Comparative study of biphasic calcium phosphates with different HA/TCP ratios in mandibular bone defects. A long-term histomorphometric study in minipigs

Three biphasic calcium phosphate (BCP) bone substitute materials with hydroxyapatite (HA)/tricalcium phosphate (TCP) ratios of 20/80, 60/40, and 80/20 were compared to coagulum, particulated autogenous bone, and deproteinized bovine bone mineral (DBBM) in membrane-protected bone defects. The defects were prepared in the mandibles of 24 minipigs that were divided into four groups of six with healing times of 4, 13, 26, and 52 weeks, respectively. The histologic and histomorphometric evaluation focused on differences in amount and pattern of bone formation, filler degradation, and the interface between bone and filler. Collapse of the expanded polytetrafluoroethylene barrier membrane into the coagulum defects underlined the necessity of a filler material to maintain the augmented volume. Quantitatively, BCP 20/80 showed bone formation and degradation of the filler material similar to autografts, whereas BCP 60/40 and BCP 80/20 rather equaled DBBM. Among the three BCP's, the amount of bone formation and degradation of filler material seemed to be inversely proportional to the HA/TCP ratio. The fraction of filler surface covered with bone was highest for autografts at all time points and was higher for DBBM than BCP 80/20 and 60/40 at the early healing phase. TRAP-positive multinucleated cells were identified on BCP and DBBM surfaces without showing typical signs of resorption lacunae.

Optimized Demineralization Technique for the Measurement of Stable Isotope Ratios of Nonexchangeable H in Soil Organic Matter

To make use of the isotope ratio of nonexchangeable hydrogen (δ2Hn (nonexchangeable)) of bulk soil organic matter (SOM), the mineral matrix (containing structural water of clay minerals) must be separated from SOM and samples need to be analyzed after H isotope equilibration. We present a novel technique for demineralization of soil samples with HF and dilute HCl and recovery of the SOM fraction solubilized in the HF demineralization solution via solid-phase extraction. Compared with existing techniques, organic C (Corg) and organic N (Norg) recovery of demineralized SOM concentrates was significantly increased (Corg recovery using existing techniques vs new demineralization method: 58% vs 78%; Norg recovery: 60% vs 78%). Chemicals used for the demineralization treatment did not affect δ2Hn values as revealed by spiking with deuterated water. The new demineralization method minimized organic matter losses and thus artificial H isotope fractionation, opening up the opportunity to use δ2Hn analyses of SOM as a new tool in paleoclimatology or geospatial forensics.

ROSINA/DFMS capabilities to measure isotopic ratios in water at comet 67P/Churyumov–Gerasimenko

The likelihood that comets may have delivered part of the water to Earth has been reinforced by the recent observation of the earth-like D/H ratio in Jupiter-family comet 103P/Hartley 2 by Hartogh et al. (2011). Prior to this observation, results from several Oort cloud comets indicated a factor of 2 enrichment of deuterium relative to the abundance at Earth. The European Space Agency’s Rosetta spacecraft will encounter comet 67P/Churyumov-Gerasimenko, another Jupiter-family comet of likely Kuiper belt origin, in 2014 and accompany it from almost aphelion to and past perihelion. Onboard Rosetta is the Rosetta Orbiter Spectrometer for Ion and Neutral Analysis (ROSINA) which consists of two mass spectrometers and a pressure sensor [Balsiger et al. 2007]. With its unprecedented mass resolution, for a space-borne instrument, the Double Focusing Mass Spectrometer (DFMS), one of the major subsystems of ROSINA, will be able to obtain unambiguously the ratios of the isotopes in water from in situ measurements in the coma around the comet. We will discuss the performance of this sensor on the basis of measurements of the terrestrial hydrogen and oxygen isotopic ratios performed with the flight spare instrument in the lab. We also show that the instrument on Rosetta is capable of measuring the D/H even in the very low density water background released by the spacecraft. This capability demonstrates that ROSINA should obtain very sensitive measurements of these ratios in the cometary environment. These measurements will allow detection of fractionation as function of the distance from the nucleus as well as fractionation due to mechanisms that are correlated with heliocentric distance.

