Meridional Survey of the Central Pacific Reveals Iodide Accumulation in Equatorial Surface Waters and Benthic Sources in the Abyssal Plain

The distributions of iodate and iodide were measured along the GEOTRACES GP15 meridional transect at 152°W from the shelf of Alaska to Papeete, Tahiti. The transect included oxygenated waters near the shelf of Alaska, the full water column in the central basin in the North Pacific Basin, the upper water column spanning across seasonally mixed regimes in the north, oligotrophic regimes in the central gyre, and the equatorial upwelling. Iodide concentrations are highest in the permanently stratified tropical mixed layers, which reflect accumulation due to light-dependent biological processes, and decline rapidly below the euphotic zone. Vertical mixing coefficients (Kz), derived from complementary 7Be data, enabled iodide oxidation rates to be estimated at two stations. Iodide half-lives of 3–4 years show the importance of seasonal mixing processes in explaining north-south differences in the transect, and also contribute to the decrease in iodide concentrations with depth below the mixed layer. These estimated half-lives are consistent with a recent global iodine model. No evidence was found for significant inputs of iodine from the Alaskan continental margin, but there is a significant enrichment of iodide in bottom waters overlying deep sea sediments from the interior of the basin

Uncovering the spatial heterogeneity of Ediacaran carbon cycling

Author Posting. © The Author(s), 2016. 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 Geobiology 15 (2017): 211–224, doi:10.1111/gbi.12222.Records of the Ediacaran carbon cycle (635 to 541 million years ago) include the Shuram excursion (SE), the largest negative carbonate-carbon isotope excursion in Earth history (down to -12 ‰). The nature of this excursion remains enigmatic given the difficulties of interpreting a perceived extreme global decrease in the δ13C of seawater dissolved inorganic carbon (DIC). Here, we present carbonate and organic carbon isotope (δ13Ccarb and δ13Corg) records from the Ediacaran Doushantuo Formation along a proximal-to-distal transect across the Yangtze Platform of South China as a test of the spatial variation of the SE. Contrary to expectations, our results show that the magnitude and morphology of this excursion and its relationship with coexisting δ13Corg are highly heterogeneous across the platform. Integrated geochemical, mineralogical, petrographic, and stratigraphic evidence indicates that the SE is a primary marine signature. Data compilations demonstrate that the SE was also accompanied globally by parallel negative shifts of δ34S of carbonate-associated sulfate (CAS) and increased 87Sr/86Sr ratio and coastal CAS concentration, suggesting elevated continental weathering and coastal marine sulfate concentration during the SE. In light of these observations, we propose a heterogeneous oxidation model to explain the high spatial heterogeneity of the SE and coexisting δ13Corg records of the Doushantuo, with likely relevance to the SE in other regions. In this model, we infer continued marine redox stratification through the SE but with increased availability of oxidants (e.g., O2 and sulfate) limited to marginal near-surface marine environments. Oxidation of limited spatiotemporal extent provides a mechanism to drive heterogeneous oxidation of subsurface reduced carbon mostly in shelf areas. Regardless of the mechanism driving the SE, future models must consider the evidence for spatial heterogeneity in δ13C presented in this study.We thank the National Key Basic Research Program of China (Grant 2013CB955704) and the State Key R&D project of China (Grant 2016YFA060104) as well as the NSF-ELT program and the NASA Astrobiology Institute (TWL) for funding

Perspectives on Proterozoic surface ocean redox from iodine contents in ancient and recent carbonate

© 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 Earth and Planetary Science Letters 463 (2017): 159-170, doi:10.1016/j.epsl.2017.01.032.The Proterozoic Eon hosted the emergence and initial recorded diversification of eukaryotes. Oxygen levels in the shallow marine settings critical to these events were lower than today’s, although how much lower is debated. Here, we use concentrations of iodate (the oxidized iodine species) in shallow-marine limestones and dolostones to generate the first comprehensive record of Proterozoic near-surface marine redox conditions. The iodine proxy is sensitive to both local oxygen availability and the relative proximity to anoxic waters. To assess the validity of our approach, Neogene-Quaternary carbonates are used to demonstrate that diagenesis most often decreases and is unlikely to increase carbonate-iodine contents. Despite the potential for diagenetic loss, maximum Proterozoic carbonate iodine levels are elevated relative to those of the Archean, particularly during the Lomagundi and Shuram carbon isotope excursions of the Paleo- and Neoproterozoic, respectively. For the Shuram anomaly, comparisons to Neogene-Quaternary carbonates suggest that diagenesis is not responsible for the observed iodine trends. The baseline low iodine levels in Proterozoic carbonates, relative to the Phanerozoic, are linked to a shallow oxic-anoxic interface. Oxygen concentrations in surface waters would have at least intermittently been above the threshold required to support eukaryotes. However, the diagnostically low iodine data from mid-Proterozoic shallow-water carbonates, relative to those of the bracketing time intervals, are consistent with a dynamic chemocline and anoxic waters that would have episodically mixed upward and laterally into the shallow oceans. This redox instability may have challenged early eukaryotic diversification and expansion, creating an evolutionary landscape unfavorable for the emergence of animals.TL, ZL, and DH thank NSF EAR-1349252. ZL further thanks OCE-1232620. DH, ZL, and TL acknowledge further funding from a NASA Early Career Collaboration Award. TL, AB, NP, DH, and AK thank the NASA Astrobiology Institute. TL and NP received support from the Earth-Life Transitions Program of the NSF. AB acknowledges support from NSF grant EAR-05-45484 and an NSERC Discovery and Accelerator Grants. CW acknowledges support from NSFC grant 40972021

