Rapid Extraction Chemistry Using a Single Column for 230Th/U Dating of Quaternary Hydrothermal Sulfides

230Th/U dating can provide high-precision age constraints on Quaternary hydrothermal sulfides. However, low content of U and Th often involves extraction chemistry for the separation and enrichment of U and Th, but these chemical processes are very complex. We developed a simplified procedure consisting of total sample dissolution and single-column extraction chemistry, which can reduce the time and improve the accuracy of the dating. Concentrated HCl-HF followed by HNO3 was added to ensure complete dissolution. A single column filled with 0.4 mL of AG 1-X8 anion resin was used, then 8 M HNO3, 8 M HCl and 0.1 M HNO3 were used to elute most of the matrix metals, Th and U. This process provided more than 95% recoveries for U and Th, and negligible blanks. Meanwhile, Pb and Bi interferences were tested and showed no effect on the U and Th isotope ratio. The 230Th/238U activity of the Geological Survey of Japan geochemical reference material JZn-1 in secular equilibrium was determined and showed a radioactive equilibrium (1.00 ± 0.01, n = 5, all errors 2σ) and an in-house standard QS-1 was consistent to 0.0078 ± 0.0001 (n = 8, ±2σ) with an average age of 705 ± 10 yrs BP (n = 8, ±2σ). The technique greatly shortens the sample preparation time and allows more concise and effective analysis of U-Th isotopes. It is ideally suited for the high-precision 230Th/U dating of Quaternary submarine hydrothermal sulfides and sulfides from other settings.

Supplemental Material: U-Pb speleothem geochronology reveals a major ca. 6 Ma uplift phase along the western margin of Dead Sea Transform

Description of the study sites, Research Methods, U-Th analytical results and Supplemental Figures (Word Document). Dataset 1: Initial 234U/238U activity ratios of Israeli speleothems. Dataset 2: Raw U-Pb geochronological data.

Supplemental Material: U-Pb speleothem geochronology reveals a major ca. 6 Ma uplift phase along the western margin of Dead Sea Transform

Description of the study sites, Research Methods, U-Th analytical results and Supplemental Figures (Word Document). Dataset 1: Initial 234U/238U activity ratios of Israeli speleothems. Dataset 2: Raw U-Pb geochronological data.

Effects of ²³⁸U variability and physical transport on water column ²³⁴Th downward fluxes in the coastal upwelling system off Peru

The eastern boundary region of the southeastern Pacific Ocean hosts one of the world's most dynamic and productive upwelling systems with an associated oxygen minimum zone (OMZ). The variability in downward export fluxes in this region, with strongly varying surface productivity, upwelling intensities and water column oxygen content, is however poorly understood. Thorium-234 (234Th) is a powerful tracer to study the dynamics of export fluxes of carbon and other elements, yet intense advection and diffusion in nearshore environments impact the assessment of depth-integrated 234Th fluxes when not properly evaluated. Here we use vessel-mounted acoustic Doppler current profiler (VmADCP) current velocities, satellite wind speed and in situ microstructure measurements to determine the magnitude of advective and diffusive fluxes over the entire 234Th flux budget at 25 stations from 11 to 16∘ S in the Peruvian OMZ. Contrary to findings along the GEOTRACES P16 eastern section, our results showed that weak surface wind speed during our cruises induced low upwelling rates and minimal upwelled 234Th fluxes, whereas vertical diffusive 234Th fluxes were important only at a few shallow shelf stations. Horizontal advective and diffusive 234Th fluxes were negligible because of small alongshore 234Th gradients. Our data indicated a poor correlation between seawater 238U activity and salinity. Assuming a linear relationship between the two would lead to significant underestimations of the total 234Th flux by up to 40 % in our study. Proper evaluation of both physical transport and variability in 238U activity is thus crucial in coastal 234Th flux studies. Finally, we showed large temporal variations on 234Th residence times across the Peruvian upwelling zone and cautioned future carbon export studies to take these temporal variabilities into consideration while evaluating carbon export efficiency.

Comparison of Uranium Isotopes and Classical Geochemical Tracers in Karst Aquifer of Ljubljanica River catchment (Slovenia)

The karst aquifer of the Ljubljanica River catchment, which has numerous springs and sinks, presents an interesting environment for studying hydrogeological processes. This study aims to explore the behavior of U isotopes and to evaluate their use as tracers of hydrogeochemical processes as an alternative to classical geochemical tracers (i.e., physicochemical parameters, elemental ratios, and alkalinity) involved in water–rock interactions and water flow in this karst water system. Basic hydrochemical parameters, as well as the spatiotemporal variations of total U concentrations, 234U/238U activity ratios, and δ238U values, were monitored in water samples from springs and sinks under different hydrological conditions. The bedrock as the source of dissolved and detrital U was also analyzed. Multi-collector inductively couple plasma-mass spectrometry results reveal variations of the 234U/238U activity ratios, which are consistently negatively correlated with the discharge at most analyzed sites. Large 238U/235U isotope fractionation occurred during bedrock weathering, and the large variability of the measured δ238U values is seemingly unrelated to the lithological characteristics of the bedrock or discharge. Our results confirm that 234U/238U activity ratios in water can be used as a tracer for studying changes in groundwater flows and the mixing of waters of different origins under different hydrological conditions.

Effects of ²³⁸U variability and physical transport on water column ²³⁴Th downward fluxes in the coastal upwelling system off Peru

The eastern boundary region of the southeast Pacific Ocean hosts one of the world's most dynamic and productive upwelling systems with an associated oxygen minimum zone (OMZ). The variability in downward export fluxes in this region, with strongly varying surface productivity, upwelling intensities and water column oxygen content, is however poorly understood. Thorium-234 (234Th) is a powerful tracer to study the dynamics of export fluxes of carbon and other elements, yet intense advection and diffusion in nearshore environments impact the assessment of depth-integrated 234Th fluxes when not properly evaluated. Here we use ADCP current velocities, satellite wind stress and in situ microstructure measurements to determine the magnitude of advective and diffusive fluxes over the entire 234Th flux budget at 25 stations from 11° S to 16° S in the Peruvian OMZ. Contrary to findings along the GEOTRACES P16 eastern section, our results showed that weak surface wind stress during our cruises induced low upwelling rates and minimal upwelling 234Th fluxes, whereas vertical diffusive 234Th fluxes were important only at a few shallow shelf stations. Similarly, horizontal advective and diffusive 234Th fluxes were negligible due to small alongshore 234Th gradients. Our data indicated a poor correlation between seawater 238U activity and salinity. Assuming a linear relationship between the two would lead to significant underestimations of the total 234Th flux by up to 40 % in our study. Proper evaluation of both physical transport and variability in 238U activity is thus crucial in coastal 234Th flux studies. Finally, we showed large temporal variations on 234Th residence times across the Peruvian upwelling zone, and cautioned future carbon export studies to take these temporal changes into consideration while evaluating carbon export efficiency.