In-depth magnetometry and EPR analysis of the spin structure of human-liver ferritin: from DC to 9 GHz.

Ferritin, the major iron storage protein in organisms, stores iron in the form of iron oxyhydroxide most likely involving phosphorous as a constituent, the mineral form of which is not well understood. Therefore, the question of how the ca. 2000 iron atoms in the ferritin core are magnetically coupled is still largely open. The ferritin core, with a diameter of 5-8 nm, is encapsulated in a protein shell that also catalyzes the uptake of iron and protects the core from outside interactions. Neurodegenerative disease is associated with iron imbalance, generating specific interest in the magnetic properties of ferritin. Here we present 9 GHz continuous wave EPR and a comprehensive set of magnetometry techniques including isothermal remanent magnetization (IRM) and AC susceptibility to elucidate the magnetic properties of the core of human liver ferritin. For the analysis of the magnetometry data, a new microscopic model of the ferritin-core spin structure is derived, showing that magnetic moment is generated by surface-spin canting, rather than defects. The analysis explicitly includes the distribution of magnetic parameters, such as the distribution of the magnetic moment. This microscopic model explains some of the inconsistencies resulting from previous analysis approaches. The main findings are a mean magnetic moment of 337µB with a standard deviation of 0.947µB. In contrast to previous reports, only a relatively small contribution of paramagnetic and ferrimagnetic phases is found, in the order of maximally 3%. For EPR, the over 30 mT wide signal of the ferritin core is analyzed using the model of the giant spin system [Fittipaldi et al., Phys. Chem. Chem. Phys., 2016, 18, 3591-3597]. Two components are needed minimally, and the broadening of these components suggests a broad distribution of the magnetic resonance parameters, the zero-field splitting, D, and the spin quantum number, S. We compare parameters from EPR and magnetometry and find that EPR is particularly sensitive to the surface spins of the core, revealing the potential to use EPR as a diagnostic for surface-spin disorder.

Multiscale Brazil nut effects in bioturbated sediment.

Size segregation in granular materials is a universal phenomenon popularly known as the Brazil nut effect (BNE), from the tendency of larger nuts to end on the top of a shaken container. In nature, fast granular flows bear many similarities with well-studied mixing processes. Instead, much slower phenomena, such as the accumulation of ferromanganese nodules (FN) on the seafloor, have been attributed to the BNE but remain essentially unexplained. Here we document, for the first time, the BNE on sub-millimetre particles in pelagic sediment and propose a size segregation model for the surface mixed layer of bioturbated sediments. Our model explains the size distribution of FN seeds, pointing to a uniform segregation mechanism over sizes ranging from < 1 mm to > 1 cm, which does not depend on selective ingestion by feeding organisms. In addition to explaining FN nucleation, our model has important implications for microfossil dating and the mechanism underlying sedimentary records of the Earth's magnetic field.

Key Signatures of Magnetofossils Elucidated by Mutant Magnetotactic Bacteria and Micromagnetic Calculations.

Magnetotactic bacteria (MTB) produce single-stranded or multi-stranded chains of magnetic nanoparticles that contribute to the magnetization of sediments and rocks. Their magnetic fingerprint can be detected in ancient geological samples and serve as a unique biosignature of microbial life. However, some fossilized assemblages bear contradictory signatures pointing to magnetic components that have distinct origin(s). Here, using micromagnetic simulations and mutant MTB producing looped magnetosome chains, we demonstrate that the observed magnetofossil fingerprints are produced by a mixture of single-stranded and multi-stranded chains, and that diagenetically induced chain collapse, if occurring, must preserve the strong uniaxial anisotropy of native chains. This anisotropy is the key factor for distinguishing magnetofossils from other populations of natural magnetite particles, including those with similar individual crystal characteristics. Furthermore, the detailed properties of magnetofossil signatures depend on the proportion of equant and elongated magnetosomes, as well as on the relative abundances of single-stranded and multi-stranded chains. This work has important paleoclimatic, paleontological, and phylogenetic implications, as it provides reference data to differentiate distinct MTB lineages according to their chain and magnetosome morphologies, which will enable the tracking of the evolution of some of the most ancient biomineralizing organisms in a time-resolved manner. It also enables a more accurate discrimination of different sources of magnetite particles, which is pivotal for gaining better environmental and relative paleointensity reconstructions from sedimentary records.

Rapid light carbon releases and increased aridity linked to Karoo-Ferrar magmatism during the early Toarcian oceanic anoxic event.

