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A point-of-use electrochemical phosphate sensor is achieved with electrodeposited mixed-valence molybdenum oxide on flexible electrodes, enabling selective detection in complex aqueous environments. 

Abstract Fully and accurately reconstructing changes in oceanic productivity and carbon export and their controls is critical to determining the efficiency of the biological pump and its role in the global carbon cycle through time, particularly in modern CO₂source regions like the eastern equatorial Pacific (EEP). Here we present new high-resolution records of sedimentary²³⁰Th-normalized opal and nannofossil carbonate fluxes and [²³¹Pa/²³⁰Th]xs ratios from site MV1014-02-17JC in the Panama Basin. We find that, across the last deglaciation, phytoplankton community structure is driven by changing patterns of nutrient (nitrate, iron, and silica) availability which, in turn, are caused by variability in the position of the Intertropical Convergence Zone (ITCZ) and associated changes in biogeochemical cycling and circulation in the Southern Ocean. Our multi-proxy work suggests greater scrutiny is required in the interpretation of common geochemical proxies of productivity and carbon export in the EEP. 

Abstract North African dust is known to be deposited in the Gulf of Mexico, but its deposition rate and associated supply of lithogenic dissolved metals, such as the abiotic metal thorium or the micronutrient metal iron, have not been well‐quantified.²³²Th is an isotope with similar sources as iron and its input can be quantified using radiogenic²³⁰Th. By comparing dissolved²³²Th fluxes at three sites in the northern Gulf of Mexico with upwind sites in the North Atlantic, we place an upper bound on North African dust contributions to²³²Th and Fe in the Gulf of Mexico, which is about 30% of the total input. Precision on this bound is hindered by uncertainty in the relative rates of dust deposition in the North Atlantic and the northern Gulf of Mexico. Based on available radium data, shelf sources, including rivers, submarine groundwater discharge, and benthic sedimentary releases are likely as important if not more important than dust in the budget of lithogenic metals in the Gulf of Mexico. In other words, it is likely there is no one dominant source of Th and Fe in the Gulf of Mexico. Finally, our estimated Fe input in the northern Gulf of Mexico implies an Fe residence time of less than 6 months, similar to that in the North Atlantic despite significantly higher supply rates in the Gulf of Mexico. 

Abstract Ocean time‐series sites are influenced by both temporal variability, as in situ conditions change, as well as spatial variability, as water masses move across the fixed observation point. To remove the effect of spatial variability, this study made sub‐daily Lagrangian observations of trace elements and isotopes (Al, Sc, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb,²³²Th, and²³⁰Th) in surface water over a 12‐day period (July–August 2015) in the North Pacific near the Hawaii Ocean Time‐series Station ALOHA. Additionally, a vertical profile in the upper 250 m was analyzed. This dataset is intercalibrated with GEOTRACES standards and provides a consistent baseline for trace element studies in the oligotrophic North Pacific. No diel changes in trace elements could be resolved, although day‐to‐day variations were resolved for some elements (Fe, Cu, and Zn), which may be related to organic matter cycling or ligand availability. Pb concentrations remained relatively constant during 1997–2015, presenting a change from previous decreases. Nutrient to trace element stoichiometric ratios were compared to those observed in phytoplankton as an indication of the extent of biological trace element utilization in this ecosystem, providing a basis for future ecological trace element studies. 

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. 

Abstract Sinking particles strongly regulate the distribution of reactive chemical substances in the ocean, including particulate organic carbon and other elements (e.g., P, Cd, Mn, Cu, Co, Fe, Al, and²³²Th). Yet, the sinking fluxes of trace elements have not been well described in the global ocean. The U.S. GEOTRACES campaign in the North Atlantic (GA03) offers the first data set in which the sinking flux of carbon and trace elements can be derived using four different radionuclide pairs (²³⁸U^:234Th^;210Pb:²¹⁰Po;²²⁸Ra:²²⁸Th; and²³⁴U:²³⁰Th) at stations co‐located with sediment trap fluxes for comparison. Particulate organic carbon, particulate P, and particulate Cd fluxes all decrease sharply with depth below the euphotic zone. Particulate Mn, Cu, and Co flux profiles display mixed behavior, some cases reflecting biotic remineralization, and other cases showing increased flux with depth. The latter may be related to either lateral input of lithogenic material or increased scavenging onto particles. Lastly, particulate Fe fluxes resemble fluxes of Al and²³²Th, which all have increasing flux with depth, indicating a dominance of lithogenic flux at depth by resuspended sediment transported laterally to the study site. In comparing flux estimates derived using different isotope pairs, differences result from different timescales of integration and particle size fractionation effects. The range in flux estimates produced by different methods provides a robust constraint on the true removal fluxes, taking into consideration the independent uncertainties associated with each method. These estimates will be valuable targets for biogeochemical modeling and may also offer insight into particle sinking processes. 

Abstract ²³⁰Th normalization is a valuable paleoceanographic tool for reconstructing high‐resolution sediment fluxes during the late Pleistocene (last ~500,000 years). As its application has expanded to ever more diverse marine environments, the nuances of²³⁰Th systematics, with regard to particle type, particle size, lateral advective/diffusive redistribution, and other processes, have emerged. We synthesized over 1000 sedimentary records of²³⁰Th from across the global ocean at two time slices, the late Holocene (0–5,000 years ago, or 0–5 ka) and the Last Glacial Maximum (18.5–23.5 ka), and investigated the spatial structure of²³⁰Th‐normalized mass fluxes. On a global scale, sedimentary mass fluxes were significantly higher during the Last Glacial Maximum (1.79–2.17 g/cm²kyr, 95% confidence) relative to the Holocene (1.48–1.68 g/cm²kyr, 95% confidence). We then examined the potential confounding influences of boundary scavenging, nepheloid layers, hydrothermal scavenging, size‐dependent sediment fractionation, and carbonate dissolution on the efficacy of²³⁰Th as a constant flux proxy. Anomalous²³⁰Th behavior is sometimes observed proximal to hydrothermal ridges and in continental margins where high particle fluxes and steep continental slopes can lead to the combined effects of boundary scavenging and nepheloid interference. Notwithstanding these limitations, we found that²³⁰Th normalization is a robust tool for determining sediment mass accumulation rates in the majority of pelagic marine settings (>1,000 m water depth).