Copper is of importance in geosciences, biosciences, and industry. Its isotopes can be used to study planetary processes, trace Cu biogeochemical cycling, identify the type of Cu-bearing ore minerals, investigate the formation of ore deposits, and explore concealed ore-bodies. However, Cu isotope fractionation parameters of the majority of copper minerals remain poorly known, impeding the application of Cu isotopes as a geochemical tracer. In this study, the first-principles methods are used to compute Cu isotope fractionation parameters of chalcocite (Cu₂S), covellite (CuS), villamaninite (CuS₂), chalcopyrite (CuFeS₂), cubanite (CuFe₂S₃), bornite (Cu₅FeS₄), cuprite (Cu₂O), malachite (Cu₂(CO₃)(OH)₂), azurite (Cu₃(CO₃)₂(OH)₂), antlerite (Cu₃(SO₄)(OH)₄), brochantite (Cu₄(SO₄)(OH)₆), liebauite (Ca₃Cu₅Si₉O₂₆), Cu-bearing enstatite (Mg_31/16Cu_1/16Si₂O₆), and native copper (Cu). The reduced partition function ratio of ⁶⁵Cu/⁶³Cu (10³ ln β₆₅₋₆₃) decreases in the order of Cu silicates > Cu carbonates > Cu sulfates > Cu oxide > native Cu > Cu sulfides. The10³ ln β₆₅₋₆₃values of these minerals display a weak correlation with oxidation state and Cu coordination number, while display a strong correlation with the average Cu-S bond lengths in Cu sulfides and the average Cu-O bond lengths in Cu oxysalt minerals with the same Cu coordination number. For Cu₂S and Cu₅FeS₄ polymorphs, the extent of Cu isotope fractionation arising from polymorphic transformations is different. Our calculated results are useful for understanding the enrichment of Cu isotopes in nature. Cu isotope fractionation between sulfides and silicates may be a potential geothermometer.

铜在地球科学，生物科学和工业中至关重要。它的同位素可用于研究行星过程，追踪铜的生物地球化学循环，识别含铜矿石矿物的类型，调查矿床的形成以及探索隐蔽的矿体。但是，大多数铜矿物的铜同位素分馏参数仍然知之甚少，这阻碍了铜同位素作为地球化学示踪剂的应用。在这项研究中，第一原理方法用于计算菱锰矿（Cu ₂ S），铜锌矿（CuS ），钙锰矿（CuS ₂），黄铜矿（CuFeS ₂），绿铅矿（CuFe ₂ S ₃）的Cu同位素分馏参数，斑铜矿（Cu ₅ FeS ₄），铜铁矿（Cu ₂ O），孔雀石（Cu ₂（CO ₃）（OH）₂），蓝铜矿（Cu ₃（CO ₃）₂（OH）₂），硬铁矿（Cu ₃（SO ₄）（OH）₄），方晶石（Cu ₄（SO ₄）（OH）₆），利勃石（Ca ₃ Cu ₅ Si ₉ O ₂₆），含铜顽辉石（Mg _31/16 Cu _1/16 Si ₂ O ₆）和天然铜（铜）。降低的分区函数比率⁶⁵铜/ ⁶³的Cu（10 ³  LN  β _65-63）在Cu的顺序降低硅酸盐>铜碳酸盐>铜硫酸盐> Cu氧化物>天然铜>铜的硫化物。块10 ³  LN  β _65-63这些矿物质的值显示与氧化态和Cu配位数弱相关，而与显示在Cu中的硫化物的平均的Cu-S键的长度和平均的Cu-O键长在Cu中含氧盐的强相关性具有相同的铜配位数的矿物。对于Cu ₂ S和Cu ₅ FeS ₄多晶型物，多态性转变引起的铜同位素分馏程度不同。我们的计算结果对于理解自然界中铜同位素的富集是有用的。硫化物和硅酸盐之间的铜同位素分馏可能是潜在的地热仪。