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  1. Phosphate fertilizers may contain elevated concentrations of toxic metals and metalloids and therefore, their excessive application can result in the accumulation of both phosphorus (P) and metal(loid)s in agricultural soils. This study aims to investigate the occurrence, distribution, and potential plant-availability of metal(loid)s originating from phosphate fertilizer in a long-term experimental field at the Tidewater Research Station in North Carolina, where topsoil (10-20 cm deep) and subsoil (up to 150 cm deep) samples were collected from five plots with consistent and individually different application rates of P-fertilizer since 1966. We conducted systematic analyses of P and metal(loid)s in bulk soils, in the plant available fraction, and in four sequentially extracted soil fractions (exchangeable, reducible, oxidizable, and residual). The results show that P content in topsoils were directly associated with the rate of P-fertilizer application (=1, p<0.05). Furthermore, P concentrations were highly correlated with concentrations of Cd, U, Cr, V, and As in the bulk topsoil (>0.58, p<0.05), as well as the potential plant-available fraction (>0.67, p<0.01), indicating the accumulation of the fertilizer-derived toxic metal(loid)s in the topsoil. Significant correlations (p<0.001) of metal(loid)s concentrations between the bulk soil and the potential plant-available fraction raises the possibility that P-fertilizer application could increase the accumulation of toxic metal(loid)s in plants, which could increase human exposure. Results from sequential leaching experiments revealed that large portions of the trace elements, in particular Cd, occur in the soluble (exchangeable and reducing) fractions of topsoil with higher P-fertilizer input, whereas the levels of redox-sensitive elements (As, V, U, Cr) were higher in the reducible and oxidizable fractions of the soils. Overall, the data presented in this study demonstrate the effect of long-term P-fertilizer application on the occurrence and accumulation of a wide range of toxic metal(loid)s in agricultural topsoil. 
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    Free, publicly-accessible full text available January 1, 2025
  2. Phosphate rock bears both geologically and environmentally significant information. Rare earth elements and yttrium (i.e., REY) characteristics have been commonly used for reconstructing the redox conditions of depositional environments of and the effects of post-depositional diagenetic alteration on phosphate rock. In addition, phosphate rock is typically enriched in a range of trace elements such as uranium (U) and cadium (Cd) that can be dispersed as contaminants into the environment with phosphate mining and phosphate fertilizer application. Here we report the lead (Pb) isotope compositions combined with Pb and REY concentrations of both global sedimentary and igneous phosphate rocks, aiming to evalute the geological origin of phosphate rocks over time and the potential of using them for environmental tracing. Phopshate rocks samples analyzed in this study were sourced from major economic phosphate deposits in the world, including China, Southern Tethys (e.g., Morocco, Tunisia, Israel), the U.S., India, South Africa and Russia. Our results show a wide range of 208Pb/204Pb (35.70 to 60.58), 207Pb/204Pb (15.20 to 18.25), and 206Pb/204Pb (16.369 to 71.806) ratios in phosphate rocks, with sedimentary phosphate rocks being significantly more radiogenic than igneous rocks. The majority of the sedimentray phosphate rocks show a notable isotopic overprinting by non-radiogenic terrestrial Pb, except for those from Israel and Morocco that have the most radiogenic Pb isotope compositions. Correspondingly, phosphate rocks with more radiogenic Pb isotope ratios show relatively pristine seawater REY features, likely suggesting their preservation of the original oxic seawater conditions and/or minimal diagenetic alteration. In contrast, phosphate rocks with less radiogenic Pb isotope compositions show REY indications for more anoxic seawater redox conditions and/or greater diagenetic alteration. We further evaluate the potential utility of Pb isotopes for tracing the associated contamination with phosphate rock mining and fertilizer application in the environment. In most cases, the radiogenic Pb isotope composition of phosphate rocks and corresponding P-fertilizers is distinctive from both natural crustal Pb and major anthropogenic Pb sources (e.g., Pb ore deposits and pesticides), which provides a great advantage for applying Pb isotopes as environmental tracers for metal(loid) contamination from phosphate sources. The combination of Pb isotope ratios and REY proxies could further constrain the Pb source discrimination. Overall, this study provides new Pb isotopic and REY geochemical data on global phosphate rocks and fertilizers, which lays the groundwork for future regional and local studies on both their geological and environmental implications. 
