Discriminating fluid source regions in orogenic gold deposits using B-isotopes

The genesis of orogenic gold deposits is commonly linked to hydrothermal ore fluids derived from metamorphic devolatilization reactions. However, there is considerable debate as to the ultimate source of these fluids and the metals they transport. Tourmaline is a common gangue mineral in orogenic gold deposits. It is stable over a very wide P–T range, demonstrates limited volume diffusion of major and trace elements and is the main host of B in most rock types. We have used texturally resolved B-isotope analysis by secondary ion mass spectrometry (SIMS) to identify multiple fluid sources within a single orogenic gold ore district. The Loulo Mining District in Mali, West Africa hosts several large orogenic gold ore bodies with complex fluid chemistry, associated with widespread pre-ore Na- and multi-stage B-metasomatism. The Gara deposit, as well as several smaller satellites, formed through partial mixing between a dilute aqueous-carbonic fluid and a hypersaline brine. Hydrothermal tourmaline occurs as a pre-ore phase in the matrix of tourmalinite units, which host mineralization in several ore bodies. Clasts of these tourmalinites occur in mineralized breccias. Disseminated hydrothermal and vein hosted tourmaline occur in textural sites which suggest growth during and after ore formation. Tourmalines show a large range in δ11B values from −3.5 to 19.8‰, which record a change in fluid source between paragenetic stages of tourmaline growth. Pre-mineralization tourmaline crystals show heavy δ11B values (8–19.8‰) and high X-site occupancy (Na ± Ca; 0.69–1 apfu) suggesting a marine evaporite source for hydrothermal fluids. Syn-mineralization and replacement phases show lighter δ11B values (−3.5 to 15.1‰) and lower X-site occupancy (0.62–0.88 apfu), suggesting a subsequent influx of more dilute fluids derived from devolatilization of marine carbonates and clastic metasediments. The large, overlapping range in isotopic compositions and a skew toward the opposing population in the δ11B data for both tourmaline groups reflects continual tourmaline growth throughout mineralization, which records the process of fluid mixing. A peak in δ11B values at ∼8‰ largely controlled by tourmalines of syn- to post-ore timing represents a mixture of the two isotopically distinct fluids. This paper demonstrates that B-isotopes in tourmaline can be instrumental in interpreting complex and dynamic hydrothermal systems. The importance of B as an integral constituent of orogenic ore forming fluids and as a gangue phase in orogenic gold deposits makes B-isotope analysis a powerful tool for testing the level of source region variability in these fluids, and by extension, that of metal sources

Boron isotope composition of the cold-water coral Lophelia pertusa along the Norwegian margin: Zooming into a potential pH-proxy by combining bulk and high-resolution approaches

High-latitude cold-water coral reefs are particularly vulnerable to climate change due to enhanced CO2 uptake in these regions. To evaluate their physiological functioning and potential application as pH archives, we retrieved both recent and fossil samples of Lophelia pertusa along the Norwegian margin from Oslofjord (59°N), over to Trondheimsfjord, Sula and Lopphavet (70.6°N). Boron isotope analyses (δ11B) were undertaken using solution-based and laser ablation multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS; LA-ICP-MS), and secondary ion mass spectrometry (SIMS). Epi-fluorescence microscopy was employed to provide a rapid pre-screening routine for structure-specific subsampling in the coral skeleton. This integrated approach enabled us to assess heterogeneities within single specimens, as well as to investigate the role of local environmental influences including recent and past variations. All three mass spectrometry methods show substantial differences in the δ11B of the theca wall (TW) and the centres of calcification (COC's). Micro-bulk subsamples milled from the theca wall of modern specimens originating from different habitats but with comparable seawater pH (8–8.16) gave consistent δ11B values averaging 26.7 (±0.2‰, 2σ, n = 4), while COC subsamples systematically deviated towards lower B/Ca (by ~40%) and depleted δ11B values (minimum 22.7 ± 0.3‰, 2σ), implying a difference of at least 4‰ between TW and COC. SIMS and LA-ICP-MS measurements identified much larger internal heterogeneities with maximum variation of ~10‰ between the distinct skeletal structures; minimal SIMS δ11B values of ~17.3 ± 1.2‰ (2σ) were associated with the pure COC material. Our findings may be interpreted in terms of the occurrence of two main, but likely different, biomineralisation mechanisms in L. pertusa, with the COC's generally exhibiting minimal pH up-regulation, potentially supporting the use of bicarbonate in the early stages of biomineralisation. Furthermore, we highlight the potential utility of L. pertusa for palaeo-proxy studies if targeting the compositionally homogenous TW zones devoid of COC admixtures, which appear to provide highly reproducible measurements

Impact-related crystallization and modification of small zircons in Apollo 15 and 16 impactites at 4.2 Ga

Because of their robustness against resetting, in situ U-Pb ages of zircons in lunar impactites have the potential to provide constraints on the lunar bombardment history that may complement the more common K-Ar ages. Most previous work has focused on relatively large zircons that show growth zoning and ages were mostly interpreted as early igneous crystallization ages. Here we combine high-resolution mineralogical imaging and in situ U-Pb dating by ion microprobe to identify, characterize and date <20 μm size zircons in thin sections of lunar impact breccias. Several tens of grains of zircons of this size range were identified in thin sections of impactites from the Apollo 15 and 16 landing sites. Small zircons are more abundant in both noritic and evolved clinopyroxene, SiO2 or K-feldspar bearing lithologies compared to anorthositic bulk compositions. Both granular zircon aggregates and overgrowth on existing zircon or baddeleyite (in breccias 15455 and 67915) are interpreted to reflect high-temperature recrystallization of zircons or its high-temperature-pressure precursor phases, following shock heating events by impact. In contrast, conchoidal or poikilitic zircons <10 μm in Fe-Ni metal bearing noritic clasts or matrix (67915, 67955) crystallized in situ from impact melt. Most U-Pb ages of the 24 analyzed grains are either concordant or reverse discordant with 207Pb-206Pb ages ranging from 4.15 to 4.25 Ga. The small age range, combined with a large textural spectrum and the frequent presence of Fe-Ni metal suggest zircon crystallization from impact melt and recrystallization of pre-existing zirconium-bearing minerals by impact heating. Such ‘impact’ zircons with 4.2 Ga ages have now been reported from most Apollo landing sites, suggesting widespread formation and modification of zircons by basin-forming impacts at this time. The contrast between U-Pb zircon (predominantly 4.2 Ga) and K-Ar feldspar ages (predominantly 3.9 Ga) likely reflects resetting of the latter chronometer by impact heating

(Tabel S5e) Olivine-hosted melt inclusions (corrected for post-entrapment crystallization), host olivine composition adjacent to inclusion, and thermometry of melt inclusion - host mineral pairs

Belgium Herbarium image of Meise Botanic Garden