Spatial and temporal trends of iron and iron isotope cycling in the Peruvian oxygen minimum zone

Iron (Fe) is a key element in the global ocean’s biogeochemical framework because of its essential role in numerous biological processes. A poorly studied link in the oceanic Fe cycle is the reductive release of Fe from sediments in oxygen depleted ocean regions - the oxygen minimum zones (OMZs). Changing rates of Fe release from OMZ sediments may have the potential to modulate ocean fertility which has far-reaching implications considering the high amplitude oxygen fluctuations throughout earth history as well as the ongoing ocean deoxygenation projected for the near future. In order to explore spatial and temporal trends of Fe cycling in OMZs, we present here Fe isotope and speciation data for surface sediments from a transect across the Peruvian upwelling area, one of the most pronounced OMZs of the modern ocean. Because of continuous dissimilatory Fe reduction and diffusive loss across the benthic boundary, sediments within the OMZ are strongly depleted in reactive Fe components, and the little reactive Fe left behind has a heavy isotope composition. In contrast, surface sediments below the OMZ are enriched in reactive Fe, with the majority being present as Fe oxides with comparably light isotope composition. This lateral pattern of Fe depletion and enrichment indicates that Fe released from sediments within the OMZ is reoxidized and precipitated at the oxycline. First-order calculations suggest that the amount of Fe mobilized within the OMZ and that accumulated at the boundaries are largely balanced. Therefore, benthic Fe fluxes in OMZs should be carefully evaluated prior to incorporation into global models, as much of the initially released Fe may be reprecipitated prior to vertical or offshore transport. First XRF core scanning results for partly laminated piston cores from the OMZ boundaries reveal downcore oscillations in the content of reactive Fe and redox-sensitive trace metals that are attributed to past changes in OMZ extension. Ongoing work on these cores will focus on their dating and the downcore investigation of Fe and trace metal records in order to better understand past Fe cycling within the Peruvian OMZ and potential interactions with climate variability

Rock magnetic and geochemical evidence for authigenic magnetite formation via iron reduction in coal-bearing sediments offshore Shimokita Peninsula, Japan (IODP Site C0020)

Sediments recovered at Integrated Ocean Drilling Program (IODP) Site C0020, in a fore‐arc basin offshore Shimokita Peninsula, Japan, include numerous coal beds (0.3–7 m thick) that are associated with a transition from a terrestrial to marine depositional environment. Within the primary coal‐bearing unit (∼2 km depth below seafloor) there are sharp increases in magnetic susceptibility in close proximity to the coal beds, superimposed on a background of consistently low magnetic susceptibility throughout the remainder of the recovered stratigraphic sequence. We investigate the source of the magnetic susceptibility variability and characterize the dominant magnetic assemblage throughout the entire cored record, using isothermal remanent magnetization (IRM), thermal demagnetization, anhysteretic remanent magnetization (ARM), iron speciation, and iron isotopes. Magnetic mineral assemblages in all samples are dominated by very low‐coercivity minerals with unblocking temperatures between 350 and 580°C that are interpreted to be magnetite. Samples with lower unblocking temperatures (300–400°C), higher ARM, higher‐frequency dependence, and isotopically heavy δ56Fe across a range of lithologies in the coal‐bearing unit (between 1925 and 1995 mbsf) indicate the presence of fine‐grained authigenic magnetite. We suggest that iron‐reducing bacteria facilitated the production of fine‐grained magnetite within the coal‐bearing unit during burial and interaction with pore waters. The coal/peat acted as a source of electron donors during burial, mediated by humic acids, to supply iron‐reducing bacteria in the surrounding siliciclastic sediments. These results indicate that coal‐bearing sediments may play an important role in iron cycling in subsiding peat environments and if buried deeply through time, within the subsequent deep biosphere

The Amundsen Sea Polynya International Research Expedition (ASPIRE)

