Fluxes of total mercury (Hg(T)) and monomethylmercury (MMHg) associated with submarine groundwater discharge (SGD) at two sites onthe central California coast were estimated by combining measurements of Hg(T) and MMHg in groundwater with the use of short-lived, naturally occurring radium isotopes as tracers of groundwater inputs. Concentrations of Hg(T) were relatively low, ranging from 1.2 to 28.3 pM in filtered groundwater, 0.8 to 11.6 pM in filtered surface waters, and 2.5 to 12.9 pM in unfiltered surface waters. Concentrations of MMHg ranged from < 0.04 to 3.1 pM in filtered groundwater, < 0.04 to 0.53 pM in filtered surface waters, and 0.07 to 1.2 pM in unfiltered surface waters. Multiple linear regression analysis identified significant (p < 0.05) positive correlations between dissolved groundwater concentrations of Hg(T) and those of NH4+ and SiO2, and between dissolved groundwater concentrations of MMHg and those of Hg(T) and NH4+. However, such relationships did not account for the majority of the variability in concentration data for either mercury species in groundwater. Fluxes of Hg(T) via SGD were estimated to be 250 +/- 160 nmol day m(-1) of shoreline at Stinson Beach and 3.0 +/- 2.0 nmol m(-2) day(-1) at Elkhorn Slough. These Hg(T) fluxes are substantially greater than net atmospheric inputs of Hg(T) reported for waters in nearby San Francisco Bay. Calculated fluxes of MMHg to coastal waters via SGD were 10 +/- 12 nmol day(-1) m(-1) of shoreline at Stinson Beach and 0.24 +/- 0.21 nmol m(-2) day at Elkhorn Slough. These MMHg fluxes are similar to benthic fluxes of MMHg out of surface sediments commonly reported for estuarine and coastal environments. Consequently, this work demonstrates that SGD is an important source of both Hg(T) and MMHg to coastal waters along the central California coast.
We integrate benthic foraminiferal stable isotopes, X‐ray fluorescence elemental ratios, and carbonate accumulation estimates in a continuous sedimentary archive recovered at International Ocean Discovery Program Site U1443 (Ninetyeast Ridge, Indian Ocean) to reconstruct changes in carbonate deposition and climate evolution over the interval 13.5 to 8.2 million years ago. Declining carbonate percentages together with a marked decrease in carbonate accumulation rates after ~13.2 Ma signal the onset of a prolonged episode of reduced carbonate deposition. This extended phase, which lasted until ~8.7 Ma, coincides with the middle to late Miocene carbonate crash, originally identified in the eastern equatorial Pacific Ocean and the Caribbean Sea. Interocean comparison reveals that intense carbonate impoverishment at Site U1443 (~11.5 to ~10 Ma) coincides with prolonged episodes of reduced carbonate deposition in all major tropical ocean basins. This implies that global changes in the intensity of chemical weathering and riverine input of calcium and carbonate ions into the ocean reservoir were instrumental in driving the carbonate crash. An increase in U1443 Log (Ba/Ti) together with a change in sediment color from red to green indicate a rise in organic export flux to the sea floor after ~11.2 Ma, which predates the global onset of the biogenic bloom. This early rise in export flux from biological production may have been linked to increased advection of nutrients and intensification of upper ocean mixing, associated with changes in the seasonality and intensity of the Indian Monsoon.
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