Gerald Falkenberg

A novel concept of Fe-mineral-based magnetoreception: histological and physicochemical data from the upper beak of homing pigeons

Animals make use of the Earth’s magnetic field for navigation and regulation of vegetative functions; however, the anatomical and physiological basis for the magnetic sense has not been elucidated yet. Our recent results from histology and X-ray analyses support the hypothesis that delicate iron-containing structures in the skin of the upper beak of homing pigeons might serve as a biological magnetometer. Histology has revealed various iron sites within dendrites of the trigeminal nerve, their arrangement along strands of axons, the existence of three dendritic fields in each side of the beak with specific 3D-orientations, and the bilateral symmetry of the whole system. Element mapping by micro-synchrotron X-ray fluorescence analysis has shown the distribution of iron and its quantities. Micro-synchrotron X-ray absorption near-edge-structure spectroscopy has allowed us to unambiguously identify maghemite as the predominating iron mineral (90 vs 10% magnetite). In this paper, we show that iron-based magnetoreception needs the presence of both of these iron minerals, their specific dimensions, shapes, and arrangements in three different subcellular compartments. We suggest that an inherent magnetic enhancement process via an iron-crusted vesicle and the attached chains of iron platelets might be sufficient to account for the sensitivity and specificity required by such a magnetoreceptor. The appropriate alignment between the Earth’s magnetic field and the maghemite bands would induce a multiple attraction of the magnetite bullets perpendicular to the membrane, thus, triggering strain-sensitive membrane channels and a primary receptor potential. Due to its 3D architecture and physicochemical nature, the dendritic system should be able to separately sense the three vector components of the Earth’s local field, simultaneously—allowing birds to detect their geographic position by the magnetic vector, i.e., amplitude and direction of the local magnetic field, irrespective of the animal’s posture or movement and photoreception.

Avian Magnetoreception: Elaborate Iron Mineral Containing Dendrites in the Upper Beak Seem to Be a Common Feature of Birds

The magnetic field sensors enabling birds to extract orientational information from the Earths magnetic field have remained enigmatic. Our previously published results from homing pigeons have made us suggest that the iron containing sensory dendrites in the inner dermal lining of the upper beak are a candidate structure for such an avian magnetometer system. Here we show that similar structures occur in two species of migratory birds (garden warbler, Sylvia borin and European robin, Erithacus rubecula) and a non-migratory bird, the domestic chicken (Gallus gallus). In all these bird species, histological data have revealed dendrites of similar shape and size, all containing iron minerals within distinct subcellular compartments of nervous terminals of the median branch of the Nervus ophthalmicus. We also used microscopic X-ray absorption spectroscopy analyses to identify the involved iron minerals to be almost completely Fe III-oxides. Magnetite (Fe II/III) may also occur in these structures, but not as a major Fe constituent. Our data suggest that this complex dendritic system in the beak is a common feature of birds, and that it may form an essential sensory basis for the evolution of at least certain types of magnetic field guided behavior.

Hard x-ray scanning microscopy with coherent radiation: Beyond the resolution of conventional x-ray microscopes

We demonstrate x-ray scanning coherent diffraction microscopy (ptychography) with 10 nm spatial resolution, clearly exceeding the resolution limits of conventional hard x-ray microscopy. The spatial resolution in a ptychogram is shown to depend on the shape (structure factor) of a feature and can vary for different features in the object. In addition, the resolution and contrast are shown to increase with increasing coherent fluence. For an optimal ptychographic x-ray microscope, this implies a source with highest possible brilliance and an x-ray optic with a large numerical aperture to generate the optimal probe beam.

