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1. Early Diagenetic Controls on Sedimentary Iodine Release and Iodine‐To‐Organic Carbon Ratios in the Paleo‐Record

   https://doi.org/10.1029/2023GB007919  

   Scholz, Florian; Hardisty, Dalton S; Dale, Andrew W (February 2024, Global Biogeochemical Cycles)

   Abstract Iodine cycling in the ocean is closely linked to productivity, organic carbon export, and oxygenation. However, iodine sources and sinks at the seafloor are poorly constrained, which limits the applicability of iodine as a biogeochemical tracer. We present pore water and solid phase iodine data for sediment cores from the Peruvian continental margin, which cover a range of bottom water oxygen concentrations, organic carbon rain rates and sedimentation rates. By applying a numerical reaction‐transport model, we evaluate how these parameters determine benthic iodine fluxes and sedimentary iodine‐to‐organic carbon ratios (I:C_org) in the paleo‐record. Iodine is delivered to the sediment with organic material and released into the pore water as iodide (I⁻) during early diagenesis. Under anoxic conditions in the bottom water, most of the iodine delivered is recycled, which can explain the presence of excess dissolved iodine in near‐shore anoxic seawater. According to our model, the benthic I⁻efflux in anoxic areas is mainly determined by the organic carbon rain rate. Under oxic conditions, pore water dissolved I⁻is oxidized and precipitated at the sediment surface. Much of the precipitated iodine re‐dissolves during early diagenesis and only a fraction is buried. Particulate iodine burial efficiency and I:C_orgburial ratios do increase with bottom water oxygen. However, multiple combinations of bottom water oxygen, organic carbon rain rate and sedimentation rate can lead to identical I:C_org, which limits the utility of I:C_orgas a quantitative oxygenation proxy. Our findings may help to better constrain the ocean's iodine mass balance, both today and in the geological past. 

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2. Geochemical conditions regulating chromium preservation in marine sediments

   https://doi.org/10.1016/j.gca.2023.03.003  

   Bruggmann, S.; Severmann, S.; McManus, J. (May 2023, Geochimica et Cosmochimica Acta)

   In the marine sediment record, concentrations and isotope ratios of chromium (Cr) can be used to reconstruct ocean biogeochemical conditions. These reconstructions rely on a detailed understanding of the chemical pathways that Cr undergoes as it is transferred from the water column to the sediment record. We examined Cr concentrations in marine pore fluids and sediments from six continental margin sites, which can be grouped into two basic environments: (1) sites where sediments are oxygenated and rich in solid phase Mn (herein termed oxic), and (2) sites where sediments are organic C (Corg)-rich and oxygen is depleted (anoxic). We found Cr concentrations to be lower (maximum of 12 nM in pore fluids and 124 ppm sediment solid phase) at oxic sites compared with anoxic sites (maximum of 77 nM and 184 ppm). Our findings confirm previously published interpretations of dissolved Cr in pore fluids (Brumsack and Gieskes, 1983; Shaw et al., 1990). In oxic surface sediments, particulate Cr(III) can be oxidised by Mn oxides, which leads to elevated concentrations of dissolved Cr co-occurring at the same depth as elevated Mn concentrations in the sediment. Under these oxidising conditions, down-core sediments contain relatively low solid-phase Cr concentrations. In oxic sediments, Cr speciation reveals that most of the pore fluid Cr is in the Cr(VI) state. At the site where Mn oxide-rich sediments rest below an oxic water column, oxidative loss of Cr from the sediment to the bottom water leads to the lowest estimated Cr burial efficiency of the sites examined here. Under anoxic Corg-rich conditions, both pore fluids and sediment solid phases contain high Cr concentrations, with 40–80% of dissolved pore fluid Cr present as Cr(III). This enrichment of Cr appears to be tightly linked to the presence of high total organic carbon (TOC) content and scavenging of Cr by (organic) particles in the water column. Combined, these data highlight the strong dependence of Cr on both sedimentary redox conditions as well as biological productivity. Based on the data from modern continental margin sediments, we propose that Cr concentrations and isotope compositions of the authigenic sediment fraction may record a combination of redox conditions and biological productivity in the water column. If confirmed by Cr isotope analyses, these findings will add support for the notion that Cr may serve as a proxy for ocean biological and chemical sedimentological conditions. Thus, careful assessment of the impact of organic matter on Cr is required for reconstructions of redox conditions with sedimentary records. 

