Stable isotope and multi-analytical investigation of Monte da Cegonha: A Late Antiquity population in southern Portugal

This study presents for the first time the diet of a Late Antiquity population in southern Portugal (Civitas of Pax Julia), from the Roman villa of Monte da Cegonha (predominantly 7th century CE). Stable isotope analysis (δ13C, δ15N, δ18O, 87Sr/86Sr) of human and faunal bone collagen and apatite was conducted in order to understand the influence of Roman subsistence strategies on the way of life of rural inhabitants of the area of Pax Julia and to explore their diet (types of ingested plants, amount of animal resources, terrestrial versus marine resources). X-ray diffraction (XRD) and Fourier transform infra-red spectroscopy (FTIR) analyses were used to determine the degree of bone diagenesis and assess the reliability of the bone stable isotopic composition for palaeodietary reconstruction. Anthropological analysis revealed a cariogenic diet, rich in starchy food and carbohydrates, in at least in two individuals based on the frequency of dental caries. Collagen and apatite carbon isotopic analysis suggested that C3 plants were the basis of the population's diet, complemented with some terrestrial meat and its by-products as reflected by the observed bone collagen nitrogen isotopic composition. Moreover, whilst the fairly low apatite-collagen spacing recorded in some skeletons (at around 4‰) may have been due to freshwater organisms intake, the relatively low nitrogen values observed indicate that this consumption did not occur very often, unless in the form of fresh fish of low trophic level or fish sauces. There were no significant differences in isotopic values depending on gender or burial type. Strontium and oxygen isotopic composition of bone apatite revealed a sedentary community, with the exception of a male individual who probably did not spend his childhood in Monte da Cegonha.

In search of a hidden long-term isolated sub-chondritic 142Nd/144Nd reservoir in the deep mantle : implications for the Nd isotope systematics of the Earth

Here we search for evidence of the existence of a sub-chondritic 142Nd/144Nd reservoir that balances the Nd isotope chemistry of the Earth relative to chondrites. If present, it may reside in the source region of deeply sourced mantle plume material. We suggest that lavas from Hawai’i with coupled elevations in 186Os/188Os and 187Os/188Os, from Iceland that represent mixing of upper mantle and lower mantle components, and from Gough with sub-chondritic 143Nd/144Nd and high 207Pb/206Pb, are favorable samples that could reflect mantle sources that have interacted with an Early-Enriched Reservoir (EER) with sub-chondritic 142Nd/144Nd. High-precision Nd isotope analyses of basalts from Hawai’i, Iceland and Gough demonstrate no discernable 142Nd/144Nd deviation from terrestrial standards. These data are consistent with previous high-precision Nd isotope analysis of recent mantle-derived samples and demonstrate that no mantle-derived material to date provides evidence for the existence of an EER in the mantle. We then evaluate mass balance in the Earth with respect to both 142Nd/144Nd and 143Nd/144Nd. The Nd isotope systematics of EERs are modeled for different sizes and timing of formation relative to ε143Nd estimates of the reservoirs in the μ142Nd = 0 Earth, where μ142Nd is ((measured 142Nd/144Nd/terrestrial standard 142Nd/144Nd)−1 * 10−6) and the μ142Nd = 0 Earth is the proportion of the silicate Earth with 142Nd/144Nd indistinguishable from the terrestrial standard. The models indicate that it is not possible to balance the Earth with respect to both 142Nd/144Nd and 143Nd/144Nd unless the μ142Nd = 0 Earth has a ε143Nd within error of the present-day Depleted Mid-ocean ridge basalt Mantle source (DMM). The 4567 Myr age 142Nd–143Nd isochron for the Earth intersects μ142Nd = 0 at ε143Nd of +8 ± 2 providing a minimum ε143Nd for the μ142Nd = 0 Earth. The high ε143Nd of the μ142Nd = 0 Earth is confirmed by the Nd isotope systematics of Archean mantle-derived rocks that consistently have positive ε143Nd. If the EER formed early after solar system formation (0–70 Ma) continental crust and DMM can be complementary reservoirs with respect to Nd isotopes, with no requirement for significant additional reservoirs. If the EER formed after 70 Ma then the μ142Nd = 0 Earth must have a bulk ε143Nd more radiogenic than DMM and additional high ε143Nd material is required to balance the Nd isotope systematics of the Earth.

