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.     

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     

How Cr<Superscript>3+</Superscript> and Fe<Superscript>3+</Superscript> affect Mg–Al order–disorder transformation at high temperature in natural spinels

Three natural Mg(Al_2-yCr_y)O₄ spinels (y 0.07–0.16), highly ordered in terms of Mg–Al, and one Mg(Al_2–yFe³⁺_y)O₄ spinel (y0.08), highly ordered also in terms of Fe³⁺, were studied by means of X-ray single-crystal diffraction. All samples were heated in situ from 25 to 1000 °C in order to follow both thermal expansion and evolution of the structural state of spinel with temperature. Thermal expansion was monitored by means of the variation of cell edge a with temperature, and found to be well represented throughout the temperature range by a regression line a = a₀ (1+T), slightly different at lower and higher temperatures. Thermal expansion coefficient ₁, referring to the lower temperature range (i.e. during pure thermal expansion), was slightly lower than ₂, calculated only over the highest temperatures. The trend showed different slopes for individual crystals. Structural evolution with temperature was studied by means of the variation of oxygen positional parameter u, which is strongly influenced by intersite cation exchange and thus closely correlated with inversion parameter x. In particular, in the three Cr samples, in which Cr resides only in the octahedral site, u parameter variations and hence the order–disorder process, started at about 700 °C. Instead, in the Fe³⁺ sample, this process was triggered at lower temperatures, starting at 550 °C with Fe³⁺–Mg exchange followed at higher temperatures by that of Mg–Al. Cr contents in the Cr samples affected the occupancy of Al in the tetrahedral site at the highest temperatures. In both Mg–Al–Cr and Mg–Al–Fe³⁺ compositions, if CrFe³⁺, parameter u reached the same value only when the Mg–Al exchange was dominant, i.e. at the highest temperatures, but not before. Cation distribution at each temperature was obtained by the bond-length model, applying thermal expansion to pure bond lengths. This method is applied here to complex compositions for the first time.     

Molecular simulation study on K<Superscript>+</Superscript>–Cl<Superscript>−</Superscript> ion pair in geological fluids

This paper reports a classical molecular dynamics study of the potential of mean forces (PMFs), association constants, microstructures K⁺–Cl^? ion pair in supercritical fluids. The constrained MD method is used to derive the PMFs of K⁺–Cl^? ion pair from 673 to 1273 K in low-density water (0.10–0.60 g/cm³). The PMF results show that the contact ion-pair (CIP) state is the one most energetically favored for a K⁺–Cl^? ion pair. The association constants of the K⁺–Cl^? ion pair are calculated from the PMFs, indicating that the K⁺–Cl^? ion pair is thermodynamically stable. It gets more stable as T increases or water density decreases. The microstructures of the K⁺–Cl^? ion pair in the CIP and solvent-shared ion-pair states are characterized in detail. Moreover, we explore the structures and stabilities of the KCl–Au(I)/Cu(I) complexes by using quantum mechanical calculations. The results reveal that these complexes can remain stable for T up to 1273 K, which indicates that KCl may act as a ligand complexing ore-forming metals in hydrothermal fluids.     

Geochronological (U–Pb,U–Th–total Pb,Sm–Nd) and geochemical (REE, <Superscript>87</Superscript>Sr/<Superscript>86</Superscript>Sr, δ<Superscript>18</Superscript>O, δ<Superscript>13</Superscript>C) tracing of intraplate tectonism and associated fluid flow in the Warburton Basin,Australia

The Warburton Basin of central Australia has experienced a complex tectonic and fluid-flow history, resulting in the formation of various authigenic minerals. Geochemical and geochronological analyses were undertaken on vein carbonates from core samples of clastic sediments. Results were then integrated with zircon U–Pb dating and uraninite U–Th–total Pb dating from the underlying granite. Stable and radiogenic isotopes (δ¹⁸O, Sr and εNd), as well as trace element data of carbonate veins indicate that >200 °C basinal fluids of evolved meteoric origin circulated through the Warburton Basin. Almost coincidental ages of these carbonates (Sm–Nd; 432 ± 12 Ma) with primary zircon (421 ± 3.8 Ma) and uraninite (407 ± 16 Ma) ages from the granitic intrusion point towards a substantial period of active tectonism and an elevated thermal regime during the mid Silurian. We hypothesise that such a thermal regime may have resulted from extensional tectonism and concomitant magmatic activity following regional orogenesis. This study shows that the combined application of geochemical and geochronological analyses of both primary and secondary species may constrain the timing of tectonomagmatic events and associated fluid flow in intraplate sedimentary basins. Furthermore, this work suggests that the Sm–Nd-isotopic system is surprisingly robust and can record geologically meaningful age data from hydrothermal mineral species.     

<Superscript>190</Superscript>Pt–<Superscript>4</Superscript>He age of PGE ores in the Alkaline–Ultramafic Kondyor Massif (Khabarovsk District,Russia)

A new ¹⁹⁰Pt–⁴He method for dating isoferroplatinum has been developed at the Institute of Precambrian Geology and Geochronology, Russian Academy of Sciences. Here we publish the first results of dating of isoferroplatinum from the main mineralogical and geochemical types of PGE mineralization in dunite. The obtained ¹⁹⁰Pt–⁴He age of isoferroplatinum is 129 ± 6 Ma. The gained ¹⁹⁰Pt–⁴He age of isoferroplatinum specimens of different genesis (magmatic, fluid–metamorphogenic, and metasomatic) from the Kondyor Massif indicates that the PGM mineralization took place synchronously and successively with evolution of primarily picrite, followed by subalkaline and alkaline melts of the Mesozoic tectonic–magmatic activation of the Aldan Shield.     