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3. Isotopically Light Cd in Sediments Underlying Oxygen Deficient Zones

   https://doi.org/10.3389/feart.2021.623720  

   Chen, Lena; Little, Susan H.; Kreissig, Katharina; Severmann, Silke; McManus, James (March 2021, Frontiers in Earth Science)

   null (Ed.)

   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/PO 4 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 × 10 7  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 ( δ 114/110 Cd NIST-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. 

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4. K isotopes as a tracer for continental weathering and geological K cycling

   https://doi.org/10.1073/pnas.1811282116  

   Li, Shilei; Li, Weiqiang; Beard, Brian L.; Raymo, Maureen E.; Wang, Xiaomin; Chen, Yang; Chen, Jun (April 2019, Proceedings of the National Academy of Sciences)

   The causal effects among uplift, climate, and continental weathering cannot be fully addressed using presently available geochemical proxies. However, stable potassium (K) isotopes can potentially overcome the limitations of existing isotopic proxies. Here we report on a systematic investigation of K isotopes in dissolved load and sediments from major rivers and their tributaries in China, which have drainage basins with varied climate, lithology, and topography. Our results show that during silicate weathering, heavy K isotopes are preferentially partitioned into aqueous solutions. Moreover, δ⁴¹K values of riverine dissolved load vary remarkably and correlate negatively with the chemical weathering intensity of the drainage basin. This correlation allows an estimate of the average K isotope composition of global riverine runoff (δ⁴¹K = −0.22‰), as well as modeling of the global K cycle based on mass balance calculations. Modeling incorporating K isotope mass balance better constrains estimated K fluxes for modern global K cycling, and the results show that the δ⁴¹K value of seawater is sensitive to continental weathering intensity changes. Thus, it is possible to use the δ⁴¹K record of paleo-seawater to infer continental weathering intensity through Earth’s history. 

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5. Dissolved and Particulate Barium Distributions Along the US GEOTRACES North Atlantic and East Pacific Zonal Transects (GA03 and GP16): Global Implications for the Marine Barium Cycle

   https://doi.org/10.1029/2022GB007330  

   Rahman, Shaily; Shiller, Alan M.; Anderson, Robert F.; Charette, Matthew A.; Hayes, Christopher T.; Gilbert, Melissa; Grissom, Karen R.; Lam, Phoebe J.; Ohnemus, Daniel C.; Pavia, Frank J.; et al (June 2022, Global Biogeochemical Cycles)

   Abstract Processes controlling dissolved barium (dBa) were investigated along the GEOTRACES GA03 North Atlantic and GP16 Eastern Tropical Pacific transects, which traversed similar physical and biogeochemical provinces. Dissolved Ba concentrations are lowest in surface waters (∼35–50 nmol kg⁻¹) and increase to 70–80 and 140–150 nmol kg⁻¹in deep waters of the Atlantic and Pacific transects, respectively. Using water mass mixing models, we estimate conservative mixing that accounts for most of dBa variability in both transects. To examine nonconservative processes, particulate excess Ba (pBa_xs) formation and dissolution rates were tracked by normalizing particulate excess²³⁰Th activities. Th‐normalized pBa_xsfluxes, with barite as the likely phase, have subsurface maxima in the top 1,000 m (∼100–200 μmol m⁻² year⁻¹average) in both basins. Barite precipitation depletes dBa within oxygen minimum zones from concentrations predicted by water mass mixing, whereas inputs from continental margins, particle dissolution in the water column, and benthic diffusive flux raise dBa above predications. Average pBa_xsburial efficiencies along GA03 and GP16 are ∼37% and 17%–100%, respectively, and do not seem to be predicated on barite saturation indices in the overlying water column. Using published values, we reevaluate the global freshwater dBa river input as 6.6 ± 3.9 Gmol year⁻¹. Estuarine mixing processes may add another 3–13 Gmol year⁻¹. Dissolved Ba inputs from broad shallow continental margins, previously unaccounted for in global marine summaries, are substantial (∼17 Gmol year⁻¹), exceeding terrestrial freshwater inputs. Revising river and shelf dBa inputs may help bring the marine Ba isotope budget more into balance. 

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