Institutskolloquium

Title: Quantification of ^239,24xPu in environmental samples – method development, applications and perspectives

Summary: The measurement of ^239,240Pu in environmental samples can play a key role in investigating Earth (sub-)surface processes. Earth’s outermost skin has been enriched in such anthropogenic fallout radionuclides (FRNs) as a consequence of atmospheric nuclear weapon tests conducted in the 1950s and 1960s, providing distinct geochronological markers. The application of FRNs is well established, with ¹³⁷Cs (and the naturally occurring ²¹⁰Pb) being most commonly measured. However, ^239,240Pu activities are more decay-insensitive (t_1/2 ²³⁹Pu: ~24.1 ka; ²⁴⁰Pu: ~6.6 ka), and there is less soil inventory contamination arising from nuclear power plant accidents compared to ¹³⁷Cs. Additionally, only a few grams of sample material are required for a measurement.

Several years of research at the University of Cologne (UoC) have resulted in the development of tailored sample processing protocols that enable the routine extraction of ^239,24xPu from environmental samples. The set of isotopes in focus is completed by ²⁴⁴Pu (t_1/2 = 81.1 Myrs), whose natural abundances are of primordial origin with minimal interstellar influx (<1000 atoms cm^-2 Myr^-1). Any measurement of ^239,24xPu can be calibrated against the Cologne Pu-multiisotope Standard (ColPuS). Furthermore, a significant increase in measurement precision of isotopic ^239,24xPu concentrations has been achieved through Accelerator Mass Spectrometry (AMS), as compared to earlier methods such as conventional mass spectrometry or decay counting techniques. The development of such measurement capabilities at the UoC Centre for Accelerator Mass Spectrometry (CologneAMS) has enabled the exploration of the numerous potential applications of ^239,240Pu in deciphering modern Earth (sub-)surface processes in different settings. The sample processing workflow, combined with the precision of AMS measurements, allows for resolving specific ²³⁹Pu activities below ~5 mBq kg^-1 (~10^-15og/g). Consequently, spatial focus is placed on study sites where ultra-high precision measurements are required, such as in drylands in the southern hemisphere. A recent study traces dust influx into CaSO₄ crust in the Atacama Desert in northern Chile, while another application focuses on agroecosystems located in the Free State Province of South Africa. Here, plutonium concentrations indicate that SOM loss in arable land can primarily be caused by wind erosion dominating over other factors at play, such as mineralisation processes.

With the foundation for successful measurements of ^239,24xPu being laid, future work aims to further increase the measurement precision of ²⁴⁰Pu at CologneAMS. Additionally, an alternative measurement method employing a next generation MS/MS MC-ICP-MS (Thermo Fisher Neoma) is being considered to improve measurement sensitivities as compared to older systems. Together with the prospective implementation of further advances made in chemical processing, the overall sample throughput for samples containing ultra-low concentrations of ^239,24xPu may be increased.

Titel:  Slow and not-so-steady: Studying fault behavior at plate-rate speeds

Despite many advances in earthquake science, the tendency for faults to host earthquake slip, aseismic slip or slow slip events is far from well understood.  Existing data is usually gathered at slip velocities orders of magnitude faster than plate convergence rates; therefore, a fundamental question is how faults slip when driven at such slow velocities.  I discuss here laboratory friction experiments conducted at cm/yr driving rates, simulating the natural in-situ forcing condition.

The dataset includes a wide range of materials in two groups: synthetic and natural gouges. The synthetic gouges are powders of nearly pure individual minerals, including various phyllosilicate species, and some common rock types. The natural gouges are sampled from fault zones or fault-related locations (e.g. subduction zone input sediments) by scientific drilling projects.  The rock and mineral standards establish a basic and widely applicable framework for frictional behavior, whereas the natural fault samples can be connected to known, recorded slip events that have occurred at a specific major fault zones.  Examples include the Nankai and Tohoku regions offshore Japan, the Hikurangi subduction zone offshore New Zealand, and the Middle America trench offshore Costa Rica.