In search of an explanation for some of the greenest waters ever seen in coastal Antarctica and their possible link to some of the fastest melting glaciers and declining summer sea ice, the Amundsen Sea Polynya International Research Expedition (ASPIRE) challenged the capabilities of the US Antarctic Program and RVIB Nathaniel B. Palmer during Austral summer 2010–2011. We were well rewarded by both an extraordinary research platform and a truly remarkable oceanic setting. Here we provide further insights into the key questions that motivated our sampling approach during ASPIRE and present some preliminary findings, while highlighting the value of the Palmer for accomplishing complex, multifaceted oceanographic research in such a challenging environment

Four-Hundred-and-Ninety-Million-Year Record of Bacteriogenic Iron Oxide Precipitation at Sea-Floor Hydrothermal Vents

Fe oxide deposits are commonly found at hydrothermal vent sites at mid-ocean ridge and back-arc sea floor spreading centers, seamounts associated with these spreading centers, and intra-plate seamounts, and can cover extensive areas of the seafloor. These deposits can be attributed to several abiogenic processes and commonly contain micron-scale filamentous textures. Some filaments are cylindrical casts of Fe oxyhydroxides formed around bacterial cells and are thus unquestionably biogenic. The filaments have distinctive morphologies very like structures formed by neutrophilic Fe oxidizing bacteria. It is becoming increasingly apparent that Fe oxidizing bacteria have a significant role in the formation of Fe oxide deposits at marine hydrothermal vents. The presence of Fe oxide filaments in Fe oxides is thus of great potential as a biomarker for Fe oxidizing bacteria in modern and ancient marine hydrothermal vent deposits. The ancient analogues of modern deep-sea hydrothermal Fe oxide deposits are jaspers. A number of jaspers, ranging in age from the early Ordovician to late Eocene, contain abundant Fe oxide filamentous textures with a wide variety of morphologies. Some of these filaments are like structures formed by modern Fe oxidizing bacteria. Together with new data from the modern TAG site, we show that there is direct evidence for bacteriogenic Fe oxide precipitation at marine hydrothermal vent sites for at least the last 490 Ma of the Phanerozoic

Isotopically Light Cd in Sediments Underlying Oxygen Deficient Zones

Cadmium is a trace metal of interest in the ocean partly because its concentration mimics that of phosphate. However, deviations from the global mean dissolved Cd/PO4 relationship are present in oxygen deficient zones, where Cd is depleted relative to phosphate. This decoupling has been suggested to result from cadmium sulphide (CdS) precipitation in reducing microenvironments within sinking organic matter. We present Cd concentrations and Cd isotope compositions in organic-rich sediments deposited at several upwelling sites along the northeast Pacific continental margin. These sediments all have enriched Cd concentrations relative to crustal material. We calculate a net accumulation rate of Cd in margin settings of between 2.6 to 12.0 × 107 mol/yr, higher than previous estimates, but at the low end of a recently published estimate for the magnitude of the marine sink due to water column CdS precipitation. Cadmium in organic-rich sediments is isotopically light (δ114/110CdNIST-3108 = +0.02 ± 0.14‰, n = 26; 2 SD) compared to deep seawater (+0.3 ± 0.1‰). However, isotope fractionation during diagenesis in continental margin settings appears to be small. Therefore, the light Cd isotope composition of organic-rich sediments is likely to reflect an isotopically light source of Cd. Non-quantitative biological uptake of light Cd by phytoplankton is one possible means of supplying light Cd to the sediment, which would imply that Cd isotopes could be used as a tracer of past ocean productivity. However, water column CdS precipitation is also predicted to preferentially sequester light Cd isotopes from the water column, which could obfuscate Cd as a tracer. We also observe notably light Cd isotope compositions associated with elevated solid phase Fe concentrations, suggesting that scavenging of Cd by Fe oxide phases may contribute to the light Cd isotope composition of sediments. These multiple possible sources of isotopically light Cd to sediments, along with evidence for complex particle cycling of Cd in the water column, bring into question the straightforward application of Cd isotopes as a paleoproductivity proxy

