Chemical Procedures for Rhenium Extraction from Geological Samples: Optimising the Anion Resin Bead Clean‐up Step

Rhenium–osmium geochronometry for samples with low Re and complex matrices requires improved Re extraction methods. Here, we investigate plausible controls on efficiency and efficacy of Re extraction during our anion resin bead purification. Four different protocols are compared, each isolating a single variable to test. Rhenium concentrations for solutions at each step of each protocol document differences in chemical recovery/yield. The negative‐thermal ionisation mass spectrometry (N‐TIMS) signal intensity serves as a proxy for Re yield and purity. These data document correlations between the N‐TIMS signal intensity and (a) the duration of anion resin bead conditioning prior to loading with Re‐bearing solution, and (b) both duration and strength of nitric acid used during rinsing of the Re‐loaded anion resin bead. The optimal protocol improved Re signal intensity around fourteen times compared with our current Re extraction protocol, an aggregate of 2.4 times improvement in chemical recovery (yield) and 5.8 times improvement in emission efficiency (purity). Repeated N‐TIMS isotopic measurements on our in‐house Re standard solution (1407) verify that our optimal protocol‐3 does not fractionate Re isotopes. The improved anion resin bead method considerably lowers the Re detection limit and allows Re‐Os isotopic analysis of picogram‐level Re hosted in geological samples with complex matrices.     

P–T evolution of kyanite eclogite from the Pirin Mountains (SW Bulgaria): implications for the Rhodope UHP Metamorphic Complex

A new occurrence of kyanite eclogite in the Pirin Mountains of southwestern Bulgaria within the rocks belonging to the Obidim Unit of the Rhodope Metamorphic Complex is presented. This eclogite provides important information about the peak–pressure conditions despite strong thermal overprint at low pressure. Textural relationships, phase equilibrium modelling and conventional geothermobarometry were used to constrain the metamorphic evolution. Garnet porphyroblasts with inclusions of omphacite (up to 43 mol.% Jd), phengite (up to 3.5 Si p.f.u.), kyanite, polycrystalline quartz, pargasitic amphibole, zoisite and rutile in the Mg‐rich cores (X_Mg = 0.44–0.46) record a prograde increase in P–T conditions from ～2.5 GPa and 650 °C to ～3 GPa and 700–750 °C. Maximum pressure values fall within the stability field of coesite. During exhumation, the peak–pressure assemblage garnet + omphacite + phengite + kyanite was variably overprinted by a lower pressure one forming symplectitic textures, such as diopside + plagioclase after omphacite and biotite + plagioclase after phengite. The development of spinel (X_Mg = 0.4–0.45) + corundum + anorthite assemblage in the kyanite‐bearing domains at ～1.1 GPa and 800–850 °C suggests a thermal overprint in the high‐pressure granulite facies stability field. This thermal event was followed by cooling at ～0.8 GPa under amphibolite facies conditions; retrograde kelyphite texture involving plagioclase and amphibole was developed around garnet. Our results add to the already existing evidence for ultra high pressure (UHP) metamorphism in the Upper Allochthon of the Rhodope Metamorphic Complex as in the Kimi Unit and show that it is more widespread than previously known. Published age data and field structural relations suggest that the Obidim Unit represents Variscan continental crust involved into the Alpine nappe edifice of the Rhodopes and that eclogite facies metamorphism was Palaeozoic, in contrast to the Kimi Unit where age determinations suggest a Jurassic or Cretaceous age for UHP metamorphism. This implies that UHP metamorphism in the Upper Allochthon of the Rhodopes may have occurred twice, during Alpine and pre‐Alpine orogenic events, and that two independent HP/UHP provinces of different age overlap in this area.