Upper ocean oxygenation dynamics from I/Ca ratios during the Cenomanian-Turonian OAE 2

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.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.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/1.2015-11-1

Trace elements at the intersection of marine biological and geochemical evolution

Life requires a wide variety of bioessential trace elements to act as structural components and reactive centers in metalloenzymes. These requirements differ between organisms and have evolved over geological time, likely guided in some part by environmental conditions. Until recently, most of what was understood regarding trace element concentrations in the Precambrian oceans was inferred by extrapolation, geochemical modeling, and/or genomic studies. However, in the past decade, the increasing availability of trace element and isotopic data for sedimentary rocks of all ages has yielded new, and potentially more direct, insights into secular changes in seawater composition – and ultimately the evolution of the marine biosphere. Compiled records of many bioessential trace elements (including Ni, Mo, P, Zn, Co, Cr, Se, and I) provide new insight into how trace element abundance in Earth's ancient oceans may have been linked to biological evolution. Several of these trace elements display redox-sensitive behavior, while others are redox-sensitive but not bioessential (e.g., Cr, U). Their temporal trends in sedimentary archives provide useful constraints on changes in atmosphere-ocean redox conditions that are linked to biological evolution, for example, the activity of oxygen-producing, photosynthetic cyanobacteria. In this review, we summarize available Precambrian trace element proxy data, and discuss how temporal trends in the seawater concentrations of specific trace elements may be linked to the evolution of both simple and complex life. We also examine several biologically relevant and/or redox-sensitive trace elements that have yet to be fully examined in the sedimentary rock record (e.g., Cu, Cd, W) and suggest several directions for future studies

Evaluating the fidelity of the cerium paleoredox tracer during variable carbonate diagenesis on the Great Bahamas Bank

Inferring redox conditions for ancient marine environments is critical to our understanding of biogeochemical cycles over Earth history. Because of the redox sensitivity of cerium (Ce) relative to other rare earth elements (REEs) and its uptake in marine carbonates, the Ce anomaly (Ce/Ce*) is widely applied to ancient carbonates as a proxy for local redox conditions in the water column. However, carbonate sediments and rocks are particularly vulnerable to multiple stages and styles of post-depositional diagenetic alteration where the diagenetic redox conditions and fluid compositions can vary widely from overlying seawater. Evaluations of the effects of this post-depositional alteration for the Ce anomaly have mostly been limited to ancient carbonate rocks rather than recent, well-characterized analog facies. Here, we report on analyses of REE plus yttrium concentrations (REY) and Ce anomalies in bulk carbonate samples from drill cores collected in the Bahamas (Clino and Unda) that allow us to track loss or retention of primary signals of initial oxic deposition through a range of subsequent alteration scenarios mostly under anoxic conditions. Specifically, these materials have experienced well-constrained overprints linked to meteoric processes and marine burial diagenesis, including dolomitization. Our results show that, regardless of mineralogy, diagenetic fluid composition, and redox state, the REY patterns in these carbonates, including the Ce anomaly, are similar to those of modern oxic seawater, indicating that they likely record the seawater signatures of primary deposition. As such, the Ce anomaly in shallow marine carbonates has the potential to preserve records of primary deposition even when subject to multiple stages and styles of diagenetic alteration, confirming its utility in studies of ancient marine redox

Table_1_Rates and pathways of iodine speciation transformations at the Bermuda Atlantic Time Series.xlsx

