Elizabeth M. Griffith

A Dynamic Marine Calcium Cycle During the Past 28 Million Years

Multiple lines of evidence have shown that the isotopic composition and concentration of calcium in seawater have changed over the past 28 million years. A high-resolution, continuous seawater calcium isotope ratio curve from marine (pelagic) barite reveals distinct features in the evolution of the seawater calcium isotopic ratio suggesting changes in seawater calcium concentrations. The most pronounced increase in the δ44/40Ca value of seawater (of 0.3 per mil) occurred over roughly 4 million years following a period of low values around 13 million years ago. The major change in marine calcium corresponds to a climatic transition and global change in the carbon cycle and suggests a reorganization of the global biogeochemical system.

Accuracy and precision of 88Sr/86Sr and 87Sr/86Sr measurements by MC‐ICPMS compromised by high barium concentrations

Barite (BaSO4) is a widely distributed mineral that incorporates strontium (Sr) during formation. Mass-dependent fractionation of Sr isotopes occurs during abiotic precipitation of barite and formation of barite associated with biological processes (e.g., bacterial sulfide oxidation). Sr isotopes in barite can provide provenance information as well as potentially reconstruct sample formation conditions (e.g., saturation state, temperature, biotic versus abiotic). Incomplete separation of Ba from Sr has complicated measurements of Sr isotopes by MC-ICPMS. In this study, we tested the effects of Ba in Sr sample solutions and modified extraction chromatography of Sr using Eichrom Sr Spec (Eichrom Technologies LLC, USA) resin to enable rapid, accurate, and precise measurements of 88Sr/86Sr and 87Sr/86Sr ratios from Ba-rich matrices. Sr isotope ratios of sample solutions doped with Ba were statistically indistinguishable from Ba-free sample solutions below 1 ppm Ba. Deviations in both 87Sr/86Sr and δ88/86Sr occurred above 1 ppm Ba. An updated extraction chromatography method tested with barite and Ba-doped seawater produces Sr sample solutions containing 10–100 ppb levels of Ba. The practice of Zr spiking for external mass-discrimination correction of 88Sr/86Sr ratios was also evaluated, and it was confirmed that variable Zr levels do not have adverse effects on the accuracy and precision of 87Sr/86Sr ratios in the Zr concentration range required to produce accurate δ88/86Sr values.

Seawater calcium isotope ratios across the Eocene-Oligocene transition

During the Eocene-Oligocene transition (EOT, ca. 34 Ma), Earths climate cooled significantly from a greenhouse to an icehouse climate, while the calcite (CaCO3) compensation depth (CCD) in the Pacific Ocean increased rapidly. Fluctuations in the CCD could result from various processes that create an imbalance between calcium (Ca) sources to, and sinks from, the ocean (e.g., weathering and CaCO3 deposition), with different effects on the isotopic composition of dissolved Ca in the oceans due to differences in the Ca isotopic composition of various inputs and outputs. We used Ca isotope ratios (δ44/40Ca) of coeval pelagic marine barite and bulk carbonate to evaluate changes in the marine Ca cycle across the EOT. We show that the permanent deepening of the CCD was not accompanied by a pronounced change in seawater δ44/40Ca, whereas time intervals in the Neogene with smaller carbonate depositional changes are characterized by seawater δ44/40Ca shifts. This suggests that the response of seawater δ44/40Ca to changes in weathering fluxes and to imbalances in the oceanic alkalinity budget depends on the chemical composition of seawater. A minor and transient fluctuation in the Ca isotope ratio of bulk carbonate may reflect a change in isotopic fractionation associated with CaCO3 precipitation from seawater due to a combination of factors, including changes in temperature and/or in the assemblages of calcifying organisms.

