusions. Hydrothermal phlogopite samples from the skarn ores at Chengchao and Jinshandian have the plateau ⁴⁰Ar–³⁹Ar ages of 132.6 ± 1.4 and 131.6 ± 1.2 Ma, respectively. These results confirm that both intrusions and associated skarn Fe mineralization were formed contemporaneously in the middle Early Cretaceous time. New zircon U–Pb and phlogopite ⁴⁰Ar–³⁹Ar ages in this study, when combined with available precise geochronological data, demonstrate that there were two discontinuous igneous events, corresponding to two episodes of skarn Fe-bearing mineralization in the southeast Hubei Province: (1) 140–136 Ma diorites and quartz diorites and 141–137 Ma skarn Cu–Fe or Fe–Cu deposits and (2) 133–127 Ma quartz diorites and granites and 133–132 Ma skarn Fe deposits. This scenario is similar to that proposed for the entire MLYRVMB. The intrusions related to skarn Fe deposits show obviously petrological and geochemical differences from those related to skarn Cu–Fe or Fe–Cu deposits. The former are quartz diorite and diorite in petrology and have similar adakitic geochemical signatures and in equilibrium with a garnet-rich residue, whereas the latter are petrologically granite and quartz diorite that are distinguishable from adakitic rocks and in equilibrium with a plagioclase residue. These features indicated that two episodes of magmatism and the formation of skarn Fe-bearing deposits in the southeast Hubei Province, MLYRVMB, might be associated lithosphere thinning induced by asthenosphere upwelling during the Late Mesozoic.     

Carbonate Rocks from the Riphean–Vendian Boundary Deposits of the Anabar Uplift: Isotope (<Superscript>87</Superscript>Sr/<Superscript>86</Superscript>Sr, δ<Superscript>13</Superscript>C, δ<Superscript>18</Superscript>O) Systematics and Chemostratigraphic Consequences

New ⁸⁷Sr/⁸⁶Sr, δ¹³C, and δ¹⁸О chemostratigraphic data were obtained for carbonate rocks of the Lower Riphean Yusmastakh and the Vendian Starorechenskaya formations. The δ¹³С values in dolomites of the Yusmastakh Formation varies from–0.6 to–0.1‰ and in dolomites and dolomitic limestones of the Starorechenskaya Formation, from–1.2 to–0.4‰ PDB, and δ¹⁸О values, from 24.4 to 26.4‰ and from 25.3 to 27.6‰ SMOW, respectively. The Rb–Sr systematics of carbonate rocks was studied using the refined method of stepwise dissolution of samples in acetic acid, including chemical removal of up to one-third of the ground sample by preliminary acid leaching and subsequent partial dissolution of the rest of the sample. Owing to this procedure, secondary carbonate material is removed, which enables one to improve the quality of the Sr-chemostratigraphic data obtained. The initial ⁸⁷Sr/⁸⁶Sr ratios in carbonate rocks of the Yusmastakh (0.70468–0.70519) and Starorechenskaya (0.70832–0.70883) formations evidence the Riphean–Vendian boundary in the Precambrian sequence of the Anabar Uplift.     

Behavior of isotope (<Superscript>18</Superscript>O/<Superscript>16</Superscript>O, <Superscript>234</Superscript>U/<Superscript>238</Superscript>U) systems during the formation of uranium deposits of the “sandstone” type

The uneven character of the distribution of ¹⁸O/¹⁶O and ²³⁴U/²³⁸U values was established in the vertical cross section of the productive sequence of the Dybryn uranium deposit (Vitim uranium-ore region, Buryatia). Both a deficiency and an excess of ²³⁴U in relation to the equilibrium ²³⁴U/²³⁸U ratio in the vertical sequence may provide evidence for the extremely low rate of the infiltration water flow. The behavior of oxygen isotope characteristics for different size fractions of terrigenous rocks provides evidence for active uranium redistribution and openness of the isotope system of this element during interaction of terrigenous–sedimentary rocks with infiltration waters.     

