Evidence of trepanation in Late Iron Age Switzerland (420–240BC)

In Europe the procedure of trepanation is known since the Neolithic and is still practiced today in East African native tribes. Trepanation is the oldest known surgical intervention and is defined as the intentional penetration of the cranial vault with removal of piece of a skull bone. Therefore, it is believed that neurosurgery is one of the world’s oldest professions. In this study two skulls with lesions from the Late Iron Age cemetery of Münsingen (420–240 BC), Switzerland, are presented. Aim of the study was to analyse the lesions and to assess whether they were caused by surgical interventions. Sex and age of the individuals were determined by current morphologic-anthropological methods. Radiological examinations were performed with a multislice CT-scanner. Different trepanation methods and signs of healing are discussed. In Switzerland about 33 skulls with possible trepanations dating from Neolithic to medieval times are known and are presented in a short review. Studies of ancient surgical interventions provide important information of pre- and early historic populations. Trepanations of the skull such as the presented cases prove a profound understanding of the human body in ancient times.

Modeling episodic fluid-release events in the ductile carbonates of the Glarus thrust

The exposed Glarus thrust displays midcrustal deformation with tens of kilometers of displacement on an ultrathin layer, the principal slip zone (PSZ). Geological observations indicate that this structure resulted from repeated stick-slip events in the presence of highly overpressured fluids. Here we show that the major characteristics of the Glarus thrust movement (localization, periodicity, and evidence of pressurized fluids) can be reconciled by the coupling of two processes, namely, shear heating and fluid release by carbonate decomposition. During this coupling, slow ductile creep deformation raises the temperature through shear heating and ultimately activates the chemical decomposition of carbonates. The subsequent release of highly overpressurized fluids forms and lubricates the PSZ, allowing a ductile fault to move tens of kilometers on millimeter-thick bands in episodic stick-slip events. This model identifies carbonate decomposition as a key process for motion on the Glarus thrust and explains the source of overpressured fluids accessing the PSZ.

Iron-Promoted Nucleophilic Additions to Diimine-Type Ligands: A Synthetic and Structural Study

We report here three examples of the reactivity of protic nucleophiles with diimine-type ligands in the presence of FeII salts. In the first case, the iron-promoted alcoholysis reaction of one nitrile group of the ligand 2,3-dicyano-5,6-bis(2-pyridyl)-pyrazine (L1) permitted the isolation of an stable E-imido−ester, [Fe(L1‘)2](CF3SO3)2 (1), which has been characterized by spectroscopic studies (IR, ES-MS, Mössbauer), elemental analysis, and crystallographically. Compound 1 consists of mononuclear octahedrally coordinated FeII complexes where the FeII ion is in its low-spin state. The iron-mediated nucleophilic attack of water to the asymmetric ligand 2,3-bis(2-pyridyl)pyrido[3,4-b]pyrazine (L2) has also been studied. In this context, the crystal structures of two hydration−oxidation FeIII products, [Fe(L2‘)2](ClO4)3·3CH3CN (2) and trans-[FeL2‘‘Cl2] (3), are described. Compounds 2 and 3 are both mononuclear FeIII complexes where the metals occupy octahedral positions. In principle, L2 is expected to coordinate to metal ions through its bipyridine-type units to form a five-membered ring; however, this is not the case in compounds 2 and 3. In 2, the ligand coordinates through its pyridines and through the hydroxyl group attached to the pyrazine imino carbon after hydration, that is, in an N,O,N tridentate manner. In compound 3, the ligand has suffered further transformations leading to a very stable diamido complex. In this case, the metal ion achieves its octahedral geometry by means of two pyridines, two amido N atoms, and two axial chlorine atoms. Magnetic susceptibility measurements confirmed the spin state of these two FeIII species:  compounds 2 and 3 are low-spin and high-spin, respectively.

Interpretation of fluid inclusions in quartz deformed by weak ductile shearing: reconstruction of differential stress magnitudes and pre-deformation fluid properties