Within this large dataset, the slow-driving experiments produce the full range of sliding modes: stick-slip instabilities representing fast earthquakes, slow slip events (SSEs), intermediate events that may be very-low-frequency earthquakes or tremor, and stable sliding.  The steady-sliding materials can be evaluated with rate- and state-dependent friction laws to quantify velocity-strengthening or velocity-weakening frictional behavior, useful for predictions of fault slip in numerical models.  Some intriguing results include a general difference in behavior between synthetic and natural samples, laboratory-reproduced SSEs in natural samples from regions where such events have been recorded, the confirmation of a “cutoff velocity” that causes SSEs in some natural samples, and the possibility that some SSEs occur as earthquake precursors. 

Titel:  O Isotope Evidence for the Recycling of Ocean Crust through the Mantle

Ilya Bindemann ist Isotopengeochemiker an der University of Oregon, USA. Kürzlich wurde ihm ein renommiertes Humboldt-Stipendium verliehen, das es ihm ermöglicht, in den kommenden Jahren auch an der Universität Mainz zu arbeiten. Seine Forschung konzentriert sich auf endogene und exogene Prozesse auf der frühen Erde. Zu den Fragen, die Ilya zu beantworten versucht, gehören: „Entstand frühes Leben auf einer heißen oder kalten Erde?“, „Wann entstanden die Kontinente?“ oder „Wann begann die Plattentektonik?“. In diesem Vortrag wird Ilya erläutern, wie das (dreifache) Sauerstoffisotopensystem in Bezug auf den Rückfluss von Oberflächenmaterial in den Erdmantel funktioniert, welche Signaturen Mantelplumes aufweisen, wie sich kontinentale Kruste bildet und welche Debatten es über die Bedingungen auf der frühen Erde gibt.

(Erick Prince)

Figure 1: Summary of dating results including the a) ESR Saturation levels for the measured samples with the respective mean for each fault, b) minimum and maximum ages for the measured samples c) location of the samples along the PAF, Lavanttal Fault, and Šoštanj Fault with the respective ages. The results from Prince et al. (2024) are marked with an asterisk (*) in the upper panel. (Prince et al., accepted).

Identifying fossil fault activity along the eastern Periadriatic Fault system by combined OSL- and ESR-dating of fault gouges

Abstract: Faults regions with low deformation rates such as in the Eastern Alps accumulate strain over long periods, this results in faults with low slip rates and infrequent occurrence of large magnitude (Mw > 6) surface-rupturing earthquakes that may even remain undetected in instrumental and historical records. In the Eastern Alps, the Pleistocene glaciations further obscure seismic evidence by eroding or burying fault-related features, limiting the effectiveness of traditional paleoseismology. The Periadriatic Fault (PAF) System is one of the largest faults in the Alpine chain, with a main onset of activity during post-collisional lateral extrusion during the Oligocene to Miocene times, and slowing down in the second half of the Neogene. Its seismic activity is debated. The application of electron spin resonance (ESR, quartz) and optically stimulated luminescence (OSL, K-feldspar) dating to fault gouges allows to determine whether they released earthquakes during the Quaternary. These methods are sensitive to low temperatures (below 100 °C) and can record a system reset due to shear heating during surface-rupturing earthquakes. This approach was applied to the eastern PAF and two of its neighboring faults (Lavanttal Fault and Šoštanj Fault). The saturation level of the signals from the dating methods was used as a metric of seismic activity to compare between the faults.

Our findings revealed varying levels of Quaternary seismic activity among the studied faults (Figure 1). The Lavanttal Fault samples displayed a complete signal saturation (saturation level > 86 %) for ESR, indicating limited seismic activity since ~2 Ma. The gouges from the eastern PAF yielded ages across the Pleistocene, with maximum ages of the last complete reset of the system given by ESR ranging between 1,075 ± 48 and 305 ± 25 ka, and minimum ages given by the saturation of OSL signals ranging between 281 ± 16 ka and 62 ± 4 ka. The mean saturation level of 66 ± 4 % for ESR indicated similar levels of seismic activity along the fault. For the Šoštanj Fault, both systems were below saturation with levels of 49 ± 3 % and 14 ± 4 % for ESR and OSL, respectively, corresponding to ages of 644 ± 30 ka for ESR and 30 ± 4 ka for OSL. In this case, the results suggest a shorter earthquake recurrence interval than for the other two faults. Numerical models shed further information on the recurrence interval of the PAF, suggesting that surface-rupturing earthquakes along the PAF likely occurred at intervals between tens of thousands to over a million years, depending on the magnitude of the earthquakes.

