Dissolved strontium in the subterranean estuary – Implications for the marine strontium isotope budget

Submarine groundwater discharge (SGD) to the ocean supplies Sr with less radiogenic ⁸⁷Sr/⁸⁶Sr than seawater, and thus constitutes an important term in the Sr isotope budget of the modern ocean. However, few data exist for Sr in coastal groundwater or in the geochemically dynamic subterranean estuary (STE). We examined Sr concentrations and isotope ratios from nine globally-distributed coastal sites and characterized the behavior of Sr in the STE. Dissolved Sr generally mixed conservatively in the STE, although large differences were observed in the meteoric groundwater end-member Sr concentrations among sites (0.1–24μM Sr). Strontium isotope exchange was observed in the STE at five of the sites studied, and invariably favored the meteoric groundwater end-member signature. Most of the observed isotope exchange occurred in the salinity range 5–15, and reached up to 40% exchange at salinity 10. Differences in fresh groundwater Sr concentrations and isotope ratios (⁸⁷Sr/⁸⁶Sr=0.707–0.710) reflected aquifer lithology. The SGD end-member ⁸⁷Sr/⁸⁶Sr must be lower than modern seawater (i.e., less than 0.70916) in part because groundwater Sr concentrations are orders of magnitude higher in less-radiogenic carbonate and volcanic island aquifers. A simple lithological model and groundwater Sr data compiled from the literature were used to estimate a global average groundwater end-member of 2.9μM Sr with ⁸⁷Sr/⁸⁶Sr=0.7089. This represents a meteoric-SGD-driven Sr input to the ocean of 0.7–2.8×10¹⁰molSry⁻¹. Meteoric SGD therefore accounts for 2–8% of the oceanic Sr isotope budget, comparable to other known source terms, but is insufficient to balance the remainder of the budget. Using reported estimates for brackish SGD, the estimated volume discharge at salinity 10 (7–11×10¹⁵Ly⁻¹) was used to evaluate the impact of isotope exchange in the STE on the brackish SGD Sr flux. A moderate estimate of 25% isotope exchange in the STE gives an SGD Sr end-member ⁸⁷Sr/⁸⁶Sr of 0.7091. The brackish SGD Sr flux thus accounts for 11–23% of the marine Sr isotope budget, but does not appear sufficient to balance the ∼40% remaining after other known sources are included. Substantial uncertainties remain for estimating the SGD source of Sr to the global ocean, especially in the determination of the volume flux of meteoric SGD, and in the paucity of measurements of groundwater Sr isotope composition in major SGD regions such as Papua New Guinea, the South America west coast, and West Africa. Consequently, our global estimate should be viewed with some caution. Nevertheless, we show that the combined sources of meteoric SGD and brackish SGD coupled with isotope exchange in the STE may constitute a substantial component (∼13–30%) of the modern oceanic ⁸⁷Sr/⁸⁶Sr budget, likely exceeding less radiogenic Sr inputs by sedimentary diagenesis and hydrothermal circulation through the mid-ocean ridge system. Temporal variation in SGD Sr fluxes and isotope composition may have contributed to fluctuations in the oceanic ⁸⁷Sr/⁸⁶Sr ratio over geologic time.