Recovering the primary geochemistry of Jack Hills zircons through quantitative estimates of chemical alteration

Despite the robust nature of zircon in most crustal and surface environments, chemical alteration, especially associated with radiation damaged regions, can affect its geochemistry. This consideration is especially important when drawing inferences from the detrital record where the original rock context is missing. Typically, alteration is qualitatively diagnosed through inspection of zircon REE patterns and the style of zoning shown by cathodoluminescence imaging, since fluid-mediated alteration often causes a flat, high LREE pattern. Due to the much lower abundance of LREE in zircon relative both to other crustal materials and to the other REE, disturbance to the LREE pattern is the most likely first sign of disruption to zircon trace element contents. Using a database of 378 (148 new) trace element and 801 (201 new) oxygen isotope measurements on zircons from Jack Hills, Western Australia, we propose a quantitative framework for assessing chemical contamination and exchange with fluids in this population. The Light Rare Earth Element Index is scaled on the relative abundance of light to middle REE, or LREE-I = (Dy/Nd) + (Dy/Sm). LREE-I values vary systematically with other known contaminants (e.g., Fe, P) more faithfully than other suggested proxies for zircon alteration (Sm/La, various absolute concentrations of LREEs) and can be used to distinguish primary compositions when textural evidence for alteration is ambiguous. We find that zircon oxygen isotopes do not vary systematically with placement on or off cracks or with degree of LREE-related chemical alteration, suggesting an essentially primary signature. By omitting zircons affected by LREE-related alteration or contamination by mineral inclusions, we present the best estimate for the primary igneous geochemistry of the Jack Hills zircons. This approach increases the available dataset by allowing for discrimination of on-crack analyses (and analyses with ambiguous or no information on spot placement or zircon internal structures) that do not show evidence for chemical alteration. It distinguishes between altered and unaltered samples in ambiguous cases (e.g., relatively high Ti), identifying small groups with potentially differing provenance from the main Jack Hills population. Finally, filtering of the population using the LREE-I helps to more certainly define primary correlations among trace element variables, potentially relatable to magmatic compositional evolution.