A well developed theoretical framework is available in which paleofluid properties, such as chemical composition and density, can be reconstructed from fluid inclusions in minerals that have undergone no ductile deformation. The present study extends this framework to encompass fluid inclusions hosted by quartz that has undergone weak ductile deformation following fluid entrapment. Recent experiments have shown that such deformation causes inclusions to become dismembered into clusters of irregularly shaped relict inclusions surrounded by planar arrays of tiny, new-formed (neonate) inclusions. Comparison of the experimental samples with a naturally sheared quartz vein from Grimsel Pass, Aar Massif, Central Alps, Switzerland, reveals striking similarities. This strong concordance justifies applying the experimentally derived rules of fluid inclusion behaviour to nature. Thus, planar arrays of dismembered inclusions defining cleavage planes in quartz may be taken as diagnostic of small amounts of intracrystalline strain. Deformed inclusions preserve their pre-deformation concentration ratios of gases to electrolytes, but their H2O contents typically have changed. Morphologically intact inclusions, in contrast, preserve the pre-deformation composition and density of their originally trapped fluid. The orientation of the maximum principal compressive stress (σ1σ1) at the time of shear deformation can be derived from the pole to the cleavage plane within which the dismembered inclusions are aligned. Finally, the density of neonate inclusions is commensurate with the pressure value of σ1σ1 at the temperature and time of deformation. This last rule offers a means to estimate magnitudes of shear stresses from fluid inclusion studies. Application of this new paleopiezometer approach to the Grimsel vein yields a differential stress (σ1–σ3σ1–σ3) of ∼300 MPa∼300 MPa at View the MathML source390±30°C during late Miocene NNW–SSE orogenic shortening and regional uplift of the Aar Massif. This differential stress resulted in strain-hardening of the quartz at very low total strain (<5%<5%) while nearby shear zones were accommodating significant displacements. Further implementation of these experimentally derived rules should provide new insight into processes of fluid–rock interaction in the ductile regime within the Earth's crust.

Iron uptake and ferrokinetics in healthy male subjects of an iron-based oral phosphate binder (SBR759) labeled with the stable isotope 58 Fe

SBR759 is a novel polynuclear iron(III) oxide–hydroxide starch·sucrose·carbonate complex being developed for oral use in chronic kidney disease (CKD) patients with hyperphosphatemia on hemodialysis. SBR759 binds inorganic phosphate released by food uptake and digestion in the gastro-intestinal tract increasing the fecal excretion of phosphate with concomitant reduction of serum phosphate concentrations. Considering the high content of ∼20% w/w covalently bound iron in SBR759 and expected chronic administration to patients, absorption of small amounts of iron released from the drug substance could result in potential iron overload and toxicity. In a mechanistic iron uptake study, 12 healthy male subjects (receiving comparable low phosphorus-containing meal typical for CKD patients: ≤1000 mg phosphate per day) were treated with 12 g (divided in 3 × 4 g) of stable 58Fe isotope-labeled SBR759. The ferrokinetics of [58Fe]SBR759-related total iron was followed in blood (over 3 weeks) and in plasma (over 26 hours) by analyzing with high precision the isotope ratios of the natural iron isotopes 58Fe, 57Fe, 56Fe and 54Fe by multi-collector inductively coupled mass spectrometry (MC-ICP-MS). Three weeks following dosing, the subjects cumulatively absorbed on average 7.8 ± 3.2 mg (3.8–13.9 mg) iron corresponding to 0.30 ± 0.12% (0.15–0.54%) SBR759-related iron which amounts to approx. 5-fold the basal daily iron absorption of 1–2 mg in humans. SBR759 was well-tolerated and there was no serious adverse event and no clinically significant changes in the iron indices hemoglobin, hematocrit, ferritin concentration and transferrin saturation.

An iron stable isotope comparison between human erythrocytes and plasma

We present precise iron stable isotope ratios measured by multicollector-ICP mass spectrometry (MC-ICP-MS) of human red blood cells (erythrocytes) and blood plasma from 12 healthy male adults taken during a clinical study. The accurate determination of stable isotope ratios in plasma first required substantial method development work, as minor iron amounts in plasma had to be separated from a large organic matrix prior to mass-spectrometric analysis to avoid spectroscopic interferences and shifts in the mass spectrometer's mass-bias. The 56Fe/54Fe ratio in erythrocytes, expressed as permil difference from the “IRMM-014” iron reference standard (δ56/54Fe), ranges from −3.1‰ to −2.2‰, a range typical for male Caucasian adults. The individual subject erythrocyte iron isotope composition can be regarded as uniform over the 21 days investigated, as variations (±0.059 to ±0.15‰) are mostly within the analytical precision of reference materials. In plasma, δ56/54Fe values measured in two different laboratories range from −3.0‰ to −2.0‰, and are on average 0.24‰ higher than those in erythrocytes. However, this difference is barely resolvable within one standard deviation of the differences (0.22‰). Taking into account the possible contamination due to hemolysis (iron concentrations are only 0.4 to 2 ppm in plasma compared to approx. 480 ppm in erythrocytes), we model the pure plasma δ56/54Fe to be on average 0.4‰ higher than that in erythrocytes. Hence, the plasma iron isotope signature lies between that of the liver and that of erythrocytes. This difference can be explained by redox processes involved during cycling of iron between transferrin and ferritin.