Lead Sources to the Amundsen Sea, West Antarctica

This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. https://pubs.acs.org/page/policy/authorchoice_termsofuse.htmlThe global prevalence of industrial lead (Pb) contamination was exemplified decades ago by the predominance of anthropogenic Pb in samples of Antarctic surface ice and in Southern Ocean surface waters. Decreases in environmental Pb contamination corresponding with the near-global phase-out of leaded automobile gasoline beginning in the 1970s have since been observed. Measurements of Pb concentration in snow and ice core samples from Antarctica show that recent fluxes of industrial Pb to Antarctica have similarly declined. Here, we present measurements of Pb concentrations and isotopic compositions in seawater and surface sediments from the Amundsen Sea continental shelf including the Amundsen Sea Polynya. Both sets of measurements show that most (∼60–95%) of the Pb at our sites, at the time of sampling, is natural in source: that is, derived from the weathering of Antarctic continental rocks. These fluxes of natural Pb then become entrained into polynya waters either from sediment resuspension or from the transport of sediment-laden glacial melt waters to the polynya.publishedVersio

Controls on the evolution of Ediacaran metazoan ecosystems: A redox perspective

A growing number of detailed geochemical studies of Ediacaran (635–541 Ma) marine successions have provided snapshots into the redox environments that played host to the earliest known metazoans. Whilst previous compilations have focused on the global evolution of Ediacaran water column redox chemistry, the inherent heterogeneity evident in palaeogeographically distinct environments demands a more dissected approach to better understand the nature, interactions and evolution of extrinsic controls on the development of early macrobenthic ecosystems. Here, we review available data of local-scale redox conditions within a palaeogeographic and sequence stratigraphic framework, to explore the mechanisms controlling water column redox conditions and their potential impact on the record of metazoans. The openly connected Laurentian margin, North America (632–540 Ma) and Nama basin, Namibia (550–538 Ma), and the variably restricted Yangtze Block, South China (635–520 Ma), show continued redox instability after the first fossil evidence for metazoans. This may support opportunistic benthic colonisation during periods of transient oxygenation amidst episodic upwelling of anoxic waters beneath a very shallow, fluctuating chemocline. The first skeletal metazoans appeared under conditions of continued redox stratification, such as those which characterise the Dengying Formation of the Yangtze Block and the Kuibis Subgroup of the Nama basin. Current data, however, suggests that successful metazoan reef-building demanded more persistent oxia. We propose that cratonic positioning and migration throughout the Ediacaran Period, in combination with gradually increasing dissolved oxygen loading, may have provided a first-order control on redox evolution through regulating circulation mechanisms in the Mirovian Ocean. Some unrestricted lower slope environments from mid-high latitudes benefited from sustained oxygenation via downwelling, whilst transit of isolated cratons towards more equatorial positions stifled pervasive ventilation either through ineffective surface ocean mixing, Ekman-induced upwelling, elevated surface ocean productivity or a combination of these processes

Molybdenum behavior during early diagenesis: Insights from Mo isotopes

We present molybdenum isotope and concentration data from 14 sites in the eastern Pacific from the central California to the Peru margin. The environments studied have been chosen to represent a broad range in oxidation-reduction (redox) potential, which provide a framework for the behavior of this redox-sensitive element. Manganese-rich hemipelagic sediments from the eastern tropical Pacific have a mean characteristic Mo isotope signature (δ⁹⁸/⁹⁵Mo = -0.49 ± 0.04%₀, two times the standard deviation of the mean (2 SDOM) with n = 14) that reflects fractionation between ocean water and authigenic Mo associated with Mn oxides. Authigenic Fe-Mo-S deposits from reducing continental margin settings also have a characteristic Mo isotopic signature (δ⁹⁸/⁹⁵Mo = 1.64 ± 0.04%₀, 2 SDOM with n = 136). Both of these values are in contrast to highly sulfidic (>11 μM H₂Saq) restricted basin environments, which contain Mo isotope values analytically indistinguishable from seawater. In terms of the Mo isotope composition, the modern oceanic Mo sink is dominated by continental margin "type" environments where δ⁹⁸/⁹⁵Mo = ~1.6%₀ and Mn-rich sediments where δ⁹⁸/⁹⁵Mo = approximately -0.5%₀, with a minor contribution from euxinic settings where H₂Saq > 11 μM.Keywords: diagenesis, isotopes, molybdenumKeywords: diagenesis, isotopes, molybdenu

