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A Model Study of the Relative Influences of Scavenging and Circulation on 230Th and 231Pa in the Western North Atlantic

The oceanic cycles of thorium-230 and protactinium-231 are affected by a number of processes, such as removal by adsorption to settling particles and transport by ocean currents. Measurements obtained as part of GEOTRACES and earlier programs have shown that, in the North Atlantic, the activities of dissolved 230Th (230Thd) and 231Pa (231Pad) at abyssal depths are lower near the western margin than in the basin interior. At least two factors could explain the lower 230Thd and 231Pad near the margin: (i) intensified scavenging in benthic nepheloid layers (BNLs) extending a thousand meters or more above the seafloor; and (ii) ventilation by relatively 230Thd- and 231Pad-poor waters emanating from the Deep Western Boundary Current (DWBC).Here a regional ocean circulation model with ?eddy-permitting' resolution (1/4) that incorporates 230Th and 231Pa is used in an effort to reproduce the observed distributions of 230Th and 231Pa in the western North Atlantic. In this model, 230Th and 231Pa removal from solution is governed by a prescribed distribution of particulate matter that is derived from a recent synthesis of nephelometer and transmissometer data. The model simulates a meandering Gulf Stream and a DWBC along the continental slope and rise, although noticeable differences with physical observations also exist. A model solution is found that explains most of the variance of 230Thd measurements (85%) and 231Pad measurements (81%) from (pre-)GEOTRACES cruises. On the other hand, measurements of particulate 230Th (230Thp) and 231Pa (231Pap) are more difficult to reproduce, with the same solution accounting for only 49% (11%) of the 230Thp (231Pap) variance. Sensitivity experiments suggest that the low 230Thd and 231Pad activities observed near the western margin are due to enhanced removal rates of both nuclides in BNLs rather than to deep water ventilation from the western boundary. The radionuclide activities present in the DWBC at its inflow location are also found to strongly influence the basin-scale distributions of 230Th and 231Pa. Overall, our study points to BNLs as important sites of 230Th and 231Pa scavenging in the ocean and illustrates the difficulty to explain simultaneously radionuclide measurements in dissolved and particulate forms in the studied area.

Lerner, Paul↗

230Th Normalization: New Insights on an Essential Tool for Quantifying Sedimentary Fluxes in the Modern and Quaternary Ocean

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 of 230Th systematics, with regard to particle type, particle size, lateral advective/diffusive redistribution, and other processes, have emerged. We synthesized over 1000 sedimentary records of 230Th 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 of 230Th‐normalized mass fluxes. On a global scale, sedimentary mass fluxes were significantly higher during the Last Glacial Maximum (1.79–2.17 g/sq.cmkyr, 95% confidence) relative to the Holocene (1.48–1.68 g/sq.cmkyr, 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 of 230Th as a constant flux proxy. Anomalous 230Th 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 that 230Th normalization is a robust tool for determining sediment mass accumulation rates in the majority of pelagic marine settings (>1,000 m water depth).

Costa, Kassandra M.↗

Influence of sediment resuspension on deep-ocean Pa-231 and Th-230 cycling: A PROGRESS REPORT

The naturally-occurring particle-reactive radionuclides protactinium-231 (231Pa) and thorium-230 (230Th) are used as tracers of a variety of oceanic processes, both at present and in the past. Most notably, the sediment 231Pa/230Th ratio has been used to infer changes in the Atlantic Meridional Overturning Circulation over the last (de)glaciation. However, recent measurements along the U.S. GEOTRACES North Atlantic transect (GA03) revealed two features which are at odds with current understanding about 231Pa and 230Th behaviour in the ocean: (i) a sharp decrease in dissolved 231Pa and 230Th activities with depth below 2000-4000 m and (ii) very large particulate 231Pa and 230Th activities near the bottom, at a number of stations between the New England continental shelf and Bermuda. Concomitant measurements of particulate matter concentration and potential temperature showed that both features are associated with the benthic nepheloid layer (BNL) and the bottom mixed layer (BML) that are present at these stations. Here we develop and apply a simplified model of the exchange of particles, 231Pa, and 230Th between the BNL and the upper sediment, to explore the extent to which the radionuclide anomalies observed near the bottom at a number of GA03 stations can be explained by local sediment resuspension. We find that the model can broadly reproduce the observed anomalies at two stations where samples for radionuclide analyses were collected near the seafloor. Sensitivity tests with the model show that the 231Pa/230Th ratio of particles in the BML and the sediment varies by a factor of 3 as the sediment resuspension rate fluctuates within a range consistent with observational estimates. The modelled variability is comparable to the spatial variability of 231Pa/230Th of suspended particles in the modern North Atlantic and to the variability of Atlantic sediment 231Pa/230Th records across the last (de)glacial period. Two factors are found to contribute to the modelled sensitivity of the sediment 231Pa/230Th to sediment resuspension rate: the vertical turbulent mixing in the BML and the differential scavenging intensity of Pa and Th due to variation in particle concentration. Overall, our study indicates that the exchange of material between the BNL and the upper sediment can affect the particulate 231Pa/230Th ratio in the bottom water and the sediment, which may complicate the use of sediment 231Pa/230Th as a palaeoceanographic tracer.

particle-reactive radionuclides↗

Separation of thorium from uranium ore

Thorium-230 has many research applications, but there is not a commercial source of this isotope. However, since 230 Th is part of the 238 U decay chain, it can be separated from naturally occurring uranium. In this work, a novel procedure was developed to separate thorium from uranium ore, consisting of leaching, liquid–liquid extraction, precipitations and ion exchange chromatography. Here, the final product was 91.32 ± 0.77 mg of thorium with a purity of 99.5 ± 1.2 wt%. Of that, 7.65 ± 0.10 mg was 230 Th and the remainder 232 Th. The total yield of 230 Th was 71.1 ± 5.4%. Ways to improve the yield by further processing the back-extraction solution are suggested.

230Th↗

Temperature dependence of uranium and thorium partitioning in igneous zircons

Zircon is a key mineral in geochronology because of its chemical and physical durability and tendency to incorporate radioactive trace elements such as U and Th. Quantifying the partitioning of the actinide elements is critical to constrain initial non-secular equilibrium amounts of 230 Th in zircon. An excess or deficit of 206 Pb will be produced from such an initial excess/deficit of 230 Th from the secular equilibrium condition, which influences the calculated 206 Pb/ 238 U age (Schärer, 1984, Mattinson, 1973). However, there is no standard way to calculate Th/U partitioning ratios when applying age corrections to young igneous zircon, making uncertainties hard to estimate. To better understand U and Th partitioning of zircon/melt that is the cornerstone of the secular disequilibrium correction, zircon was synthesized in one-atmosphere experiments using basaltic andesite, andesite, and rhyolite starting materials, doped with Zr, U, and Th. Different experimental temperatures and oxygen fugacity conditions (ΔQFM−4 to ΔQFM+4) were explored to examine their effects on U and Th partitioning. In addition, we specifically quantify the effects of sector zoning, fractional crystallization, and melt composition on U and Th partitioning. By combining experimental and natural zircon data, we find that temperature has the primary control on the partitioning of U and Th in the zircon and calibrate an inverse relationship between these partition coefficients and crystallization temperatures. The calibrated equation can be applied to the 230 Th correction for an improvement in the accuracy of Th-corrected 206 Pb/ 238 U dates when the zircon crystallization temperature is known.

206Pb/238U dating↗