Large-scale release of isotopically light carbon is responsible for the carbon isotope excursion (CIE) of the Toarcian Oceanic Anoxic Event during the Lower Jurassic. Proposed sources include methane hydrate dissociation, volcanogenic outgassing of carbon dioxide and/or thermogenic methane release from the Karoo-Ferrar magmatic province (southern Africa). Distinct small-scale shifts superimposed on the long-term CIE have been interpreted as rapid methane pulses linked to astronomically forced climate changes. In the Peniche reference section (Portugal), these small-scale shifts correspond to distinct brownish marly layers featuring markedly high mercury (Hg) and magnetic mineral concentration. Total organic carbon and Hg increase are uncorrelated, which suggests input of Hg into the atmosphere, possibly released after the intrusion of the Karoo-Ferrar sills into organic-rich sediments. Enhanced magnetic properties are associated with the presence of martite, washed-in oxidized magnetite, inferred to be due to increased aridity on the continental hinterland. This study provides strong evidence for a direct link between the Karoo-Ferrar magmatism, the carbon-isotope shifts and the resulting environmental changes.

Magnetotactic advantage in stable sediment by long-term observations of magnetotactic bacteria in Earth's field, zero field and alternating field.

Magnetotactic bacteria (MTB) rely on magnetotaxis to effectively reach their preferred living habitats, whereas experimental investigation of magnetotactic advantage in stable sediment is currently lacking. We studied two wild type MTB (cocci and rod-shaped M. bavaricum) in sedimentary environment under exposure to geomagnetic field in the laboratory, zero field and an alternating field whose polarity was switched every 24 hours. The mean concentration of M. bavaricum dropped by ~50% during 6 months in zero field, with no clear temporal trend suggesting an extinction. Cell numbers recovered to initial values within ~1.5 months after the Earth's field was reset. Cocci displayed a larger temporal variability with no evident population changes in zero field. The alternating field experiment produced a moderate decrease of M. bavaricum concentrations and nearby extinction of cocci, confirming the active role of magnetotaxis in sediment and might point to a different magnetotactic mechanism for M. bavaricum which possibly benefited them to survive field reversals in geological periods. Our findings provide a first quantification of magnetotaxis advantage in sedimentary environment.

Intermediate field directions recorded in Pliocene basalts in Styria (Austria): evidence for cryptochron C2r.2r-1.

Pliocene volcanic rocks from south-east Austria were paleomagnetically investigated. Samples were taken from 28 sites located on eight different volcanoes. Rock magnetic investigations revealed that magnetic carriers are Ti-rich or Ti-poor titanomagnetites with mainly pseudo-single-domain characteristics. Characteristic remanent magnetization directions were obtained from alternating field as well as from thermal demagnetization. Four localities give reversed directions agreeing with the expected direction from secular variation. Another four localities of the Klöch-Königsberg volcanic complex (3) and the Neuhaus volcano (1) have reversed directions with shallow inclinations and declinations of about 240° while the locality Steinberg yields a positive inclination of about 30° and 200° declination. These aberrant directions cannot be explained by local or regional tectonic movements. All virtual geomagnetic pole positions are located on the southern hemisphere. Four virtual geomagnetic poles lie close to the geographic pole, while all others are concentrated in a narrow longitude sector offshore South America (310°-355°) with low virtual geomagnetic pole latitudes ranging from - 15° to - 70°. The hypothesis that a transitional geomagnetic field configuration was recorded during the short volcanic activity of these five localities is supported by 9 paleointensity results and 39Ar/40Ar dating. Virtual geomagnetic dipole moments range from 1.1 to 2.9·1022 Am2 for sites with low VGP latitudes below about 60° and from 3.0 to 9.3·1022 Am2 for sites with higher virtual geomagnetic pole latitudes. The new 39Ar/40Ar ages of 2.51 ± 0.27 Ma for Klöch and 2.39 ± 0.03 Ma for Steinberg allow for the correlation of the Styrian transitional directions with cryptochron C2r.2r-1 of the geomagnetic polarity time scale. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1186/s40623-021-01518-w.

In situ magnetic identification of giant, needle-shaped magnetofossils in Paleocene-Eocene Thermal Maximum sediments.

Near-shore marine sediments deposited during the Paleocene-Eocene Thermal Maximum at Wilson Lake, NJ, contain abundant conventional and giant magnetofossils. We find that giant, needle-shaped magnetofossils from Wilson Lake produce distinct magnetic signatures in low-noise, high-resolution first-order reversal curve (FORC) measurements. These magnetic measurements on bulk sediment samples identify the presence of giant, needle-shaped magnetofossils. Our results are supported by micromagnetic simulations of giant needle morphologies measured from transmission electron micrographs of magnetic extracts from Wilson Lake sediments. These simulations underscore the single-domain characteristics and the large magnetic coercivity associated with the extreme crystal elongation of giant needles. Giant magnetofossils have so far only been identified in sediments deposited during global hyperthermal events and therefore may serve as magnetic biomarkers of environmental disturbances. Our results show that FORC measurements are a nondestructive method for identifying giant magnetofossil assemblages in bulk sediments, which will help test their ecology and significance with respect to environmental change.

