Li, B and Be Contents of Harzburgites from the Dramala Complex (Pindos Ophiolite, Greece): Evidence for a MOR-type Mantle in a Supra-subduction Zone Environment

The Pindos ophiolite represents oceanic lithosphere obducted during the Jurassic. The Dramala mantle section mainly consists of highly depleted spinel harzburgite and minor plagioclase-bearing harzburgite. Textural observations and major element compositions of minerals indicate that the harzburgites experienced impregnation by a mafic, depleted melt and subsequent high-temperature (high-T) hydration and cooling (>750°C) forming pargasite and edenitic hornblende. During further cooling (from ≥ 350-400°C to < 100°C), talc + tremolite ± serpentine ± olivine, serpentine + magnetite, and finally plagioclase alteration phases formed. To test the hypothesis of a supra-subduction zone origin for the Dramala mantle, we measured Li, B and Be contents of minerals by secondary ion mass spectrometry. Whole-rock contents were measured using inductively coupled plasma-mass spectrometry and prompt gamma neutron activation analysis. We observe low Li and B contents of primary minerals (olivine, orthopyroxene, clinopyroxene) consistent with values for unmetasomatized mantle minerals; only Li contents of clinopyroxene (up to 3·7 μg/g) are slightly elevated. The bulk Li contents (0·5-1·1 μg/g) are in the upper range of values for unmetasomatized mantle, whereas B contents (<0·04-1·1 μg/g) are variable and slightly elevated compared with the unmetasomatized mantle as a result of serpentinization. Beryllium abundances in all minerals are very low (<0·005 μg/g), except for pargasite, where a maximum Be content of 0·012 μg/g was measured. The selective addition of Li to clinopyroxene can be related to the interaction with a depleted melt, and/or to partitioning of Li into clinopyroxene upon cooling. During high-T hydration and cooling, the fluid calculated to be in equilibrium with the pargasite or edenitic hornblende (based on Li, Be and B) could have been reaction-modified seawater. Low-T hydration may have led to a very minor increase in bulk B content of most samples and to the formation of serpentine with highly variable B contents (0·1-28 μg/g). Low-T hydration decreased the Li content of orthopyroxene, and Li was probably leached from some samples. The lack of correlation between degree of serpentinization and bulk B contents as well as the presence of high- and low-B serpentine can be explained by low fluid-rock ratios, decreasing T during serpentinization and lack of equilibrium as a result of fast obduction-exhumation. The low light-element contents of primary minerals and whole-rock samples clearly argue against a supra-subduction zone (SSZ) origin of the Dramala mantle section, and against the previous hypothesis of hydrous melting of the Pindos mantle above a subduction zone. We therefore conclude that the Dramala harzburgites represent a mid-ocean ridge (MOR)-type mantle, and not an SSZ-type mantle, juxtaposed with MOR-type and SSZ-type oceanic crust, either in a back-arc or in an intra-oceanic subduction zone settin

Neogene calc-alkaline intrusive magmatism of post-collisional origin along the Outer Carpathians: a comparative study of the Pieniny Mountains and adjacent areas

A petrographical and geochemical analysis was carried out on intrusive rocks from the Pieniny and Moravian areas, with special attention to boron content and K-Ar radiometric ages. The intrusions form medium- to high-potassium calc-alkaline andesitic suites, which are compositionally slightly different from each other and from the other calc-alkaline sequences in the Carpathian-Pannonian Region. No significant geochemical differences were observed within the different phase intrusions in the Pieniny areas. However, there is a slight difference in major and trace element composition between the Moravian and Pieniny intrusions. The andesitic rocks in the Pieniny and Moravian area are enriched in large ion lithophile elements and light rare earth elements and depleted in high field strength elements, indicating a metasomatized mantle source of the parent magmas. The low boron concentration of the andesitic rocks in the Pieniny area is in the range measured in back-arc, intraplate basalts of the Bakony-Balaton Highland volcanic field, whereas the higher boron content of the Moravian rocks overlaps with that of the Western Carpathian andesites. This may indicates the heterogeneity of the mantle lithosphere below the areas, or indicates different magma evolution histories. On the basis of the systematic geochronological study, the intrusive rocks along the Outer Carpathians can be divided on three groups, which overlap with each other temporally. The oldest magmatism occurred from 14.8 Ma to 11.0 Ma in the Uhersky Brod area, Moravia, which was followed by the emplacement of andesitic dikes and sills in the Pieniny Mts., south Poland (13.5–10.8 Ma). In the Pieniny area, two intrusive phases were distinguished. Partly overlapping with this area, but generally younger than this magmatism, the emplacement of the youngest intrusions is referable to the Poiana Botizei-Ţibleş-Toroiaga-Rodna-Bârgâu intrusive area, Romania, where magmatic activity started at ~11.8 Ma and terminated at 8.0 Ma

Determination of chlorine concentrations in whole rock: Comparison between prompt-gamma activation and isotope-dilution AMS analysis

Accurate determination of chlorine concentrations in terrestrial rocks is of importance for the interpretation of terrestrial in-situ cosmogenic 36Cl. Neutron capture by 35Cl, together with production from Ca and K, is one of the three major production pathways of 36Cl in rocks. Here, we present an inter-comparison of chlorine determinations by two procedures. The first approach is an independent Cl determination by prompt-gamma (neutron) activation analysis (PGAA). The second method is isotope-dilution based on isotopically enriched stable chlorine carrier added during chemical sample preparation for accelerator mass spectrometry (ID-AMS). Twenty-six (26) whole rock samples have been processed for PGAA and ID-AMS analysis. This study constitutes the first published inter-comparison for concentrations below 100 μgCl/g. Our results show no significant difference in Cl concentrations between methods. This agreement indicates good retention of chloride during the procedure we employ for whole rock sample dissolution. No significant loss of stable chlorine from either the spike or the sample occurs before isotopic equilibrium is reached, prior to AgCl precipitation. Uncertainties, which are &lt;5% for both methods, affect the uncertainty of the total 36Cl production rate less than 2% for our samples. The Cl concentration measured by PGAA can be used to calculate the amount of isotopically enriched spike for AMS-ID sample preparation with the aim to optimize 36Cl analysis. Furthermore, PGAA offers an advance for the interpretation of 36Cl measurements. It allows measurement of concentrations of major, minor and trace elements including the elements for 36Cl production (Cl, K, Ca, Ti, and Fe), as well as of neutron absorbers and neutron moderators (H, B, Sm and Gd). These measurements are performed simultaneously and with a precision necessary for calculating the relative contributions to 36Cl production from the different mechanisms

Experimental study of concrete activation compared to MCNP simulations for safety of neutron sources

The neutron activation of shielding materials and the generated decay gamma radiation are well-known issues in terms of occupational exposure. Though the trace elements of shielding concretes can be dominant sources of the produced activity in such cases, their concentrations are often missing from the input data of shielding-related Monte Carlo simulations. For this reason, three concrete types were studied, that were considered in the European Spallation Source (ESS) ERIC. Their composition - including the trace elements - were determined via XRF, PGAA and NAA techniques. Realistic input data were developed for these materials, containing the parent elements of all the dominant radioisotopes, and were validated against measured data of neutron irradiation experiments.Comment: 29 pages, 9 figure