High-Precision Measurement of B Isotopes on Low-Boron Oceanic Volcanic Rock Samples via MC-ICPMS: Evaluating Acid Leaching Effects on Boron Isotope Compositions, and B Isotopic Variability in Depleted Oceanic Basalts

Recent analytical advances have made the high precision (2SD, ±≤1‰) determination of boron (B) isotopic ratios in silicate rocks a possibility, but few such data are as yet available, especially for low B (\u3c2 ppm) samples like oceanic basalts, where issues related to cryptic seawater alteration are a concern. This study carefully assesses the reproducibility of B isotope measurement via MC-ICPMS on silicate rocks. Based on repeated measurements of the standard reference materials B-5, B-6, JB-2, JR-2, AGV-2 and JB-3 and nature samples, the external reproducibility of MC-ICPMS measurements on the same solution is generally between 0.1‰ and 0.5‰ (2SD), a similar level of accuracy to that obtained based on long-term measurement of solution standard NIST SRM 951 of 0.4‰ (2SD). For different digestions, the average external reproducibility is 0.6‰ (2SD), which represents the whole procedure reproducibility, including chemical treatment. We have tested an acid leaching experimental procedure for its effects on the B isotope compositions of ~50 Ma boninites collected from a deep ocean setting. Fresh and moderately altered boninite samples were subjected to cold HCl leaching treatments for 1, 3, 5, 7 and 9 h, using 2 N and 6 N HCl, respectively. δ11B values for the fresh sample remained unchanged within error after leaching, suggesting that leaching did not lead to any B isotopic fractionation. δ11B values for different aliquots of an altered boninite sample show lower and uniform δ11B values after 1 h of 6 N HCl leaching, while aliquots leached in 2 N HCl show similar δ11B to the unleached altered sample. These results suggest that changes in B isotopes caused by at least moderate degrees of alteration, and/or adsorption effects in volcanic rocks preserved on the ocean floor can be effectively eliminated through short-duration 6 N HCl leaches before digestion and analysis. B isotope measurements on three documentably fresh, low-B N-type mid-ocean ridge basalt (MORB) glass samples from the Southwest Indian Ridge yield δ11B values from −6.62‰ to −7.39‰, within the range of the recommended global MORB value of ≈−7.1 ± 0.9‰, determined via SIMS methodologies (2SD at ±1.5‰; Marschall and Monteleone, 2015), and the range of four fresh glass samples from the Eastern Pacific Ridge of −7.3 ± 0.8‰, measured by in-situ laser-ablation ICP-MS (2SD at ±0.7–1.0‰; Le Roux et al., 2004)