U–Pb,Re–Os,and <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar geochronology of the Nambija Au-skarn and Pangui porphyry Cu deposits,Ecuador: implications for the Jurassic metallogenic belt of the Northern Andes

New U–Pb, Re–Os, and ⁴⁰Ar/³⁹Ar dates are presented for magmatic and hydrothermal mineral phases in skarn- and porphyry-related ores from the Nambija and Pangui districts of the Subandean zone, southeastern Ecuador. Nambija has been one of the main gold-producing centers of Ecuador since the 1980s due to exceptionally high-grade ores (average 15 g/t, but frequently up to 300 g/t Au). Pangui is a recently discovered porphyry Cu–Mo district. The geology of the Subandean zone in southeastern Ecuador is dominated by the I-type, subduction-related, Jurassic Zamora batholith, which intrudes Triassic volcanosedimentary rocks. The Zamora batholith is in turn cut by porphyritic stocks, which are commonly associated with skarn formation and/or porphyry-style mineralization. High precision U–Pb and Re–Os ages for porphyritic stocks (U–Pb, zircon), associated prograde skarn (U–Pb, hydrothermal titanite), and retrograde stage skarn (Re–Os, molybdenite from veins postdating gold deposition) of the Nambija district are all indistinguishable from each other within error (145 Ma) and indicate a Late Jurassic age for the gold mineralization. Previously, gold mineralization at Nambija was considered to be Early Tertiary based on K–Ar ages obtained on various hydrothermal minerals. The new Jurassic age for the Nambija district is slightly younger than the ⁴⁰Ar/³⁹Ar and Re–Os ages for magmatic–hydrothermal minerals from the Pangui district, which range between 157 and 152 Ma. Mineralization at Nambija and Pangui is associated with porphyritic stocks that represent the last known episodes of a long-lived Jurassic arc magmatism (∼190 to 145 Ma). A Jurassic age for mineralization at Nambija and Pangui suggests that the Northern Andean Jurassic metallogenic belt, which starts in Colombia at 3° N, extends down to 5° S in Ecuador. It also adds a new mineralization style (Au-skarn) to the metal endowment of this belt. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Using stable isotopes (δD, δ<Superscript>18</Superscript>O, δ<Superscript>34</Superscript>S and <Superscript>87</Superscript>Sr/<Superscript>86</Superscript>Sr) to identify sources of water in abandoned mines in the Fengfeng coal mining district,northern China

With depleted coal resources or deteriorating mining geological conditions, some coal mines have been abandoned in the Fengfeng mining district, China. Water that accumulates in an abandoned underground mine (goaf water) may be a hazard to neighboring mines and impact the groundwater environment. Groundwater samples at three abandoned mines (Yi, Er and Quantou mines) in the Fengfeng mining district and the underlying Ordovician limestone aquifer were collected to characterize their chemical and isotopic compositions and identify the sources of the mine water. The water was HCO₃·SO₄-Ca·Mg type in Er mine and the auxiliary shaft of Yi mine, and HCO₃·SO₄-Na type in the main shaft of Quantou mine. The isotopic compositions (δD and δ¹⁸O) of water in the three abandoned mines were close to that of Ordovician limestone groundwater. Faults in the abandoned mines were developmental, possibly facilitating inflows of groundwater from the underlying Ordovician limestone aquifers into the coal mines. Although the Sr²⁺ concentrations differed considerably, the ratios of Sr²⁺/Ca²⁺ and ⁸⁷Sr/⁸⁶Sr and the ³⁴S content of SO₄^2? were similar for all three mine waters and Ordovician limestone groundwater, indicating that a close hydraulic connection may exist. Geochemical and isotopic indicators suggest that (1) the mine waters may originate mainly from the Ordovician limestone groundwater inflows, and (2) the upward hydraulic gradient in the limestone aquifer may prevent its contamination by the overlying abandoned mine water. The results of this study could be useful for water resources management in this area and other similar mining areas.     

Ab initio calculations on the O<Subscript>2</Subscript><Superscript>3−</Superscript>-Y<Superscript>3+</Superscript> center in CaF<Subscript>2</Subscript> and SrF<Subscript>2</Subscript>: its electronic structure and hyperfine constants

The O₂ ^3?-Y³⁺ center in fluorite-type structures (CaF₂ and SrF₂) has been investigated at the density functional theory (DFT) level using the CRYSTAL06 code. Our calculations were performed by means of the hybrid B3PW method in which the Hartree–Fock exchange is mixed with the DFT exchange functional, using Becke’s three parameter method, combined with the non-local correlation functionals by Perdew and Wang. Our calculations confirm the stability and the molecular character of the O₂ ^3?-Y³⁺ center. The unpaired electron is shown to be almost exclusively localized on and equally distributed between the two oxygen atoms that are separated by a bond distance of 2.47 Å in CaF₂ and 2.57 Å in SrF₂. The calculated ¹⁷O and ¹⁹F hyperfine constants for of the O₂ ^3?-Y³⁺ center are in good agreement with their corresponding experimental values reported by previous electron paramagnetic resonance and electron nuclear double resonance studies, while discrepancies are notable for the ⁸⁹Y hyperfine constants.     

