Development of three chalcopyrites and one copper metal as potential reference materials for copper isotopic analysis by LA‐MC‐ICP‐MS

Rationale Laser ablation multicollector inductively coupled plasma mass spectrometry (LA‐MC‐ICP‐MS) has become a powerful technique for in situ Cu isotopic analysis in natural geological samples. Cu isotopic compositions in natural chalcopyrites have been used to reveal aspects of the mineralization processes directly. However, internationally or commercially available matrix‐matched chalcopyrite reference materials for mass fractionation correction or quality control purposes are still lacking for in situ Cu isotopic analysis using LA‐MC‐ICP‐MS. Methods Three natural chalcopyrites 14ZJ12‐1, JGZ‐29 and JGZ‐78, and one copper metal GBW02141 with different Cu isotopic compositions were investigated as potential microanalytical reference materials by LA‐MC‐ICP‐MS. Ga element was used as an internal standard to correct the mass fractionation of Cu isotopes during LA‐MC‐ICP‐MS analysis. Results A large number of Cu isotope ratio measurements using femtosecond LA‐MC‐ICP‐MS were conducted and produced good intermediate precision of δ65CuNIST976 (0.07–0.08‰, 2 standard deviations), demonstrating the homogeneous Cu isotopic distribution in the recommended samples. The mean δ65CuNIST976 values of −0.21 ± 0.04‰, 0.46 ± 0.04‰, −0.06 ± 0.04‰ and 0.11 ± 0.05‰ (2 standard deviations) in 14ZJ12‐1, JGZ‐29, JGZ‐78 and GBW02141, respectively, were obtained using solution‐MC‐ICP‐MS in the four recommended samples. Conclusions Here, we describe three natural chalcopyrites 14ZJ12‐1, JGZ‐29, JGZ‐78, and one copper metal GBW02141 as the potential Cu isotopic reference materials for LA‐MC‐ICP‐MS analysis. Our analyses demonstrate that these recommended materials have a high degree of elemental and isotopic homogeneity, indicating that they are suitable for microanalysis techniques for data quality assurance or interlaboratory calibration.