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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.

The Paleocene-Eocene Thermal Maximum (PETM), ca. 55 Ma, was a period of extreme global warming caused by rapid emission of greenhouse gases. It is unknown what ended this episode of greenhouse warming, but high oceanic export productivity over thousands of years (as indicated by high accumulation rates of barium, Ba) may have been a factor in ending this warm period by carbon sequestration. However, Ba has a short oceanic residence time (~10 k.y.), so a prolonged global increase in Ba accumulation rates requires an increase in input of Ba to the ocean, increasing barite saturation. We use a novel proxy for barite saturation (Sr/Ba in marine barite) to demonstrate that the seawater saturation state with respect to barite did not change across the PETM. The observations of increased barite burial, no change in saturation, and the short residence time can be reconciled if Ba burial decreased at continental margin and shelf sites due to widespread occurrence of suboxic conditions, leading to Ba release into the water column, combined with increased biological export production at some pelagic sites, resulting in Ba sink reorganization.

The effect of global climate cycles driven by Earth's orbital variations on evolution is poorly understood because of difficulties achieving sufficiently-resolved records of past evolution. The fossil remains of coccolithophores, a key calcifying phytoplankton group, enable an exceptional assessment of the impact of cyclic orbital-scale climate change on evolution because of their abundance in marine sediments, and because coccolithophores demonstrate extreme morphological plasticity in response to the changing environment1,2. Recently, evolutionary genetic analyses linked broad changes in Pleistocene fossil coccolith morphology to species radiation events3. Here, using high-resolution coccolith data, we show that during the last 2.8 million years coccolithophore evolution was forced by Earth's orbital eccentricity with rhythms of ~100,000 years and 405,000 years -a distinct spectral signature to that of coeval global climate cycles4. Simulations with an Earth System Model5 including the marine carbon cycle6 demonstrate that eccentricity directly impacts the diversity of ecological niches occurring over the annual cycle in the tropical ocean. Reduced seasonality favours species with mid-size coccoliths that bloom yearround, increasing coccolith carbonate export and burial. We posit that eccentricity pacing of phytoplankton evolution contributed to the strong 405,000-year pacing seen in records of the global carbon cycle.

Abstract. In the modern northern Indian Ocean, biological productivity is intimately linked to near-surface oceanographic dynamics forced by the South Asian, or Indian, monsoon. In the late Pleistocene, this strong seasonal signal is transferred to the sedimentary record in the form of strong variance in the precession band (19–23 kyr), because precession dominates low-latitude insolation variations and drives seasonal contrast in oceanographic conditions. In addition, internal climate system feedbacks (e.g. ice-sheet albedo, carbon cycle, topography) play a key role in monsoon variability. Little is known about orbital-scale monsoon variability in the pre-Pleistocene, when atmospheric CO2 levels and global temperatures were higher. In addition, many questions remain open regarding the timing of the initiation and intensification of the South Asian monsoon during the Miocene, an interval of significant global climate change that culminated in bipolar glaciation. Here, we present new high-resolution (<1 kyr) records of export productivity and sediment accumulation from International Ocean Discovery Program Site U1443 in the southernmost part of the Bay of Bengal spanning the late Miocene (9 to 5 million years ago). Underpinned by a new orbitally tuned benthic isotope stratigraphy, we use X-ray fluorescence-derived biogenic barium variations to discern productivity trends and rhythms. Results show strong eccentricity-modulated precession-band productivity variations throughout the late Miocene, interpreted to reflect insolation forcing of summer monsoon wind strength in the equatorial Indian Ocean. On long timescales, our data support the interpretation that South Asian monsoon winds were already established by 9 Ma in the equatorial sector of the Indian Ocean, with no apparent intensification over the latest Miocene.

The sulphur isotopic composition of dissolved sulphate in seawater has varied considerably through time. Certain time intervals are characterised by distinct variations and a relatively high rate of change. These relatively rapid fluctuations allow for correlation of sediment sections using sulphur isotopes. Sulphur isotope reconstructions based on the analysis of carbonate associated sulphate or marine barite result in sulphur isotope records with an age resolution of 1-5 million years (Ma), and for some age intervals the resolution is<0.25 Ma. At these specific time intervals, where higher resolution records exist and excursions in the record are identified, the trends could be used for stratigraphic correlations. Such records are particularly useful in sections from deep marine sites that lack biostratigraphic controls or where biozones do not provide sufficient resolution.

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