The distribution of iodine in the surface ocean – of which iodide-iodine is a large destructor of tropospheric ozone (O3) – can be attributed to both in situ (i.e., biological) and ex situ (i.e., mixing) drivers. Currently, uncertainty regarding the rates and mechanisms of iodide (I-) oxidation render it difficult to distinguish the importance of in situ reactions vs ex situ mixing in driving iodine’s distribution, thus leading to uncertainty in climatological ozone atmospheric models. It has been hypothesized that reactive oxygen species (ROS), such as superoxide (O2•−) or hydrogen peroxide (H2O2), may be needed for I- oxidation to occur at the sea surface, but this has yet to be demonstrated in natural marine waters. To test the role of ROS in iodine redox transformations, shipboard isotope tracer incubations were conducted as part of the Bermuda Atlantic Time Series (BATS) in the Sargasso Sea in September of 2018. Incubation trials evaluated the effects of ROS (O2•−, H2O2) on iodine redox transformations over time and at euphotic and sub-photic depths. Rates of I- oxidation were assessed using a 129I- tracer (t1/2 ~15.7 Myr) added to all incubations, and 129I/127I ratios of individual iodine species (I-, IO3-). Our results show a lack of I- oxidation to IO3- within the resolution of our tracer approach – i.e., <2.99 nM/day, or <1091.4 nM/yr. In addition, we present new ROS data from BATS and compare our iodine speciation profiles to that from two previous studies conducted at BATS, which demonstrate long-term iodine stability. These results indicate that ex situ processes, such as vertical mixing, may play an important role in broader iodine species’ distribution in this and similar regions.</p

DataSheet_1_Rates and pathways of iodine speciation transformations at the Bermuda Atlantic Time Series.pdf

The distribution of iodine in the surface ocean – of which iodide-iodine is a large destructor of tropospheric ozone (O3) – can be attributed to both in situ (i.e., biological) and ex situ (i.e., mixing) drivers. Currently, uncertainty regarding the rates and mechanisms of iodide (I-) oxidation render it difficult to distinguish the importance of in situ reactions vs ex situ mixing in driving iodine’s distribution, thus leading to uncertainty in climatological ozone atmospheric models. It has been hypothesized that reactive oxygen species (ROS), such as superoxide (O2•−) or hydrogen peroxide (H2O2), may be needed for I- oxidation to occur at the sea surface, but this has yet to be demonstrated in natural marine waters. To test the role of ROS in iodine redox transformations, shipboard isotope tracer incubations were conducted as part of the Bermuda Atlantic Time Series (BATS) in the Sargasso Sea in September of 2018. Incubation trials evaluated the effects of ROS (O2•−, H2O2) on iodine redox transformations over time and at euphotic and sub-photic depths. Rates of I- oxidation were assessed using a 129I- tracer (t1/2 ~15.7 Myr) added to all incubations, and 129I/127I ratios of individual iodine species (I-, IO3-). Our results show a lack of I- oxidation to IO3- within the resolution of our tracer approach – i.e., <2.99 nM/day, or <1091.4 nM/yr. In addition, we present new ROS data from BATS and compare our iodine speciation profiles to that from two previous studies conducted at BATS, which demonstrate long-term iodine stability. These results indicate that ex situ processes, such as vertical mixing, may play an important role in broader iodine species’ distribution in this and similar regions.</p

Organically bound iodine as a bottom-water redox proxy : preliminary validation and application

© 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.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.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

Investigating controls on boron isotope ratios in shallow marine carbonates

The boron isotope-pH proxy has been widely used to reconstruct past ocean pH values. In both planktic foraminifera and corals, species-specific calibrations are required in order to reconstruct absolute values of pH, due to the prevalence of so-called vital effects — physiological modification of the primary environmental signals by the calcifying organisms. Shallow marine abiotic carbonate (e.g. ooids and cements) could conceivably avoid any such calibration requirement, and therefore provide a potentially useful archive for reconstructions in deep (pre-Cenozoic) time. However, shallow marine abiotic carbonates could also be affected by local shifts in pH caused by microbial photosynthesis and respiration, something that has up to now not been fully tested. In this study, we present boron isotope measurements from shallow modern marine carbonates, from the Bahama Bank and Belize to investigate the potential of using shallow water carbonates as pH archives, and to explore the role of microbial processes in driving nominally ‘abiogenic’ carbonate deposition. For Bahama bank samples, our boron-based pH estimates derived from a range of carbonate types (i.e. ooids, peloids, hardground cements, carbonate mud, stromatolitic micrite and calcified filament micrite) are higher than the estimated modern mean-annual seawater pH values for this region. Furthermore, the majority (73%) of our marine carbonate-based pH estimates fall out of the range of the estimated pre-industrial seawater pH values for this region. In shallow sediment cores, we did not observe a correlation between measured pore water pH and boron-derived pH estimates, suggesting boron isotope variability is a depositional rather than early diagenetic signal. For Belize reef cements, conversely, the pH estimates are lower than likely in situ seawater pH at the time of cement formation. This study indicates the potential for complications when using shallow marine non-skeletal carbonates as marine pH archives. In addition, variability in δ11B based pH estimates provides additional support for the idea that photosynthetic CO2 uptake plays a significant role in driving carbonate precipitation in a wide range of shallow water carbonates. •δ11B measured in a range of modern shallow marine carbonates.•Boron derived pH shows large variation compared to ambient pH.•Microbial mediation facilitates shallow marine carbonate precipitation.•Many types of shallow marine carbonates cannot be used as boron isotope pH archives