ALBERT

Description: The Cretaceous/Palaeogene mass extinction eradicated 76% of species on Earth. It was caused by the impact of an asteroid on the Yucatán carbonate platform in the southern Gulf of Mexico 66 million years ago, forming the Chicxulub impact crater. After the mass extinction, the recovery of the global marine ecosystem—measured as primary productivity—was geographically heterogeneous; export production in the Gulf of Mexico and North Atlantic–western Tethys was slower than in most other regions, taking 300 thousand years (kyr) to return to levels similar to those of the Late Cretaceous period. Delayed recovery of marine productivity closer to the crater implies an impact-related environmental control, such as toxic metal poisoning, on recovery times. If no such geographic pattern exists, the best explanation for the observed heterogeneity is a combination of ecological factors—trophic interactions, species incumbency and competitive exclusion by opportunists—and ‘chance’. The question of whether the post-impact recovery of marine productivity was delayed closer to the crater has a bearing on the predictability of future patterns of recovery in anthropogenically perturbed ecosystems. If there is a relationship between the distance from the impact and the recovery of marine productivity, we would expect recovery rates to be slowest in the crater itself. Here we present a record of foraminifera, calcareous nannoplankton, trace fossils and elemental abundance data from within the Chicxulub crater, dated to approximately the first 200 kyr of the Palaeocene. We show that life reappeared in the basin just years after the impact and a high-productivity ecosystem was established within 30 kyr, which indicates that proximity to the impact did not delay recovery and that there was therefore no impact-related environmental control on recovery. Ecological processes probably controlled the recovery of productivity after the Cretaceous/Palaeogene mass extinction and are therefore likely to be important for the response of the ocean ecosystem to other rapid extinction events.

Description: Author Posting. © The Author(s), 2018. 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 Earth and Planetary Science Letters 505 (2019): 131-140, doi:10.1016/j.epsl.2018.10.029.

Description: Vanadium (V) isotopes have been hypothesized to record irradiation processes in the early solar system through production of the minor 50V isotope. However, because V only possesses two stable isotopes it is difficult to distinguish irradiation from other processes such as stable isotope fractionation and nucleosynthetic heterogeneity that could also cause V isotope variation. Here we perform the first detailed investigation of V isotopes in ordinary and carbonaceous chondrites to investigate the origin of any variation. We also perform a three-laboratory inter-calibration for chondrites, which confirms that the different chemical separation protocols do not induce V isotope analytical artifacts as long as samples are measured using medium resolution multiple collector inductively coupled plasma mass spectrometry (MCICPMS). Vanadium isotope compositions (51V/50V) of carbonaceous chondrites correlate with previously reported nucleosynthetically derived excesses in 54Cr. Both 51V and 54Cr are the most neutron-rich of their respective elements, which may suggest that pre-solar grains rich in r-process isotopes is the primary cause of the V-Cr isotope correlation. Vanadium isotope ratios of ordinary chondrite groups and Earth form a weaker correlation with 54Cr that has a different slope than observed for carbonaceous chondrites. The offset between carbonaceous and non-carbonaceous meteorites in V-Cr isotope space is similar to differences also reported for chromium, titanium, oxygen, molybdenum and ruthenium isotopes, which has been inferred to reflect the presence in the early solar system of two physically separated reservoirs. The V isotope composition of Earth is heavier than any meteorite measured to date. Therefore, V isotopes support models of Earth accretion in which a significant portion of Earth was formed from material that is not present in our meteorite collections.

Description: This study was funded by NASA Emerging Worlds grant NNX16AD36G to SGN.

Description: Author Posting. © American Geophysical Union, 2015. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Paleoceanography 30 (2015): 510–526, doi:10.1002/2014PA002741.

