High-precision Zirconium Isotope Analysis of Pacific Seawater Reveals Large Mass-Dependent Fractionations in the Ocean

Zirconium (Zr) stable isotopes recently emerged as potential tracers of magmatic processes and, as a result, their behavior in high-temperature environments have been the focus of extensive characterization. In contrast, few studies have focused on Zr behavior and isotopic fractionation in low temperature or aqueous environments. Here, we describe a new analytical routine for highly precise and accurate analysis of Zr isotopes of water samples, using a combination of double-spike and iron co-precipitation methods. To assess the impact of potential systematic biases a series of experiments were conducted on natural and synthetic water samples. Our results show that the spike-to-sample ratio, matrix composition, and high field-strength element (HFSE) concentration have negligible effects on measured seawater Zr isotopic compositions, and that the Fe coprecipitation method used yields accurate and precise Zr isotope data. We thus apply this method to natural seawater samples collected from a water column profile in the Pacific Ocean off the coast of California, with depths ranging from 5 to 711 m. We find that the natural seawater samples are highly fractionated relative to solid-Earth values and display marked variability in delta 94/90Zr as a function of depth, ranging from - +0.650 %o near the surface, to + 1.530 %o near the profile bottom, with an analytical uncertainty of +/- -0.045 %o (2 SE, external reproducibility). The delta 94/90Zr value of seawater is much higher than that of Earth's mantle and continental crust, which has a delta 94/90Zr value near zero, indicating the presence of processes in the hydrosphere capable of inducing large mass-dependent fractionation. Furthermore, the seawater delta 94/90Zr value exhibits systematic variations with respect to water depth and salinity, suggesting that Zr isotopic compositions may be sensitive to seawater chemical properties and source highlighting its potential utility as a tracer of biogeochemical processes within the ocean.