Effects of Alzheimer's disease and formalin fixation on the different mineralised-iron forms in the human brain.

Iron accumulation in the brain is a phenomenon common to many neurodegenerative diseases, perhaps most notably Alzheimer's disease (AD). We present here magnetic analyses of post-mortem brain tissue of patients who had severe Alzheimer's disease, and compare the results with those from healthy controls. Isothermal remanent magnetization experiments were performed to assess the extent to which different magnetic carriers are affected by AD pathology and formalin fixation. While Alzheimer's brain material did not show higher levels of magnetite/maghemite nanoparticles than corresponding controls, the ferrihydrite mineral, known to be found within the core of ferritin proteins and hemosiderin aggregates, almost doubled in concentration in patients with Alzheimer's pathology, strengthening the conclusions of our previous studies. As part of this study, we also investigated the effects of sample preparation, by performing experiments on frozen tissue as well as tissue which had been fixed in formalin for a period of 5 months. Our results showed that the two different preparations did not critically affect the concentration of magnetic carriers in brain tissue, as observable by SQUID magnetometry.

Time-resolved 2-million-year-old supernova activity discovered in Earth's microfossil record.

Massive stars ([Formula: see text]), which terminate their evolution as core-collapse supernovae, are theoretically predicted to eject [Formula: see text] of the radioisotope (60)Fe (half-life 2.61 Ma). If such an event occurs sufficiently close to our solar system, traces of the supernova debris could be deposited on Earth. Herein, we report a time-resolved (60)Fe signal residing, at least partially, in a biogenic reservoir. Using accelerator mass spectrometry, this signal was found through the direct detection of live (60)Fe atoms contained within secondary iron oxides, among which are magnetofossils, the fossilized chains of magnetite crystals produced by magnetotactic bacteria. The magnetofossils were chemically extracted from two Pacific Ocean sediment drill cores. Our results show that the (60)Fe signal onset occurs around 2.6 Ma to 2.8 Ma, near the lower Pleistocene boundary, terminates around 1.7 Ma, and peaks at about 2.2 Ma.

Microbially assisted recording of the Earth's magnetic field in sediment.

Sediments continuously record variations of the Earth's magnetic field and thus provide an important archive for studying the geodynamo. The recording process occurs as magnetic grains partially align with the geomagnetic field during and after sediment deposition, generating a depositional remanent magnetization (DRM) or post-DRM (PDRM). (P)DRM acquisition mechanisms have been investigated for over 50 years, yet many aspects remain unclear. A key issue concerns the controversial role of bioturbation, that is, the mechanical disturbance of sediment by benthic organisms, during PDRM acquisition. A recent theory on bioturbation-driven PDRM appears to solve many inconsistencies between laboratory experiments and palaeomagnetic records, yet it lacks experimental proof. Here we fill this gap by documenting the important role of bioturbation-induced rotational diffusion for (P)DRM acquisition, including the control exerted on the recorded inclination and intensity, as determined by the equilibrium between aligning and perturbing torques acting on magnetic particles.

Magneto-chemotaxis in sediment: first insights.

Magnetotactic bacteria (MTB) use passive alignment with the Earth magnetic field as a mean to increase their navigation efficiency in horizontally stratified environments through what is known as magneto-aerotaxis (M-A). Current M-A models have been derived from MTB observations in aqueous environments, where a >80% alignment with inclined magnetic field lines produces a one-dimensional search for optimal living conditions. However, the mean magnetic alignment of MTB in their most widespread living environment, i.e. sediment, has been recently found to be <1%, greatly reducing or even eliminating the magnetotactic advantage deduced for the case of MTB in water. In order to understand the role of magnetotaxis for MTB populations living in sediment, we performed first M-A observations with lake sediment microcosms. Microcosm experiments were based on different combinations of (1) MTB position with respect to their preferred living depth (i.e. above, at, and below), and (2) magnetic field configurations (i.e. correctly and incorrectly polarized vertical fields, horizontal fields, and zero fields). Results suggest that polar magnetotaxis is more complex than implied by previous experiments, and revealed unexpected differences between two types of MTB living in the same sediment. Our main findings are: (1) all investigated MTB benefit of a clear magnetotactic advantage when they need to migrate over macroscopic distances for reaching their optimal living depth, (2) magnetotaxis is not used by all MTB under stationary, undisturbed conditions, (3) some MTB can rely only on chemotaxis for macroscopic vertical displacements in sediment while other cannot, and (4) some MTB use a fixed polar M-A mechanisms, while other can switch their M-A polarity, performing what can be considered as a mixed polar-axial M-A. These observations demonstrate that sedimentary M-A is controlled by complex mechanical, chemical, and temporal factors that are poorly reproduced in aqueous environments.