Description: Global warming lowers the solubility of gases in the ocean and drives an enhanced hydrological cycle with increased nutrient loads delivered to the oceans, leading to increases in organic production, the degradation of which causes a further decrease in dissolved oxygen. In extreme cases in the geological past, this trajectory has led to catastrophic marine oxygen depletion during the so-called oceanic anoxic events (OAEs). How the water column oscillated between generally oxic conditions and local/global anoxia remains a challenging question, exacerbated by a lack of sensitive redox proxies, especially for the suboxic window. To address this problem, we use bulk carbonate I/Ca to reconstruct subtle redox changes in the upper ocean water column at seven sites recording the Cretaceous OAE 2. In general, I/Ca ratios were relatively low preceding and during the OAE interval, indicating deep suboxic or anoxic waters exchanging directly with near-surface waters. However, individual sites display a wide range of initial values and excursions in I/Ca through the OAE interval, reflecting the importance of local controls and suggesting a high spatial variability in redox state. Both I/Ca and an Earth System Model suggest that the northeast proto-Atlantic had notably higher oxygen levels in the upper water column than the rest of the North Atlantic, indicating that anoxia was not global during OAE 2 and that important regional differences in redox conditions existed. A lack of correlation with calcium, lithium, and carbon isotope records suggests that neither enhanced global weathering nor carbon burial was a dominant control on the I/Ca proxy during OAE 2.

Description: Z.L. thanks NSF OCE 1232620. J.D.O. is supported by an Agouron Postdoctoral Fellowship. T.W.L. acknowledges support from the NSF-EAR and NASA-NAI. A.R. thanks the support of NERC via NE/J01043X/1.

Description: 2015-11-13

Description: © The Author(s), 2016. This is the author's version of the work and is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Geochimica et Cosmochimica Acta 181 (2016): 217-237, doi:10.1016/j.gca.2016.03.010.

Description: Sediment transport from the subducted slab to the mantle wedge is an important process in understanding the chemical and physical conditions of arc magma generation. The Aleutian arc offers an excellent opportunity to study sediment transport processes because the subducted sediment flux varies systematically along strike (Kelemen et al., 2003) and many lavas exhibit unambiguous signatures of sediment addition to the sub-arc mantle (Morris et al., 1990). However, the exact sediment contribution to Aleutian lavas and how these sediments are transported from the slab to the surface are still debated. Thallium (Tl) isotope ratios have great potential to distinguish sediment fluxes in subduction zones because pelagic sediments and low temperature altered oceanic crust are highly enriched in Tl and display heavy and light Tl isotope compositions, respectively, compared with the upper mantle and continental crust. Here, we investigate the Tl isotope composition of lavas covering almost the entire Aleutian arc a well as sediments outboard of both the eastern (DSDP Sites 178 and 183) and central (ODP Hole 886C) portions of the arc. Sediment Tl isotope compositions change systematically from lighter in the Eastern to heavier in the Central Aleutians reflecting a larger proportion of pelagic sediments when distal from the North American continent. Lavas in the Eastern and Central Aleutians mirror this systematic change to heavier Tl isotope compositions to the west, which shows that the subducted sediment composition is directly translated to the arc east of Kanaga Island. Moreover, quantitative mixing models of Tl and Pb, Sr and Nd isotopes reveal that bulk sediment transfer of ~0.6-1.0% by weight in the Eastern Aleutians and ~0.2-0.6% by weight in the Central Aleutians can account for all four isotope systems. Bulk mixing models, however, require that fractionation of trace element ratios like Ce/Pb, Cs/Tl, and Sr/Nd in the Central and Eastern Aleutians occurs after the sediment component was mixed with the mantle wedge. Models of Sr and Nd isotopes that involve sediment melting require either high degrees of sediment melting (〉50%), in which case trace element ratios like Ce/Pb, Cs/Tl, and Sr/Nd of Aleutian lavas need to be produced after mixing with the mantle, or significant fluid additions from the underlying oceanic crust with Sr and Nd isotope compositions indistinguishable from the mantle wedge as well as high Sr/Nd ratios similar to that of low (〈20%) degree sediment melts. Thallium isotope data from Western Aleutian lavas exhibit compositions slightly lighter than the upper mantle, which implies a negligible sediment flux at this location and probably involvement of low-temperature altered oceanic crust in the generation of these lavas. In general, the lightest Tl isotope compositions are observed for the highest Sr/Y ratios and most unradiogenic Sr and Pb isotope compositions, which is broadly consistent with derivation of these lavas via melting of eclogitized altered oceanic crust.

Description: This study was funded by NSF grants EAR-1119373 and -1427310 to SGN and EAR-1456814 to TP

Description: 2017-03-07

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: Author Posting. © The Author(s), 2018. 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 American Journal of Science 318 (2018): 527-556, doi:10.2475/05.2018.04.