Thermal and collisional history of Tishomingo iron meteorite: More evidence for early disruption of differentiated planetesimals

Tishomingo is a chemically and structurally unique iron with 32.5 wt.% Ni that contains 20% residual taenite and 80% martensite plates, which formed on cooling to between -75 and -200 °C, probably the lowest temperature recorded by any meteorite. Our studies using transmission (TEM) and scanning electron microscopy (SEM), X-ray microanalysis (AEM) and electron backscatter diffraction (EBSD) show that martensite plates in Tishomingo formed in a single crystal of taenite and decomposed during reheating forming 10-100 nm taenite particles with ∼50 wt.% Ni, kamacite with ∼4 wt.%Ni, along with martensite or taenite with 32 wt.% Ni. EBSD data and experimental constraints show that Tishomingo was reheated to 320-400 °C for about a year transforming some martensite to kamacite and to taenite particles and some martensite directly to taenite without composition change. Fizzy-textured intergrowths of troilite, kamacite with 2.7 wt.% Ni and 2.6 wt.% Co, and taenite with 56 wt.% Ni and 0.15 wt.% Co formed by localized shock melting. A single impact probably melted the sub-mm sulfides, formed stishovite, and reheated and decomposed the martensite plates. Tishomingo and its near-twin Willow Grove, which has 28 wt.% Ni, differ from IAB-related irons like Santa Catharina and San Cristobal that contain 25-36 wt.% Ni, as they are highly depleted in moderately volatile siderophiles and enriched in Ir and other refractory elements. Tishomingo and Willow Grove therefore resemble IVB irons but are chemically distinct. The absence of cloudy taenite in these two irons shows that they cooled through 250 °C abnormally fast at >0.01 °C/yr. Thus this grouplet, like the IVA and IVB irons, suffered an early impact that disrupted their parent body when it was still hot. Our noble gas data show that Tishomingo was excavated from its parent body about 100 to 200 Myr ago and exposed to cosmic rays as a meteoroid with a radius of ∼50-85 cm.

Interaction of corroding iron with bentonite in the ABM1 experiment at Äspö, Sweden: A microscopic approach

Bentonite and iron metals are common materials proposed for use in deep-seated geological repositories for radioactive waste. The inevitable corrosion of iron leads to interaction processes with the clay which may affect the sealing properties of the bentonite backfill. The objective of the present study was to improve our understanding of this process by studying the interface between iron and compacted bentonite in a geological repository-type setting. Samples of MX-80 bentonite samples which had been exposed to an iron source and elevated temperatures (up to 115ºC) for 2.5 y in an in situ experiment (termed ABM1) at the Äspö Hard Rock Laboratory, Sweden, were investigated by microscopic means, including scanning electron microscopy, μ-Raman spectroscopy, spatially resolved X-ray diffraction, and X-ray fluorescence. The corrosion process led to the formation of a ~100 mm thick corrosion layer containing siderite, magnetite, some goethite, and lepidocrocite mixed with the montmorillonitic clay. Most of the corroded Fe occurred within a 10 mm-thick clay layer adjacent to the corrosion layer. An average corrosion depth of the steel of 22–35 μm and an average Fe2+ diffusivity of 1–26×10–13 m2/s were estimated based on the properties of the Fe-enriched clay layer. In that layer, the corrosion-derived Fe occurred predominantly in the clay matrix. The nature of this Fe could not be identified. No indications of clay transformation or newly formed clay phases were found. A slight enrichment of Mg close to the Fe–clay contact was observed. The formation of anhydrite and gypsum, and the dissolution of some SiO2 resulting from the temperature gradient in the in situ test, were also identified. © 2014, Clay Minerals Society. All right reserved.

Diet and mobility of an Iron Age population in Switzerland; Stable carbon, nitrogen and sulphur isotope analysis of the human remains from Münsingen

The 220 abundantly equipped burials from the Late Iron Age cemetery of Münsingen (420 – 240 BC) marked a milestone for Iron Age research. The evident horizontal spread throughout the time of occupancy laid the foundation for the chronology system of the Late Iron Age. Today the skulls of 77 individuals and some postcranial bones are still preserved. The aim was to obtain information about nutrition, social stratification and migration of the individuals from Münsingen. Stable isotope ratios of carbon, nitrogen and sulphur were analysed. The results of 63 individuals show that all consumed C3 plants as staple food with significant differences between males and females in δ13C and δ15N values. The results indicate a gender restriction in access to animal protein. Stable isotope values of one male buried with weapons and meat as grave goods suggest a diet with more animal proteins than the other individuals. It is possible that he was privileged due to high status. Furthermore, the δ34S values indicate minor mobility. Assuming that the subadults represent the local signal of δ34S it is very likely that adults with enriched δ34S could have migrated to Münsingen at some point during their lives. This study presents stable isotope values of one of the most important Late Iron Age burial sites in Central Europe. The presented data provide new insight into diet, migration and social stratification of the population from Münsingen.