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    Free, publicly-accessible full text available November 1, 2024
  3. The oxygen isotopic composition of benthic foraminifera (d18Ob) is widely used to date and correlate marine sediment sequences. However, d18Ob has found comparatively little use in the Arctic Ocean due both to uncertainty in Arctic marine sediment chronology and the lack of resemblance between Arctic and open ocean d18Ob records. We address this issue by combining Arctic d18Ob records (Cronin et al., 2019) with benthic ostracode Mg/Ca-BWT reconstructions (Cronin et al., 2017) to create a composite record of the history of seawater d18O in the intermediate-to-deep Arctic Ocean over the last 600 kyr. Seawater d18O and its uncertainty was calculated using PSU Solver (Thirumalai et al., 2016). 
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  4. Abstract. The oxygen isotopic composition of benthic foraminiferal tests (δ18Ob) is one of the pre-eminent tools for correlating marine sediments and interpreting past terrestrial ice volume and deep-ocean temperatures. Despite the prevalence of δ18Ob applications to marine sediment cores over the Quaternary, its use is limited in the Arctic Ocean because of low benthic foraminiferal abundances, challenges with constructing independent sediment core age models, and an apparent muted amplitude of Arctic δ18Ob variability compared to open-ocean records. Here we evaluate the controls on Arctic δ18Ob by using ostracode Mg/Ca paleothermometry to generate a composite record of the δ18O of seawater (δ18Osw) from 12 sediment cores in the intermediate to deep Arctic Ocean (700–2700 m) that covers the last 600 kyr based on biostratigraphy and orbitally tuned age models. Results show that Arctic δ18Ob was generally higher than open-ocean δ18Ob during interglacials but was generally equivalent to global reference records during glacial periods. The reduced glacial–interglacial Arctic δ18Ob range resulted in part from the opposing effect of temperature, with intermediate to deep Arctic warming during glacials counteracting the whole-ocean δ18Osw increase from expanded terrestrial ice sheets. After removing the temperature effect from δ18Ob, we find that the intermediate to deep Arctic experienced large (≥1 ‰) variations in local δ18Osw, with generally higher local δ18Osw during interglacials and lower δ18Osw during glacials. Both the magnitude and timing of low local δ18Osw intervals are inconsistent with the recent proposal of freshwater intervals in the Arctic Ocean during past glaciations. Instead, we suggest that lower local δ18Osw in the intermediate to deep Arctic Ocean during glaciations reflected weaker upper-ocean stratification and more efficient transport of low-δ18Osw Arctic surface waters to depth by mixing and/or brine rejection. 
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  5. Abstract

    Marine Isotope Stage 11 from ~424 to 374 ka experienced peak interglacial warmth and highest global sea level ~410–400 ka. MIS 11 has received extensive study on the causes of its long duration and warmer than Holocene climate, which is anomalous in the last half million years. However, a major geographic gap in MIS 11 proxy records exists in the Arctic Ocean where fragmentary evidence exists for a seasonally sea ice‐free summers and high sea‐surface temperatures (SST; ~8–10 °C near the Mendeleev Ridge). We investigated MIS 11 in the western and central Arctic Ocean using 12 piston cores and several shorter cores using proxies for surface productivity (microfossil density), bottom water temperature (magnesium/calcium ratios), the proportion of Arctic Ocean Deep Water versus Arctic Intermediate Water (key ostracode species), sea ice (epipelagic sea ice dwelling ostracode abundance), and SST (planktic foraminifers). We produced a new benthic foraminiferal δ18O curve, which signifies changes in global ice volume, Arctic Ocean bottom temperature, and perhaps local oceanographic changes. Results indicate that peak warmth occurred in the Amerasian Basin during the middle of MIS 11 roughly from 410 to 400 ka. SST were as high as 8–10 °C for peak interglacial warmth, and sea ice was absent in summers. Evidence also exists for abrupt suborbital events punctuating the MIS 12‐MIS 11‐MIS 10 interval. These fluctuations in productivity, bottom water temperature, and deep and intermediate water masses (Arctic Ocean Deep Water and Arctic Intermediate Water) may represent Heinrich‐like events possibly involving extensive ice shelves extending off Laurentide and Fennoscandian Ice Sheets bordering the Arctic.

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