This work demonstrates the utility of ESR and OSL dating methods in reconstructing the seismic history of faults in slowly deforming regions where traditional paleoseismology is limited, bridging the temporal gap between instrumental, historical, and long-term geological records, while also contributing to methodological developments. The approaches presented here have the potential to be extended to other intraplate fault systems with low deformation rates to improve regional seismic hazard assessments.

Dr. Borhan Bagherpour

Privat

Title: Permian-Triassic Mass Extinction: Insights From Paleoenvironmental Studies and Stable Isotopes In China and Iran.

Summary: The largest mass extinction of the Phanerozoic, which occurred at the Permian-Triassic Boundary (PTB), was linked to significant paleoenvironmental shifts, including perturbation in the global carbon cycle, global warming, and changes in sedimentary regimes. In this talk, I present a multi-disciplinary approach to studying these paleoenvironmental changes during the Late Permian and earliest Triassic. This research focuses on the exceptional sedimentary records from South China and Central Iran, which offer a unique opportunity to examine the effects of these changes across a variety of marine depositional environments.

The occurrence of microbial limestones on platforms and the coeval development of oxygen-depleted black shales in deeper marine settings provide insight into the prevailing environmental conditions at different depths, as well as the importance of microbial communities in the recovery. Additionally, I discuss the paleoenvironmental impacts of the Emeishan large igneous province and the factors contributing to an earlier extinction event around the end-Guadalupian (mid-Permian), which may have also contributed to the severity of the PTB extinction. Our high-resolution data suggest that volcanic activity and carbon cycle disruptions during the Late Permian had more localized effects, in contrast to the widespread environmental changes observed at the PTB in the Early Triassic.

Ms. Elena Rogmann MSc.

Privat

Title: To garnet and beyond – The fate of aluminium in the Earth’s mantle

Summary: Subduction zones transport a variety of elements, such as aluminium and alkali earth metals, into the deep Earth. These elements, particularly aluminium, are more concentrated in subducting sediment and oceanic crust (MORB) compared to the surrounding mantle, which leads to distinct mineralogical differences. In the upper mantle and mantle transition zone, aluminium is primarily stored in garnet. However, as slabs descend through to the lower mantle, garnet becomes unstable, and aluminium is hosted by other minerals.

Two key lower mantle phases, the New Aluminous Phase (NAL) and Calcium-ferrite Type Phase (CF), are the hosts of aluminium in the lower mantle. While their stabilities in simple chemical systems (NaAlSiO₄–MgAl₂O₄) are well understood (Imada et al., 2011), more realistic chemical systems have only recently been explored. This presentation will focus on how potassium—a significant component of subducting sediments—affects the stability of NAL and CF (Rogmann et al., 2024).

We performed high-pressure experiments using a laser-heated diamond anvil cell (DAC) in the KAlSiO₄–NaAlSiO₄–MgAl₂O₄ system, under pressures corresponding to the uppermost to mid-lower mantle. To constrain the elasticity of the CF phase, we conducted Brillouin scattering experiments on CF single crystals in a DAC at an array of pressures. These measurements allow us to model seismic wave velocities, which can be compared to measured seismic data of the deep Earth and can help constrain mineralogical models of the deep Earth.

We find our measurements of the elastic moduli of CF to deviate significantly from those reported in current mineral physical databases based on theoretical calculations. We also observe the onset of the spin transition in ferric iron, expected for CF between 25 and 35~GPa (Wu et al., 2017). Additionally, we find that the addition of potassium significantly broadens the stability range of NAL by more than 25 GPa. We also observe a significant potassium solubililty in CF at high pressure, which may hold the entire MORB potassium budget.