Description: Iron speciation and trace metal proxies are commonly applied together in efforts to identify anoxic settings marked by the presence of free sulfide (euxinia) or dissolved iron (ferruginous) in the water column. Here, we use a literature compilation from modern localities to provide a new empirical evaluation of coupled Fe speciation and Mo concentrations as a proxy for pore water sulfide accumulation at non-euxinic localities. We also present new Fe speciation, Mo concentration, and S isotope data from the Friends of Anoxic Mud (FOAM) site in Long Island Sound, which is marked by pore water sulfide accumulation of up to 3 mM beneath oxygen-containing bottom waters. For the operationally defined Fe speciation scheme, ‘highly reactive’ Fe (FeHR) is the sum of pyritized Fe (Fepy) and Fe dominantly present in oxide phases that is available to react with pore water sulfide to form pyrite. Observations from FOAM and elsewhere confirm that Fepy/FeHR from non-euxinic sites is a generally reliable indicator of pore fluid redox, particularly the presence of pore water sulfide. Molybdenum (Mo) concentration data for anoxic continental margin sediments underlying oxic waters but with sulfidic pore fluids typically show authigenic Mo enrichments (2-25 ppm) that are elevated relative to the upper crust (1-2 ppm). However, compilations of Mo concentrations comparing sediments with and without sulfidic pore fluids underlying oxic and low oxygen (non-euxinic) water columns expose non-unique ranges for each, exposing false positives and false negatives. False positives are most frequently found in sediments from low oxygen water columns (for example, Peru Margin), where Mo concentration ranges can also overlap with values commonly found in modern euxinic settings. FOAM represents an example of a false negative, where, despite elevated pore water sulfide concentrations and evidence for active Fe and Mn redox cycling in FOAM sediments, sedimentary Mo concentrations show a homogenous vertical profile across 50 cm depth at 1-2 ppm. A diagenetic model for Mo provides evidence that muted authigenic enrichments are derived from elevated sedimentation rates. Consideration of a range of additional parameters, most prominently pore water Mo concentration, can replicate the ranges of most sedimentary Mo concentrations observed in modern non-euxinic settings. Together, the modern Mo and Fe data compilations and diagenetic model provide a framework for identifying paleo-pore water sulfide accumulation in ancient settings and linked processes regulating seawater Mo and sulfate concentrations and delivery to sediments. Among other utilities, identifying ancient accumulation of sulfide in pore waters, particularly beneath oxic bottom waters, constrains the likelihood that those settings could have hosted organisms and ecosystems with thiotrophy at their foundations.

Description: DSH, TWL, NJP, and CRT acknowledge support from the NASA Astrobiology Institute under Cooperative Agreement No. NNA15BB03A issued through the Science Mission Directorate. Financial support was provided to NR and TWL by NSF-OCE and an appointment to the NASA Postdoctoral Program, as well as to BCG via a postdoctoral fellowship from the Agouron Institute. DSH was supported by a WHOI postdoctoral fellowship.

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 Chemical Geology 457 (2017): 95-106, doi:10.1016/j.chemgeo.2017.03.016.

Description: Carbonate-associated iodine (I/Ca) has been used as a proxy of local, upper-ocean redox conditions, and has successfully demonstrated highly dynamic spatial and temporal patterns across different time scales of Earth history. To further explore the utility of iodine as a paleo-environmental proxy, we present here a new method of extracting organically bound iodine (Iorg) from shale using volumes of samples on the order of tens of milligrams, thus offering the potential for high-resolution work across thin shale beds. The ratio of Iorg to total organic carbon (I/TOC) in modern surface and subsurface sediments decreases with decreasing bottom-water oxygen, which may be used to reconstruct paleo-redox changes. As a proof of concept, we evaluate the I/TOC proxy in Holocene sediments from the Baltic Sea, Landsort Deep (IODP 347) and discuss those data within a framework of additional independent redox proxies, e.g., iron speciation and [Mo]. The results imply that I/TOC may be sensitive to hypoxic–suboxic conditions, complementary to proxies sensitive to more reducing, anoxic–euxinic conditions. Then, we test the usage of I/TOC in sediments deposited during Late Cretaceous, Cenomanian–Turonian Oceanic Anoxic Event (OAE) 2 from ~ 94 million years ago (Ma). We generated I/TOC and Iorg records from six OAE 2 sections: Tarfaya (Morocco), Furlo (central Italy), Demerara Rise (western equatorial Atlantic), Cape Verde Basin (eastern equatorial Atlantic), South Ferriby (UK), and Kerguelen Plateau (southern Indian Ocean), which provide a broad spatial coverage. Generally, I/TOC decreases over the interval recorded by the positive carbon-isotope excursion, the global signature of OAE 2, suggesting an expansion of more reducing bottom-water conditions and consistent with independent constraints from iron speciation and redox-sensitive trace-metals (e.g., Mo). Relatively higher I/TOC values (thus more oxic conditions) are recorded at two high latitude sites for OAE 2, supporting previous model simulations (cGENIE) that indicated higher bottom water oxygen concentrations in these regions. Our results also indicate that organic-rich and oxygenated seafloors are likely a major sink of iodine and correspondingly influence its global seawater inventory.

