Description: © The Author(s), 2017. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 213 (2017): 291-307, doi:10.1016/j.gca.2017.06.041.

Description: Thallium (Tl) isotopes are a new and potentially powerful paleoredox proxy that may track bottom water oxygen conditions based on the global burial flux of manganese oxides. Thallium has a residence time of ~20 thousand years, which is longer than the ocean mixing time, and it has been inferred that modern oxic seawater is conservative with respect to both concentration and isotopes. Marine sources of Tl have nearly identical isotopic values. Therefore, the Tl sinks, adsorption onto manganese oxides and low temperature oceanic crust alteration (the dominant seawater output), are the primary controls of the seawater isotopic composition. For relatively short-term, ~million years, redox events it is reasonable to assume that the dominant mechanism that alters the Tl isotopic composition of seawater is associated with manganese oxide burial because large variability in low temperature ocean crust alteration is controlled by long-term, multi-million years, average ocean crust production rates. This study presents new Tl isotope data for an open ocean transect in the South Atlantic, and depth transects for two euxinic basins (anoxic and free sulfide in the water column), the Cariaco Basin and Black Sea. The Tl isotopic signature of open ocean seawater in the South Atlantic was found to be homogeneous with ε205Tl = -6.0 ± 0.3 (± 2 SD, n = 41) while oxic waters from Cariaco and the Black Sea are -5.6 and -2.2, respectively. Combined with existing data from the Pacific and Arctic Oceans, our Atlantic data establish the conservatism of Tl isotopes in the global ocean. In contrast, partially- and predominantly-restricted basins reveal Tl isotope differences that vary between open-ocean (-6) and continental material (-2) ε205Tl, scaling with the degree of restriction. Regardless of the differences between basins, Tl is quantitatively removed from their euxinic waters below the chemocline. The burial of Tl in euxinic sediments is estimated to be an order of magnitude less than each of the modern ocean outputs and imparts no isotopic fractionation. Thallium removal into pyrite appears to be associated with a small negative fractionation between -1 and -3 ε205Tl, which renders Tl-depleted waters below the chemocline enriched in isotopically-heavy Tl. Due to the quantitative removal of Tl from euxinic seawater, Tl isotope analyses of the authigenic fraction of underlying euxinic sediments from both the Black Sea and Cariaco Basin capture the Tl isotope value of the oxic portion of their respective water column with no net isotope fractionation. Since the Tl isotope composition of seawater is largely dictated by the relative fraction of Mn-oxide burial versus oceanic crust alteration, we contend that the Tl isotope composition of authigenic Tl in black shales, deposited under euxinic conditions but well-connected to the open ocean, can be utilized to reconstruct the Tl isotope composition of seawater, and thus to reconstruct the global history of Mn-oxide burial.

Description: JDO and SGN would like to thank NSF and NASA for funding; JDO and TJH gratefully acknowledges support from the Agouron Institute Postdoctoral Fellowship Program.

Description: © The Author(s), 2022. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Whitmore, L., Shiller, A., Horner, T., Xiang, Y., Auro, M., Bauch, D., Dehairs, F., Lam, P., Li, J., Maldonado, M., Mears, C., Newton, R., Pasqualini, A., Planquette, H., Rember, R., & Thomas, H. Strong margin influence on the Arctic Ocean Barium Cycle revealed by pan‐Arctic synthesis. Journal of Geophysical Research: Oceans, 127(4), (2022): e2021JC017417, https://doi.org/10.1029/2021jc017417.

Description: Early studies revealed relationships between barium (Ba), particulate organic carbon and silicate, suggesting applications for Ba as a paleoproductivity tracer and as a tracer of modern ocean circulation. But, what controls the distribution of barium (Ba) in the oceans? Here, we investigated the Arctic Ocean Ba cycle through a one-of-a-kind data set containing dissolved (dBa), particulate (pBa), and stable isotope Ba ratio (δ138Ba) data from four Arctic GEOTRACES expeditions conducted in 2015. We hypothesized that margins would be a substantial source of Ba to the Arctic Ocean water column. The dBa, pBa, and δ138Ba distributions all suggest significant modification of inflowing Pacific seawater over the shelves, and the dBa mass balance implies that ∼50% of the dBa inventory (upper 500 m of the Arctic water column) was supplied by nonconservative inputs. Calculated areal dBa fluxes are up to 10 μmol m−2 day−1 on the margin, which is comparable to fluxes described in other regions. Applying this approach to dBa data from the 1994 Arctic Ocean Survey yields similar results. The Canadian Arctic Archipelago did not appear to have a similar margin source; rather, the dBa distribution in this section is consistent with mixing of Arctic Ocean-derived waters and Baffin Bay-derived waters. Although we lack enough information to identify the specifics of the shelf sediment Ba source, we suspect that a sedimentary remineralization and terrigenous sources (e.g., submarine groundwater discharge or fluvial particles) are contributors.

Description: This research was supported by the National Science Foundation [OCE-1434312 (AMS), OCE-1436666 (RN), OCE-1535854 (PL), OCE-1736949, OCE-2023456 (TJH), and OCE-1829563 (R. Anderson for open access support)], Natural Sciences and Engineering Research Council of Canada (NSERC)-Climate Change and Atmospheric Research (CCAR) Program (MTM), and LEFE-CYBER EXPATE (HP). HT acknowledges support by the Canadian GEOTRACES via NSERC-CCAR and the German Academic Exchange Service (DAAD): MOPGA-GRI (Make Our Planet Great Again—Research Initiative) sponsored by BMBF (Federal German Ministry of Education and Research; Grant No. 57429828).

Description: © The Author(s), 2020. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Martinez-Ruiz, F., Paytan, A., Gonzalez-Munoz, M. T., Jroundi, F., Abad, M. M., Lam, P. J., Horner, T. J., & Kastner, M. Barite precipitation on suspended organic matter in the mesopelagic zone. Frontiers in Earth Science, 8, (2020): 567714, doi:10.3389/feart.2020.567714.

Description: Mechanisms underlying barite precipitation in seawater and the precise depths of barite precipitation in the water column have been debated for decades. Here we present a detailed study of water column barite distribution in the mesopelagic zone at diverse stations in the open ocean by analyzing samples collected using multiple unit large volume in-situ filtration systems in the Pacific, Atlantic and Indian oceans. Our results demonstrate that barite is an organo-mineral particularly abundant at intermediate depths throughout the world’s ocean regardless of saturation state with respect to barite. This is confirming the notion of precipitation at depths of intense organic matter mineralization. Our observations further support the link between barite formation and microbial activity, demonstrated by the association of barite particles with organic matter aggregates and with extracellular polymeric substances. Evidence for microbial mediation is consistent with previous experimental work showing that in bacterial biofilms Ba binds to phosphate groups on cell surfaces and within extracellular polymeric substances. This organo-accumulation promotes high concentrations of Ba leading to saturated microenvironments and nucleation sites favoring precipitation. The distribution of Ba isotopes in the water column and in particulate matter is also consistent with the proposed precipitation mechanism.

Description: This study was supported by the European Regional Development Fund (ERDF) co-financed grants CGL2017-92600-EXP and PID2019-104624RB-I00 (Agencia Estatal de Investigación, Ministerio de Ciencia e Innovación, Spain), Research Groups RNM-179 and BIO 103, and Excellence Projects P18-RT-3804 and P18-RT-4074 (Junta de Andalucía), Unidad Científica de Excelencia UCE-PP2016-05 (University of Granada) and grant OCE-1443577.