Magma differentiation fractionates Mo isotope ratios: Evidence from the Kos Plateau Tuff (Aegean Arc)

We investigated high temperature Mo isotope fractionation in a hydrous supra-subduction volcano-plutonic system (Kos, Aegean Arc, Greece) in order to address the debate on the δ98/95Mo variability of the continental crust. In this igneous system, where differentiation is interpreted to be dominated by fractional crystallization, bulk rock data from olivine basalt to dacite show δ98/95Mo ratios increasing from +0.3 to +0.6‰ along with Mo concentrations increasing from 0.8 to 4.1 μg g−1. Data for hornblende and biotite mineral separates reveal the extraction of light Mo into crystallizing silicates, with minimum partition coefficients between hornblende- silicate melt and biotite-silicate melt of 0.6 and 0.4 δ98/95Mo, respectively. Our data document significant Mo isotope fractionation at magmatic temperatures, hence, the igneous contribution to continental runoff is variable, besides probable source-related variability. Based on these results and published data an average continental δ98/95Mo of +0.3 to +0.4‰ can be derived. This signature corresponds more closely to the average of published data of dissolved Mo loads of large rivers than previous estimates and is consistent with an upper limit of δ98/95Mo = 0.4‰ of the Earth's upper crust as derived from the analysis of molybdenites.

Diffusive equilibration of N2, O2 and CO2 mixing ratios in a 1.5-million-years-old ice core

In the framework of the International Partnerships in Ice Core Sciences, one of the most important targets is to retrieve an Antarctic ice core that extends over the last 1.5 million years (i.e. an ice core that enters the climate era when glacial–interglacial cycles followed the obliquity cycles of the earth). In such an ice core the annual layers of the oldest ice would be thinned by a factor of about 100 and the climatic information of a 10 000 yr interval would be contained in less than 1 m of ice. The gas record in such an Antarctic ice core can potentially reveal the role of greenhouse gas forcing on these 40 000 yr cycles. However, besides the extreme thinning of the annual layers, also the long residence time of the trapped air in the ice and the relatively high ice temperatures near the bedrock favour diffusive exchanges. To investigate the changes in the O2 / N2 ratio, as well as the trapped CO2 concentrations, we modelled the diffusive exchange of the trapped gases O2, N2 and CO2 along the vertical axis. However, the boundary conditions of a potential drilling site are not yet well constrained and the uncertainties in the permeation coefficients of the air constituents in the ice are large. In our simulations, we have set the drill site ice thickness at 2700 m and the bedrock ice temperature at 5–10 K below the ice pressure melting point. Using these conditions and including all further uncertainties associated with the drill site and the permeation coefficients, the results suggest that in the oldest ice the precessional variations in the O2 / N2 ratio will be damped by 50–100%, whereas CO2 concentration changes associated with glacial–interglacial variations will likely be conserved (simulated damping 5%). If the precessional O2 / N2 signal will have disappeared completely in this future ice core, orbital tuning of the ice-core age scale will be limited.

Oxygen isotope ratios (18O/16O) of hemicellulose-derived sugar biomarkers in plants, soils and sediments as paleoclimate proxy II: insight from a climate transect study

The oxygen isotopic composition of precipitation (δ18Oprec) is well known to be a valuable (paleo-)climate proxy. Paleosols and sediments and hemicelluloses therein have the potential to serve as archives recording the isotopic composition of paleoprecipitation. In a companion paper (Zech et al., 2014) we investigated δ18Ohemicellulose values of plants grown under different climatic conditions in a climate chamber experiment. Here we present results of compound-specific δ18O analyses of arabinose, fucose and xylose extracted from modern topsoils (n = 56) along a large humid-arid climate transect in Argentina in order to answer the question whether hemicellulose biomarkers in soils reflect δ18Oprec. The results from the field replications indicate that the homogeneity of topsoils with regard to δ18Ohemicellulose is very high for most of the 20 sampling sites. Standard deviations for the field replications are 1.5‰, 2.2‰ and 1.7‰, for arabinose, fucose and xylose, respectively. Furthermore, all three hemicellulose biomarkers reveal systematic and similar trends along the climate gradient. However, the δ18Ohemicellulose values (mean of the three sugars) do not correlate positively with δ18Oprec (r = −0.54, p < 0.014, n = 20). By using a Péclet-modified Craig-Gordon (PMCG) model it can be shown that the δ18Ohemicellulose values correlate highly significantly with modeled δ18Oleaf water values (r = 0.81, p < 0.001, n = 20). This finding suggests that hemicellulose biomarkers in (paleo-)soils do not simply reflect δ18Oprec but rather δ18Oprec altered by evaporative 18O enrichment of leaf water due to evapotranspiration. According to the modeling results, evaporative 18O enrichment of leaf water is relatively low (∼10‰) in the humid northern part of the Argentinian transect and much higher (up to 19‰) in the arid middle and southern part of the transect. Model sensitivity tests corroborate that changes in relative air humidity exert a dominant control on evaporative 18O enrichment of leaf water and thus δ18Ohemicellulose, whereas the effect of temperature changes is of minor importance. While oxygen exchange and degradation effects seem to be negligible, further factors needing consideration when interpreting δ18Ohemicellulose values obtained from (paleo-)soils are evaporative 18O enrichment of soil water, seasonality effects, wind effects and in case of abundant stem/root-derived organic matter input a partial loss of the evaporative 18O enrichment of leaf water. Overall, our results prove that compound-specific δ18O analyses of hemicellulose biomarkers in soils and sediments are a promising tool for paleoclimate research. However, disentangling the two major factors influencing δ18Ohemicellulose, namely δ18Oprec and relative air humidity controlled evaporative 18O enrichment of leaf water, is challenging based on δ18O analyses alone.