Description: XZ, WL and ZL are supported by NSF EAR 1349252. DH and TWL acknowledge support from the Geobiology and Low-temperature Geochemistry (GG) Program of NSF. DH would like to acknowledge a Schlanger Ocean Drilling Fellowship.

Description: © The Author(s), 2017. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Science Advances 3 (2017): e1701020, doi:10.1126/sciadv.1701020.

Description: The rates of marine deoxygenation leading to Cretaceous Oceanic Anoxic Events are poorly recognized and constrained. If increases in primary productivity are the primary driver of these episodes, progressive oxygen loss from global waters should predate enhanced carbon burial in underlying sediments—the diagnostic Oceanic Anoxic Event relic. Thallium isotope analysis of organic-rich black shales from Demerara Rise across Oceanic Anoxic Event 2 reveals evidence of expanded sediment-water interface deoxygenation ~43 ± 11 thousand years before the globally recognized carbon cycle perturbation. This evidence for rapid oxygen loss leading to an extreme ancient climatic event has timely implications for the modern ocean, which is already experiencing large-scale deoxygenation.

Description: We would like to acknowledge support from the NSF grant OCE 1434785 (to J.D.O. and S.G.N.), the NASA Exobiology grant NNX16AJ60G (to J.D.O. and S.G.N.), a WHOI Summer Student Fellowship (to C.M.O.), and an Agouron Postdoctoral Fellowship (to J.D.O.). This material is based on work supported by the NSF Graduate Research Fellowship Program under grant no. 026257-001.

Description: Author Posting. © The Author(s), 2015. This is the author's version of the work. It is posted here by permission of Royal Society of Chemistry for personal use, not for redistribution. The definitive version was published in Journal of Analytical Atomic Spectrometry 31 (2016): 531-536 , doi:10.1039/C5JA00397K.

Description: We present and verify a new method to measure vanadium isotope ratios using a Thermo Scientific Neptune multi-collector inductively-coupled plasma mass spectrometer (MCICP- MS) operated in medium mass resolution mode. We collect masses 48 through 53 simultaneously using the L2, L1, Center, H1, H2 and H3 collectors. The Center cup is equipped with a 1012 ; resistor, H1 is equipped with a 1010 ; resistor, while the rest of the collectors have standard 1011 ; resistors. Unlike previous low-resolution methods, the use of medium mass resolution (=M/M ~ 4,000) permits separation of V, Ti and Cr isotopes from all interfering molecular species representing combinations of C, N, O, S, Cl, and Ar. We show that the external reproducibility follows a power law function with respect to the number of V+ ions collected and achieve an external reproducibility of ± 0.15 ‰ with total V+ ion beam intensities of ~ 1 nA. The separation of interfering molecular species from the V mass spectrum reduces the V requirement for precise isotope data to as little as 200-300 ng V per analysis — a reduction of ~90% compared with previous methods — making several low-V matrices amenable to V isotope analysis.

Description: This study was funded by a WHOI IR&D grant to SGN and NSF OCE grant 1434785 to JDO and SGN and Agouron Geobiology Fellowships to JDO and TJH.

Description: 2016-11-10

Description: Dataset: Thallium isotopes

Description: This thallium isotope dataset from a Cretaceous Oceanic Anoxic Event constrains the magnitude and timing of oceanic deoxygenation. For a complete list of measurements, refer to the full dataset description in the supplemental file 'Dataset_description.pdf'. The most current version of this dataset is available at: https://www.bco-dmo.org/dataset/819793

Description: NSF Division of Ocean Sciences (NSF OCE) OCE-1434785, NSF Division of Ocean Sciences (NSF OCE) OCE-1624895