Imada, Saori, Kei Hirose, and Yasuo Ohishi. "Stabilities of NAL and Ca-ferrite-type phases on the join NaAlSiO 4-MgAl 2 O 4 at high pressure." Physics and Chemistry of Minerals 38 (2011): 557-560.

Rogmann, Elena-Marie, et al. "The effect of potassium on aluminous phase stability in the lower mantle." Contributions to Mineralogy and Petrology 179.5 (2024): 1-18.

Wu, Ye, et al. "Spin transition of ferric iron in the calcium‐ferrite type aluminous phase." Journal of Geophysical Research: Solid Earth 122.8 (2017): 5935-5944.

Title: Dates and rates of Earth surface processes revealed through trapped charge dating

Summary: The interactions between rates of Earth surface processes, climate and tectonics shape landscapes from mountains to oceans. A robust chronology is essential for understanding the timing of environmental change, its main drivers and how quickly landscapes have evolved over the recent past (i.e., the last few million years). Trapped charge dating techniques, such as electron spin resonance (ESR) and luminescence dating, provide valuable insights into Earth surface processes and landscape change over timescales of 10²-10⁶ years, offering critical information on the timing and pace of environmental change for evaluating processes that are important to society. In this talk, I will highlight the potential of trapped charge dating as a geochronological tool to constrain the timing and rates of landscape evolution, illustrated by selected geomorphological studies from around the world.

Title: Quantification of ^239,24xPu in environmental samples – method development, applications and perspectives

Summary: The measurement of ^239,240Pu in environmental samples can play a key role in investigating Earth (sub-)surface processes. Earth’s outermost skin has been enriched in such anthropogenic fallout radionuclides (FRNs) as a consequence of atmospheric nuclear weapon tests conducted in the 1950s and 1960s, providing distinct geochronological markers. The application of FRNs is well established, with ¹³⁷Cs (and the naturally occurring ²¹⁰Pb) being most commonly measured. However, ^239,240Pu activities are more decay-insensitive (t_1/2 ²³⁹Pu: ~24.1 ka; ²⁴⁰Pu: ~6.6 ka), and there is less soil inventory contamination arising from nuclear power plant accidents compared to ¹³⁷Cs. Additionally, only a few grams of sample material are required for a measurement.

Several years of research at the University of Cologne (UoC) have resulted in the development of tailored sample processing protocols that enable the routine extraction of ^239,24xPu from environmental samples. The set of isotopes in focus is completed by ²⁴⁴Pu (t_1/2 = 81.1 Myrs), whose natural abundances are of primordial origin with minimal interstellar influx (<1000 atoms cm^-2 Myr^-1). Any measurement of ^239,24xPu can be calibrated against the Cologne Pu-multiisotope Standard (ColPuS). Furthermore, a significant increase in measurement precision of isotopic ^239,24xPu concentrations has been achieved through Accelerator Mass Spectrometry (AMS), as compared to earlier methods such as conventional mass spectrometry or decay counting techniques. The development of such measurement capabilities at the UoC Centre for Accelerator Mass Spectrometry (CologneAMS) has enabled the exploration of the numerous potential applications of ^239,240Pu in deciphering modern Earth (sub-)surface processes in different settings. The sample processing workflow, combined with the precision of AMS measurements, allows for resolving specific ²³⁹Pu activities below ~5 mBq kg^-1 (~10^-15og/g). Consequently, spatial focus is placed on study sites where ultra-high precision measurements are required, such as in drylands in the southern hemisphere. A recent study traces dust influx into CaSO₄ crust in the Atacama Desert in northern Chile, while another application focuses on agroecosystems located in the Free State Province of South Africa. Here, plutonium concentrations indicate that SOM loss in arable land can primarily be caused by wind erosion dominating over other factors at play, such as mineralisation processes.

With the foundation for successful measurements of ^239,24xPu being laid, future work aims to further increase the measurement precision of ²⁴⁰Pu at CologneAMS. Additionally, an alternative measurement method employing a next generation MS/MS MC-ICP-MS (Thermo Fisher Neoma) is being considered to improve measurement sensitivities as compared to older systems. Together with the prospective implementation of further advances made in chemical processing, the overall sample throughput for samples containing ultra-low concentrations of ^239,24xPu may be increased.