Iron isotope systematics in estuaries : the case of North River, Massachusetts (USA)

Author Posting. © The Author(s), 2009. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 73 (2009): 4045-4059, doi:10.1016/j.gca.2009.04.026.Recent studies have suggested that rivers may present an isotopically light Fe source to the oceans. Since the input of dissolved iron from river water is generally controlled by flocculation processes that occur during estuarine mixing, it is important to investigate potential fractionation of Fe-isotopes during this process. In this study, we investigate the influence of the flocculation of Fe-rich colloids on the iron isotope composition of pristine estuarine waters and suspended particles. The samples were collected along a salinity gradient from the fresh water to the ocean in the North River estuary (MA, USA). Estuarine samples were filtered at 0.22 μm and the iron isotope composition of the two fractions (dissolved and particles) were analyzed using high resolution MC-ICP-MS after chemical purification. Dissolved iron results show positive δ56Fe values (with an average of 0.43 ± 0.04 ‰) relative to the IRMM-14 standard and do not display any relationships with salinity or with percentage of colloid flocculation. The iron isotopic composition of the particles suspended in fresh water is characterized by more negative δ56Fe values than for dissolved Fe and correlate with the percentage of Fe flocculation. Particulate δ56Fe values vary from -0.09‰ at no flocculation to ~ 0.1‰ at the flocculation maximum, which reflect mixing effects between river-borne particles, lithogenic particles derived from coastal seawaters and newly precipitated colloids. Since the process of flocculation produces minimal Fe-isotope fractionation in the dissolved Fe pool, we suggest that the pristine iron isotope composition of fresh water is preserved during estuarine mixing and that the value of the global riverine source into the ocean can be identified from the fresh water values. However, this study also suggests that δ56Fe composition of rivers can also be characterized by more positive δ56Fe values (up to 0.3 per mil) relative to the crust than previously reported. In order to improve our current understanding of the oceanic iron isotope cycling, further work is now required to determine the processes controlling the fractionation of Fe isotopes during continental run-off.This study was supported by the National Science Foundation (OCE 0550066) to O. Rouxel and Edward Sholkovitz

Uranium isotope cycling on the highly productive Peruvian margin

Uranium isotopes (δ238U values) in ancient sedimentary rocks (shales, carbonate rocks) are widely used as a tool to reconstruct paleo-redox conditions, but the behaviour of U isotopes under modern non-sulfidic anoxic vs. oxic conditions remains poorly constrained. We present U concentration and isotope data for modern sediments from the Peruvian margin, a highly productive open ocean environment with a range of redox conditions. To investigate U in different host fractions of the sediment (reactive, silicate, and HNO3-soluble fraction), we conducted a series of sequential extractions. Detrital-corrected authigenic U isotope compositions (δ238Uauth) in sediments deposited beneath an oxic water column show little deviation from the dissolved seawater U source, while anoxically deposited sediments have δ238Uauth values that are up to 0.4‰ heavier compared to seawater δ238U. Under anoxic, non-euxinic conditions, the U isotope offset between sediment and seawater is larger compared with oxic, but significantly smaller when compared with euxinic conditions from the literature. The results from sequential extractions show that the reactive sediment fraction records more pronounced differences in δ238Ureactive than δ238Uauth values depending on the oxidation state of the overlying water column. Furthermore, we found a strong correlation between total organic carbon (TOC) and both U concentrations (Uauth) and δ238Uauth values (R2 = 0.70 and 0.94, respectively) at the persistently anoxic site that we examined. These correlations can be caused by several processes including U isotope fractionation during microbially-mediated U reduction at the sediment-water interface (diffusive U input), during sorption onto and/or incorporation into organic matter in the water column (particulate U input) and diagenetic redistribution of U, or a combination of these processes. Our data show that several factors can influence δ238U values including oxidation state of U, the presence or absence of hydrogen sulfide and organic matter. These findings add new constraints to the degree of U isotope fractionation associated with U incorporation into sediments in different low-oxygen environments, thus aiding in interpretation of ancient paleo-redox conditions from U isotope data