After the atmosphere, the ocean is the most well-mixed and homogeneous global geochemical reservoir. Both physical and biological processes generate elemental and isotope variations in seawater. Contrasting geochemical behaviors cause elements to be susceptible to different fractionation mechanisms, with their isotopes providing unique insights into the composition and evolution of the ocean over the course of geological history. Supplementing the traditional stable isotopes (H, C, O, N, S) that provide information about ocean processes and past environmental conditions, radiogenic isotope (Sr, Nd, Os, Pb, U) systems can be used as time markers, indicators of terrestrial weathering, and ocean water mass mixing. Recent instrumentation advances have made possible the measurement of natural stable isotope variations produced by both mass-dependent and mass-independent fractionation for an ever-increasing number of metal elements (e.g. Li, B, Mg, Si, Ca, V, Cr, Fe, Ni, Cu, Zn, Se, Mo, Cd, Tl, U). The major emphasis in this review is on the isotopic composition of the light elements based on a comparatively large literature. Unlike O, H and S, the stable isotopes of C, N and Si do not have a constant isotopic composition in the modern ocean. The major cations Ca, Mg, and Sr fixed in carbonate shells provide the best proxies for reconstruction of the composition of the ocean in the past. Exhibiting large isotope enrichments in ocean water, B and Li are suitable for the investigation of water/rock interactions and can act as monitors of former oceanic pH. The bioessential elements Zn, Cd, and Ni are indicators of paleoproductivity in the ocean. Characteristic isotope enrichments or depletions of the multivalent elements V, Cr, Fe, Se, Mo, and U record the past redox state of the ocean/atmosphere system. Case studies describe how isotopes have been used to define the seawater composition in the geological past.
Keywords: Clumped isotopes; isotope fractionation; isotope geology; ocean history; oxygenation; radiogenic isotopes; seawater chemistry; stable isotopes.