Social stratigraphy in Late Iron Age Switzerland: Analysis of human remains from Münsingen

The Iron Age cemetery of Münsingen in Switzerland with 220 abundantly equipped burials marked a milestone for Iron Age research. The horizontal spread throughout the time of its occupancy laid the foundation for the chronology system of the Late Iron Age. Today, skulls of 77 individuals and some postcranial bones are still preserved and were investigated anthropologically. Collagen was analysed via stable isotope mass spectrometry (carbon, nitrogen, and sulphur). Additionally, some bones showed pathologies or lesions which were examined via imaging and histological methods. The aim of the study was to obtain biological-anthropological information about the Iron Age population. There are significant differences between males and females in δ13C and δ15N values. This points to a gender restriction in the access to animal protein with males having more access to meat and dairy products. Differences in δ15N values were also observed for different age classes. δ34S values indicate a terrestrial-based diet with no significant intake of marine or freshwater fish. Seven adults with enriched δ34S values might have immigrated to Münsingen, four of which were found in the oldest part of the cemetery. Furthermore, possible changes of the vegetation are indicated by the more positive stable carbon ratios in the later phases. The results lead to the suggestion that especially males buried with weapons might have played a special role in the Iron Age society. Also, skull trepanations in two males suggest that surgical treatment of injuries caused by weapons may have been performed.

Survival after trepanation—Early cranial surgery from Late Iron Age Switzerland

Trepanation is defined as the intentional perforation of the cranial vault with removal of a piece of skull bone. In Europe, trepanation is known to have been practiced at least since the Neolithic, and it can still be found today in East African native tribes. Two skulls with lesions from the Late Iron Age site Münsingen-Rain (420–240 BC) were investigated. The aim of this study was to analyse the lesions and to determine whether they were caused by surgical interventions. Both individuals were analysed by current morphologic-anthropological methods and radiological examinations were performed with a multislice CT-scanner. Additionally, this work surveys trepanations reported in Switzerland and calculates survival rates. In Switzerland, 34 individuals with trepanations have been published. As a tendency, the survival rate appears to be relatively high from the Neolithic to Late Antiquity but then decreases until Pre-Modern times. The 78% survival rate in Late Iron Age Switzerland indicates that the surgery was often performed successfully. Skull injuries sustained in conflicts could have been a reason for trepanation during the Iron Age.

Chlorophyll breakdown: Pheophorbide a oxygenase is a Rieske-type iron-sulfur protein, encoded by the accelerated cell death 1 gene

Chlorophyll (chl) breakdown during senescence is an integral part of plant development and leads to the accumulation of colorless catabolites. The loss of green pigment is due to an oxygenolytic opening of the porphyrin macrocycle of pheophorbide (pheide) a followed by a reduction to yield a fluorescent chl catabolite. This step is comprised of the interaction of two enzymes, pheide a oxygenase (PaO) and red chl catabolite reductase. PaO activity is found only during senescence, hence PaO seems to be a key regulator of chl catabolism. Whereas red chl catabolite reductase has been cloned, the nature of PaO has remained elusive. Here we report on the identification of the PaO gene of Arabidopsis thaliana (AtPaO). AtPaO is a Rieske-type iron–sulfur cluster-containing enzyme that is identical to Arabidopsis accelerated cell death 1 and homologous to lethal leaf spot 1 (LLS1) of maize. Biochemical properties of recombinant AtPaO were identical to PaO isolated from a natural source. Production of fluorescent chl catabolite-1 required ferredoxin as an electron source and both substrates, pheide a and molecular oxygen. By using a maize lls1 mutant, the in vivo function of PaO, i.e., degradation of pheide a during senescence, could be confirmed. Thus, lls1 leaves stayed green during dark incubation and accumulated pheide a that caused a light-dependent lesion mimic phenotype. Whereas proteins were degraded similarly in wild type and lls1, a chl-binding protein was selectively retained in the mutant. PaO expression correlated positively with senescence, but the enzyme appeared to be post-translationally regulated as well.