Time relationships between volcanism–plutonism–alteration–mineralization in Cu-stratabound ore deposits from the Michilla mining district,northern Chile: a <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar geochronological approach

The Michilla mining district comprises one of the most important stratabound and breccia-style copper deposits of the Coastal Cordillera of northern Chile, hosted by the Middle Jurassic volcanic rocks of the La Negra Formation. ⁴⁰Ar/³⁹Ar analyses carried out on igneous and alteration minerals from volcanic and plutonic rocks in the district allow a chronological sequence of several magmatic and alteration events of the district to be established. The first event was the extrusion of a thick lava series of the La Negra Formation, dated at 159.9 ± 1.0 Ma (2σ) from the upper part of the series. A contemporaneous intrusion is dated at 159.6 ± 1.1 Ma, and later intrusive events are dated at 145.5 ± 2.8 and 137.4 ± 1.1 Ma, respectively. Analyzed alteration minerals such as adularia, sericite, and actinolite apparently give valid ⁴⁰Ar/³⁹Ar plateau and miniplateau ages. They indicate the occurrence of several alteration events at ca. 160–163, 154–157, 143–148, and 135–137 Ma. The first alteration event, being partly contemporaneous with volcanic and plutonic rocks, was probably produced in a high thermal gradient environment. The later events may be related either to a regional low-grade hydrothermal alteration/metamorphism process or to plutonic intrusions. The Cu mineralization of the Michilla district is robustly bracketed between 163.6 ± 1.9 and 137.4 ± 1.1 Ma, corresponding to dating of actinolite coexisting with early-stage chalcocite and a postmineralization barren dyke, respectively. More precisely, the association of small intrusives (a dated stock from the Michilla district) with Cu mineralization in the region strongly suggests that the main Michilla ore deposit is related to a magmatic/hydrothermal event that occurred between 157.4 ± 3.6 and 163.5 ± 1.9 Ma, contemporaneous or shortly after the extrusion of the volcanic sequence. This age is in agreement with the Re–Os age of 159 ± 16 Ma obtained from the mineralization itself (Tristá-Aguilera et al., Miner Depos, 41:99–105,2006).     

Isotopic composition (δ<Superscript>13</Superscript>C and δ<Superscript>18</Superscript>O) and genesis of carbonates from the famennian manganiferous formation of Pai-Khoi

The results of isotope-geochemical studies of carbonates of different mineral types from manganese and host rocks of the Famennian manganiferous formation of Pai-Khoi are reported. Kutnahorite ores are characterized by δ¹³C values from–6.6 to 1.3‰ and δ¹⁸O from 20.0 to 27.4‰. Rhodonite–rhodochrosite rocks of the Silovayakha ore occurrence have δ¹³C from–5.2 to–2.9 and δ¹⁸O from 25.4 to 24.3‰. Mineralogically similar rocks of the Nadeiyakha ore occurrence show the lighter carbon and oxygen isotopic compositions: δ¹³C from–16.4 to–13.1 and δ¹⁸O from 24.8 to 22.5‰. Similar isotopic compositions were also obtained for rhodochrosite–kutnahorite rocks of this ore occurrence: δ¹³C from–13.0 to–10.4‰ and δ¹⁸O from 24.6 to 21.7‰. Siderorodochrosite ores differ in the lighter oxygen and carbon isotopic compositions: δ¹⁸O from 18.7 to 17.6‰ and δ¹³C from–10.2 to–9.3‰, respectively. In terms of the carbon and oxygen isotopic compositions, host rocks in general correspond to marine sedimentary carbonates. Geological-mineralogical and isotope data indicate that the formation of the manganese carbonates was related to the hydrothermal ore-bearing fluids with the light isotopic composition of oxygen and carbon dissolved in CO₂. The isotopic features indicate an authigenic formation of manganese carbonates under different isotopegeochemical conditions.     