Mid- to late-Holocene Indian winter monsoon variability from a terrestrial record in eastern and southeastern coastal environments of Sri Lanka

The southeastern coastal plain of Sri Lanka contains Holocene sediment archives representing the winter monsoon variability because this region is protected from both summer monsoon and cyclonic rainfall. Chemical, biological, mineralogical, and physical climate proxies were studied in sediment cores extracted from three different coastal estuaries and lagoons situated on the southeastern coast to derive winter monsoon variability. These cores displayed minimum influence of sea level-related changes in sediments. Clay normalized proxy records suggest intervals of aridity from >7300 to ~6750, semi-aridity from ~6250 to 4600 yr BP, and aridity from ~4000 to 3000 and ~1100 to <500 cal. yr BP, with a short wet interval from ~6500 to 6250 cal. yr BP, and a wet interval from ~3000 to 1500 yr BP. Our results match the timing of previously published climate events for Holocene variations in the Indian summer monsoon. Wavelet analysis of the detrended climate proxy records identify significant periodicities at: ~20 ~28–32, ~64, ~100, ~128, ~192, ~256 yr in our data. Most of these periodicities are consistent with known solar irradiance cycles, which drive the decadal- to centennial-scale variability of the summer monsoon. Our multiproxy record for mid- to late-Holocene climate in southeastern Sri Lanka documents that Indian winter monsoon variability is statistically similar to Indian summer monsoon variability, suggesting similar forcing mechanisms.

First evidence of denitrification vis-à-vis monsoon in the Arabian Sea since Late Miocene

In the Arabian Sea, South Asian monsoon (SAM)-induced high surface water productivity coupled with poor ventilation of intermediate water results in strong denitrification within the oxygen minimum zone (OMZ). Despite the significance of denitrification in the Arabian Sea, we have no long-term record of its evolution spanning the past several million years. Here, we present the first record of denitrification evolution since Late Miocene (~10.2 Ma) in the Eastern Arabian Sea, where the SAM generates moderate surface water productivity, based on the samples retrieved during the International Ocean Discovery Program (IODP) Expedition 355. We find that (i) the SAM was persistently weaker from ~10.2 to 3.1 Ma; it did not intensify at ~8 Ma in contrast to a few previous studies, (ii) on tectonic timescale, both the SAM and the East Asian Monsoon (EAM) varied synchronously, (iii) the first evidence of denitrification and productivity/SAM intensification was at ~3.2–2.8 Ma that coincided with Mid-Pliocene Warm Period (MPWP), and (iv) the modern strength of the OMZ where denitrification is a permanent feature was attained at ~1.0 Ma.

Peak intervals of equatorial Pacific export production during the middle Miocene climate transition

The middle Miocene climate transition (MMCT) is characterized by an abrupt 1‰ increase in benthic foraminiferal oxygen isotopes at ca. 13.8 Ma, marking expansion of the Antarctic Ice Sheet and transition of Earth9s climate to a cooler, relatively stable glacial state. Also occurring during this period is a globally recognized positive carbon isotope excursion (16.9–13.5 Ma) in benthic and planktonic foraminifera with shorter carbon isotope maxima (CM) events, linking hypotheses for climate change at the time with the carbon cycle. In order to test whether export production in the eastern equatorial Pacific is related to the largest such event (CM6), coincident with Antarctic Ice Sheet expansion, a high-resolution (<5 k.y.) record of export production at Integrated Ocean Drilling Program Site U1337 spanning the MMCT (14.02–13.43 Ma) was produced using marine pelagic barite mass accumulation rates. Export production is elevated with an extended period of more than double present-day values. These variations are not orbitally paced and provide evidence for a reorganization of nutrients supplied to the eastern equatorial Pacific in the Miocene and intensification of upwelling. If such changes are representative of the entire region, then this mechanism could sequester enough carbon to have a significant effect on atmospheric p CO 2 . However, continual delivery of nutrients to the surface waters of the eastern equatorial Pacific is required in order to sustain export production without depleting the surface ocean of limiting nutrients. This might be accomplished by a change in ocean circulation or a combination of other processes requiring further study.