Deciphering the mineral code of urinary stones: A first look at zinc isotopes

Zinc (Zn) is an essential element for all living organisms, and Zn isotopes play a key role in studying the formation of disease. Despite extensive studies on Zn isotopes in healthy and diseased human tissues, the role of Zn isotopes in urinary stones remains unexplored. This study investigates Zn isotopes in 37 urinary stones using multi-collector inductively coupled plasma mass spectrometry. The δ⁶⁶Zn values of urinary stones range from -0.15‰ to 0.47‰, with a mean value of 0.11‰. Carbonate apatite (CA) stones exhibit lighter Zn isotopic compositions (δ⁶⁶Zn = -0.15‰ ∼ -0.03‰) compared to calcium oxalate (CO) stones (δ⁶⁶Zn = -0.11‰ ∼ 0.47‰). The variation in Zn isotopic compositions between CO and CA stones may result from urinary pH differences during stone formation. At higher urinary pH, CA stones are enriched in lighter Zn isotopes compared to CO stones. Urinary stones are enriched in lighter Zn isotopes compared to blood and urine. This study identifies two steps influencing Zn isotope variations during kidney transport. The first step involves kidney filtration and reabsorption, enriching heavy Zn isotope in the urine. The second step is the deposition process of urinary stones, where light isotopes, due to their lower bond energy, are more prone to breaking. This kinetic fractionation effect leads to an enrichment of light Zn isotope in urinary stones. Overall, this study offers preliminary insights into the geochemical mechanisms that influence the Zn isotopic composition in urinary stones.