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.     

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).     

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.     

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.     

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.     

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.     

<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.     

Residence time distribution in a large unconfined–semiconfined aquifer in the Argentine Pampas using <Superscript>3</Superscript>H/<Superscript>3</Superscript>He and CFC tracers

The Pampa region in Argentina includes vast unconfined–semiconfined aquifers that local economies depend upon, but detailed knowledge of the associated water resources is still lacking. The Pampeano aquifer in the Pampa plain of Argentina covers around 1.5 million km². In order to achieve a better understanding of the hydrogeological system through the estimation of mean residence times (MRT), water samples were taken from 12 monitoring wells, drilled at different depths in four locations, and analyzed for environmental tracers. The concentrations of ³H, tritiogenic ³He and chlorofluorocarbons (CFCs) can be explained by mixtures of young waters adjusted to exponential piston flow models (EPM) or dispersion models (DM), and different proportions of tracer-free waters (dead water). The sampling site located very close to the water divide shows a dominance of young waters: 85 % of water best represented by a DM model with a MRT of 3 years. For the shallow wells at other sites, best-fitting models result in a DM with MRT between 20 and 35 years, and proportions of dead water between 40 and 60 %. These results lead to important updates in the conceptual model of the Pampeano aquifer. Large proportions of dead water at a few meters depth can be the consequence of upward flows in a multilayered aquifer or diffusive retardation in the inter-bedded clay layers.     

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.     

Kimberlite age in the Arkhangelsk Province,Russia: Isotopic geochronologic Rb–Sr and <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar and mineralogical data on phlogopite

The paper reports detailed data on phlogopite from kimberlite of three facies types in the Arkhangelsk Diamondiferous Province (ADP): (i) massive magmatic kimberlite (Ermakovskaya-7 Pipe), (ii) transitional type between massive volcaniclastic and magmatic kimberlite (Grib Pipe), and (iii) volcanic kimberlite (Karpinskii-1 and Karpinskii-2 pipes). Kimberlite from the Ermakovskaya-7 Pipe contains only groundmass phlogopite. Kimberlite from the Grib Pipe contains a number of phlogopite populations: megacrysts, macrocrysts, matrix phlogopite, and this mineral in xenoliths. Phlogopite macrocrysts and matrix phlogopite define a single compositional trend reflecting the evolution of the kimberlite melt. The composition points of phlogopite from the xenoliths lie on a single crystallization trend, i.e., the mineral also crystallized from kimberlite melt, which likely actively metasomatized the host rocks from which the xenoliths were captured. Phlogopite from volcaniclastic kimberlite from the Karpinskii-1 and Karpinskii-2 pipes does not show either any clearly distinct petrographic setting or compositional differentiation. The kimberlite was dated by the Rb–Sr technique on phlogopite and additionally by the ⁴⁰Ar/³⁹Ar method. Because it is highly probable that phlogopite from all pipes crystallized from kimberlite melt, the crystallization age of the kimberlite can be defined as 376 ± 3 Ma for the Grib Pipe, 380 ± 2 Ma for the Karpinskii-1 pipe, 375 ± 2 Ma for the Karpinskii-2 Pipe, and 377 ± 0.4 Ma for the Ermakovskaya-7 Pipe. The age of the pipes coincides within the error and suggests that the melts of the pipes were emplaced almost simultaneously. Our geochronologic data on kimberlite emplacement in ADP lie within the range of 380 ± 2 to 375 ± Ma and coincide with most age values for Devonian alkaline–ultramafic complexes in the Kola Province: 379 ± 5 Ma; Arzamastsev and Wu, 2014). These data indicate that the kimberlite was formed during the early evolution of the Kola Province, when alkaline–ultramafic complexes (including those with carbonatite) were emplaced.     

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.     

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.     

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.     

Kinetics of Fe<Superscript>2+</Superscript>–Mg order–disorder in orthopyroxene: experimental studies and applications to cooling rates of rocks

We determined the forward rate constant (K⁺) for the Fe²⁺–Mg order–disorder between the M2 and M1 sites of orthopyroxene (OPx), which is described by the homogeneous reaction Fe²⁺ (M2) + Mg(M1) ↔ Mg(M2) + Fe²⁺ (M1), by both ordering and disordering experiments at isothermal condition and also by continuous cooling experiments. The rate constant was determined as a function of temperature in the range of 550–750°C, oxygen fugacity between quartz–fayalite–iron and Ni–NiO buffers, and at compositions of 16 and 50 mol% ferrosilite component. The K⁺ value derived from disordering experiment was found to be larger than that derived from ordering experiment at 550°C, while at T>580°C, these two values are essentially the same. The fO₂ dependence of the rate constant can be described by the relation K⁺ α (fO₂) ⁿ with n=5.5–6.5, which is compatible with the theoretically expected relation. The Arrhenius relation at the WI buffer condition is given by