129I/127I ratios and 129I concentrations in a recent sea sediment core and in rainwater from Sevilla (Spain) by AMS

In spite of the environmental relevance of 129I, there is still a scarcity of data about its presence in the different natural compartments. In this work, results are presented on the concentration of 129I in rainwater samples taken in Sevilla (southwestern Spain) and in a sediment core taken near the Ringhals coast (Sweden). Typical concentrations of 108 and 109129I at/l are found in rainwater samples, similar to other values in literature. In the case of the sediment core, our results clearly show the impact of anthropogenic sources, with concentrations in the order of 1013129I at./kg and isotopic ratios 129I/127I in the order of 10−8 in the higher layers.

Sulfur Isotopic Ratios at 67P/Churyumov-Gerasimenko and Characterization of ROSINA-DFMS FM & FS

Comets are thought to be the most pristine bodies present in the Solar System. In consequence of spending the majority of their existence beyond 30 AU, their composition can give insights on the physical and chemical conditions during their formation. Since August 2014 the European Space Agency spacecraft Rosetta accompanies the Jupiter family comet 67P/Churyumov-Gerasimenko on its way to perihelion and beyond. In this study the isotope fractionation of 34S are reported in H2S, OCS, SO2, S2, and CS2 at 67P. In addition for the first time the isotope fractionation for 33S is presented for cometary volatiles. The ratio 32S/33S is given for H2S, SO2 and a tentative value is given for CS2. With a mean value of -50 ± 22‰ and -306 ± 31‰ for δ34S and δ33S respectively, H2S shows a significant depletion in both 34S and 33S. For SO2 the depletion is less distinct with δ34S and δ33S being -67 ± 40‰ and -130 ± 53‰, respectively. The strongest depletion is present for CS2 with -114 ± 21‰and -276 ± 55‰, respectively. For OCS and S2 only δ34S could be determined which is -252 ± 77‰ and -357 ± 145‰, respectively. A comparison with sulfur isotopic ratios measured in SiC grains revealed that both SiC grains and the five volatile species have similar sulfur isotopic ratios. However, it is beyond the scope of this work to investigate the possibility of a link between SiC grains and cometary ices. Nevertheless, mass-dependent or mass-independent fractionation due to photo dissociation can be ruled out as sole cause of the seen depletion of 33S and 34S. Furthermore, an upper limit of (9.64 ± 0.19)·10.4 for D/H in HDS has been determined. This value is about a factor two higher than D/H in H2O for the same comet reported by (Altwegg et al., 2015). Besides the investigation concerning isotopic ratios of sulfur bearing species in this work the calibration and characterization of ROSINA/DFMS has been continued. Here it is reported about the deviation of the mass scale for MCP/LEDA low resolution spectra and the calibration measurements performed in the laboratory. Furthermore the outcome of the attempt to describe the sensitivity of DFMS with an empirical function will be discussed. The last part of the characterization of DFMS is dedicated to determine the so-called individual pixel gain for the laboratory and the flight model. Moreover, correlation between the depletion’s manifestation of the MCP with respect to the applied voltages has been investigated for both models. It has been found that further measurements are needed to understand the manifestation of depletion at the laboratory model. For the model on board of Rosetta it could be shown that most of the present feature are due to the usage of the MCP and suggestions have been made in order to answer the remaining question considering the depletion of the MCP.