Real-World Emission Factors for Antimony and Other Brake Wear Related Trace Elements: Size-Segregated Values for Light and Heavy Duty Vehicles

Hourly trace element measurements were performed in an urban street canyon and next to an interurban freeway in Switzerland during more than one month each, deploying a rotating drum impactor (RDI) and subsequent sample analysis by synchrotron radiation X-ray fluorescence spectrometry (SR-XRF). Antimony and other brake wear associated elements were detected in three particle size ranges (2.5-10, 1-2.5, and 0.1-1 microm). The hourly measurements revealed that the effect of resuspended road dust has to be taken into account for the calculation of vehicle emission factors. Individual values for light and heavy duty vehicles were obtained for stop-and-go traffic in the urban street canyon. Mass based brake wear emissions were predominantly found in the coarse particle fraction. For antimony, determined emission factors were 11 +/- 7 and 86 +/- 42 microg km(-1) vehicle(-1) for light and heavy duty vehicles, respectively. Antimony emissions along the interurban freeway with free-flowing traffic were significantly lower. Relative patterns for brake wear related elements were very similar for both considered locations. Beside vehicle type specific brake wear emissions, road dust resuspension was found to be a dominant contributor of antimony in the street canyon.

Hard X-ray nanoprobe at beamline P06 at PETRA III

We describe the hard X-ray scanning microscope planned for the new synchrotron radiation source PETRA III at DESY in Hamburg, Germany. It is based on nanofocusing refractive X-ray lenses and is designed for two-dimensional mapping and scanning tomography. It supports X-ray fluorescence and (coherent) diffraction contrast, yielding elemental and structural information from inside the sample. Spatial resolutions down to well below 50 nm are aimed for in direct space. A further increase in spatial resolution is expected by applying ptychographic scanning schemes. The optical scheme with a two-stage focusing optic is described.

Micro-XANES determination of ferric iron and its application in thermobarometry

Micro-X-ray absorption near-edge structure (XANES) analysis was employed to determine the content of ferric iron in minerals formed in ultrahigh-pressure (UHP) eclogites. It is observed that omphacite and phengite contain significant amounts of Fe3+/Fetot (0.2–0.6), whereas only very low contents are present in garnet (Fe3+/Fetot=0.0–0.03), the latter being consistent with results from stoichiometric charge-balance calculations. Furthermore, considerable variations in the Fe3+/Fetot ratios of omphacite and phengite are observed depending on the textural sites and local bulk chemistry (eclogite and calc-silicate matrix) within one thin section. The oxidation state of isofacial minerals is thus likely to depend on the local fluid composition, which, in the studied case, is controlled by calcareous and meta-basic mineral compositions. These first in-situ measurements of ferric iron in an eclogite sample from the Dabie Shan, E China, are used to recalculate geothermobarometric data. Calculations demonstrate that the temperature during UHP metamorphism was as high as 780 °C, about 80–100 °C higher than previously estimated. Temperatures based on charge balance calculations often give erroneous results. Pressure estimates are in good agreement with former results and confirm metamorphism in the stability field of diamond (43.7 kbar at 750 °C). These P–T data result in a geothermal gradient of ca. 6 °C/km during UHP metamorphism in the Dabie Shan. However, accounting for ferric iron contents in geothermobarometry creates new difficulties inasmuch as calibrations of geothermometers may not be correctable for Fe3+ and the actual effect on Mg–Fe2+ partitioning is unknown. The present study further shows that micro-XANES is a promising technique for the in situ determination of ferric iron contents without destroying the textural context of the sample: a clear advantage compared to bulk methods.

Degradation process of lead chromate in paintings by Vincent van Gogh studied by means of spectromicroscopic methods : 3 : synthesis, characterization, and detection of different crystal forms of the chrome yellow pigment