Radiation-induced defects in euclase: formation of O<Superscript>−</Superscript> hole and Ti<Superscript>3+</Superscript> electron centers

Irradiation techniques are often applied to gem minerals for color enhancement purposes. Natural green, blue and colorless specimens of rare gemological quality euclase, BeAlSiO₄(OH), from Brazil were irradiated with gamma rays in the dose range from 10 to 500 kGy. Although the colors of the different specimens were not strongly influenced, two different irradiation-induced paramagnetic defect centers were found by electron paramagnetic resonance (EPR). The first one is an O⁻ hole center interacting with one Al neighbor and the second is a Ti³⁺ electron center. The EPR angular rotation patterns of both irradiation-induced defects were measured and analyzed. The results suggest that O⁻ hole centers are formed by dissociation of the hydroxyl ions, similar as in topaz crystals. In euclase the OH⁻ ions interconnect distorted Al octahedra and Be tetrahedra in O₅ positions. During irradiation, the electrons are captured by titanium ions (Ti⁴⁺ + e⁻), leading to the formation of paramagnetic Ti³⁺ ions. From the EPR rotation patterns it is clear that these ions substitute for Al ions. The spin Hamiltonian parameters of the irradiation-induced defects are analyzed and compared to similar defect centers in other mineral specimens. Thermal annealing experiments show that the O⁻ hole centers and Ti³⁺ electron centers are directly connected through the radiation process.     

Rb–Sr and <Superscript>147</Superscript>Sm–<Superscript>143</Superscript>Nd systematics of gabbro and dolerites from fragments of ophiolite complexes of the Middle Urals

The Rb–Sr and ¹⁴⁷Sm–¹⁴³Nd age data obtained for sheeted dolerite dykes and rocks of the Platinum Belt of the Urals within the Tagil segment of the paleoceanic spreading structure (Middle Urals) are discussed. The study of the Rb–Sr isotope systematics of gabbro allowed us to reveal errochronous dependencies, which yielded ages of 415 and 345 Ma at (⁸⁷Sr/⁸⁶Sr)₀ = 0.70385 ± 0.00068 and 0.7029 ± 0.0010, correspondingly. The ¹⁴⁷Sm–¹⁴³Nd isotope age data demonstrate a specific coincidence of the chronometric ages of the sheeted dolerite dyke complex (426 ± 54, 426 ± 34, and 424 ± 19 Ma) and gabbro from the Revda gabbro–ultramafic massif (431 ± 27 Ma) and from screens between dolerite dykes in the sheeted dyke complex (427 ± 32 Ma, 429 ± 26 Ma). The proximity of the ¹⁴⁷Sm–¹⁴³Nd ages of gabbro and dolerite can be explained by the thermal effect of the basaltic melt, which is the protolith for the dyke complex, on the hosting gabbro.     

Gravity anomalies over the Central Indian Ridge between 3<Superscript>∘</Superscript>S and 11<Superscript>∘</Superscript>S,Indian Ocean: Segmentation and crustal structure

High-resolution shipboard geophysical investigations along the Indian Ocean ridge system are sparse especially over the Carlsberg and Central Indian ridges. In the present study, the shipboard gravity and multibeam bathymetry data acquired over a 750 km long section of the Central Indian Ridge between 3 ^°S and 11 ^°S have been analysed to understand the crustal structure and the ridge segmentation pattern. The mantle Bouguer anomalies (MBA) and the residual mantle Bouguer anomalies (RMBA) computed in the study area have shown significant variations along the ridge segments that are separated by transform and non-transform discontinuities. The MBA lows observed over the linear ridge segments bounded by well-defined transform faults are attributed to the thickening of the crust at the middle portions of the ridge segments. The estimates of crustal thickness from the RMBA shows an average of 5.2 km thick crust in the axial part of the ridge segments. The MBA and relative RMBA highs along the two non-transform discontinuities suggests a thinner crust of up to 4.0 km. The most significant MBA and RMBA highs were observed over the Vema transform fault suggesting thin crust of 4 km in the deepest part of the transform fault where bathymetry is more than 6000 m. The identified megamullion structures have relative MBA highs suggesting thinner crust. Besides MBA lows along the ridge axis, significant off-axis MBA lows have been noticed, suggesting off-axis mantle upwelling zones indicative of thickening of the crust. The rift valley morphology varies from the typical V-shaped valley to the shallow valley floor with undulations on the inner valley floor. Segments with shallow rift valley floor have depicted well-defined circular MBA lows with persistent RMBA low, suggesting modulation of the valley floor morphology due to the variations in crustal thickness and the mantle temperature. These are supported by thicker crust and weaker lithospheric mantle.