The painter, Vincent van Gogh, and some of his contemporaries frequently made use of the pigment chrome yellow that is known to show a tendency toward darkening. This pigment may correspond to various chemical compounds such as PbCrO(4) and PbCr(1-x)S(x)O(4), that may each be present in various crystallographic forms with different tendencies toward degradation. Investigations by X-ray diffraction (XRD), mid-Fourier Transform infrared (FTIR), and Raman instruments (benchtop and portable) and synchrotron radiation-based micro-XRD and X-ray absorption near edge structure spectroscopy performed on oil-paint models, prepared with in-house synthesized PbCrO(4) and PbCr(1-x)S(x)O(4), permitted us to characterize the spectroscopic features of the various forms. On the basis of these results, an extended study has been carried out on historic paint tubes and on embedded paint microsamples taken from yellow-orange/pale yellow areas of 12 Van Gogh paintings, demonstrating that Van Gogh effectively made use of different chrome yellow types. This conclusion was also confirmed by in situ mid-FTIR investigations on Van Goghs Portrait of Gauguin (Van Gogh Museum, Amsterdam).

The Use of Synchrotron Radiation for the Characterization of Artists' Pigments and Paintings

We review methods and recent studies in which macroscopic to (sub)microscopic X-ray beams were used for nondestructive analysis and characterization of pigments, paint microsamples, and/or entire paintings. We discuss the use of portable laboratory- and synchrotron-based instrumentation and describe several variants of X-ray fluorescence (XRF) analysis used for elemental analysis and imaging and combined with X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). Macroscopic and microscopic (μ-)XRF variants of this method are suitable for visualizing the elemental distribution of key elements in paint multilayers. Technical innovations such as multielement, large-area XRF detectors have enabled such developments. The use of methods limited to elemental analysis or imaging usually is not sufficient to elucidate the chemical transformations that take place during natural pigment alteration processes. However, synchrotron-based combinations of μ-XRF, μ-XAS, and μ-XRD are suitable for such studies.

Characteristics of Picoliter Droplet Dried Residues as Standards for Direct Analysis Techniques

The characteristics of dried residues of picodroplets of single-, two-, and three-element aqueous solutions, which qualify these as reference materials in the direct analysis of single particles, single cells, and other microscopic objects using, e.g., laser ablation inductively coupled plasma time-of-flight mass spectrometry (LA-ICP-TOF-MS) and micro-X-ray fluorescence (MXRF), were evaluated. Different single-, two-, and three-element solutions (0.01-1 g/L) were prepared in picoliter volume (around 130 pL) with a thermal inkjet printing technique. An achievable dosing precision of 4-15% was calculated by total reflection X-ray fluorescence (TXRF) determination of the transferred elemental mass of an array of 100 droplets. The size of the dried residues was determined by optical microscopy to be 5-20 microm in diameter depending on the concentration and the surface material. The elemental distribution of the dried residues was determined with synchrotron micro-X-ray fluorescence (SR-MXRF) analyses. The MXRF results show high uniformity for element deposition of every single droplet with an RSTD of 4-6% depending on the concentration of spotted solution. The shape and height profile of dried residues from picoliter droplets were studied using atomic force microscopy (AFM). It was found that these dry to give symmetrical spherical segments with maximum heights of 1.7 microm. The potential of this technique for direct LA-ICP-TOF-MS analysis is shown.

X-ray Fluorescence Tomography of Aged Fluid-Catalytic-Cracking Catalyst Particles Reveals Insight into Metal Deposition Processes

Microprobe X‐ray fluorescence tomography was used to investigate metal poison deposition in individual, intact and industrially deactivated fluid catalytic cracking (FCC) particles at two differing catalytic life‐stages. 3 D multi‐element imaging, at submicron resolution was achieved by using a large‐array Maia fluorescence detector. Our results show that Fe, Ni and Ca have significant concentration at the exterior of the FCC catalyst particle and are highly co‐localized. As concentrations increase as a function of catalytic life‐stage, the deposition profiles of Fe, Ni, and Ca do not change significantly. V has been shown to penetrate deeper into the particle with increasing catalytic age. Although it has been previously suggested that V is responsible for damaging the zeolite components of FCC particles, no spatial correlation was found for V and La, which was used as a marker for the embedded zeolite domains. This suggests that although V is known to be detrimental to zeolites in FCC particles, a preferential interaction does not exist between the two.