Use of 3D visualisation to enhance groundwater stable isotope data and its interpretation, Lockyer Valley, southeast Queensland

The use of stable isotope ratios δ18O and δ2H are well established in assessment of groundwater systems and their hydrology. The conventional approach is based on x/y plots and relation to various MWL’s, and plots of either ratio against parameters such as Clor EC. An extension of interpretation is the use of 2D maps and contour plots, and 2D hydrogeological vertical sections. An enhancement of presentation and interpretation is the production of “isoscapes”, usually as 2.5D surface projections. We have applied groundwater isotopic data to a 3D visualisation, using the alluvial aquifer system of the Lockyer Valley. The 3D framework is produced in GVS (Groundwater Visualisation System). This format enables enhanced presentation by displaying the spatial relationships and allowing interpolation between “data points” i.e. borehole screened zones where groundwater enters. The relative variations in the δ18O and δ2H values are similar in these ambient temperature systems. However, δ2H better reflects hydrological processes, whereas δ18O also reflects aquifer/groundwater exchange reactions. The 3D model has the advantage that it displays borehole relations to spatial features, enabling isotopic ratios and their values to be associated with, for example, bedrock groundwater mixing, interaction between aquifers, relation to stream recharge, and to near-surface and return irrigation water evaporation. Some specific features are also shown, such as zones of leakage of deeper groundwater (in this case with a GAB signature). Variations in source of recharging water at a catchment scale can be displayed. Interpolation between bores is not always possible depending on numbers and spacing, and by elongate configuration of the alluvium. In these cases, the visualisation uses discs around the screens that can be manually expanded to test extent or intersections. Separate displays are used for each of δ18O and δ2H and colour coding for isotope values.

Tracking the magmatic evolution of island arc volcanism : insights from a high-precision Pb isotope record of Montserrat, Lesser Antilles

The volcanic succession on Montserrat provides an opportunity to examine the magmatic evolution of island arc volcanism over a ∼2.5 Ma period, extending from the andesites of the Silver Hills center, to the currently active Soufrière Hills volcano (February 2010). Here we present high-precision double-spike Pb isotope data, combined with trace element and Sr-Nd isotope data throughout this period of Montserrat's volcanic evolution. We demonstrate that each volcanic center; South Soufrière Hills, Soufrière Hills, Centre Hills and Silver Hills, can be clearly discriminated using trace element and isotopic parameters. Variations in these parameters suggest there have been systematic and episodic changes in the subduction input. The SSH center, in particular, has a greater slab fluid signature, as indicated by low Ce/Pb, but less sediment addition than the other volcanic centers, which have higher Th/Ce. Pb isotope data from Montserrat fall along two trends, the Silver Hills, Centre Hills and Soufrière Hills lie on a general trend of the Lesser Antilles volcanics, whereas SSH volcanics define a separate trend. The Soufrière Hills and SSH volcanic centers were erupted at approximately the same time, but retain distinctive isotopic signatures, suggesting that the SSH magmas have a different source to the other volcanic centers. We hypothesize that this rapid magmatic source change is controlled by the regional transtensional regime, which allowed the SSH magma to be extracted from a shallower source. The Pb isotopes indicate an interplay between subduction derived components and a MORB-like mantle wedge influenced by a Galapagos plume-like source.

Mechanical properties of graphene : effects of layer number, temperature and isotope

Herein the mechanical properties of graphene, including Young’s modulus, fracture stress and fracture strain have been investigated by molecular dynamics simulations. The simulation results show that the mechanical properties of graphene are sensitive to the temperature changes but insensitive to the layer numbers in the multilayer graphene. Increasing temperature exerts adverse and significant effects on the mechanical properties of graphene. However, the adverse effect produced by the increasing layer number is marginal. On the other hand, isotope substitutions in graphene play a negligible role in modifying the mechanical properties of graphene.

Modelling carbon membranes for gas and isotope separation

Molecular modelling has become a useful and widely applied tool to investigate separation and diffusion behavior of gas molecules through nano-porous low dimensional carbon materials, including quasi-1D carbon nanotubes and 2D graphene-like carbon allotropes. These simulations provide detailed, molecular level information about the carbon framework structure as well as dynamics and mechanistic insights, i.e. size sieving, quantum sieving, and chemical affinity sieving. In this perspective, we revisit recent advances in this field and summarize separation mechanisms for multicomponent systems from kinetic and equilibrium molecular simulations, elucidating also anomalous diffusion effects induced by the confining pore structure and outlining perspectives for future directions in this field.

Asymmetrically decorated, doped porous graphene as an effective membrane for hydrogen isotope separation

We propose a new route to hydrogen isotope separation which exploits the quantum sieving effect in the context of transmission through asymmetrically decorated, doped porous graphenes. Selectivities of D2 over H2 as well as rate constants are calculated based on ab initio interaction potentials for passage through pure and nitrogen functionalized porous graphene. One-sided dressing of the membrane with metal provides the critical asymmetry needed for an energetically favorable pathway.

The effects of low degree alteration on Sm-Nd and U-Pb isotope systematics in Eoarchean basalts from the Doolena Gap and Warralong Greenstone belts, Pilbara Craton, Western Australia

This research led to the discovery of one of the best preserved remnants of the Earth's surficial environment 3.47 billion years ago. These ancient volcanic and sedimentary rocks contain original minerals and textures that are rare in rocks of this age. The research concentrated on chemical analysis of volcanic rocks to differentiate secondary alteration from the primary magmatic signature. This study contributes to our understanding of melting processes and geochemical reservoirs in the early Earth, which is vital for forward modelling of Earth's geodynamic evolution.

Assessment of body composition in Indian adults: comparison between dual-energy X-ray absorptiometry and isotope dilution technique

Dual-energy X-ray absorptiometry (DXA) and isotope dilution technique have been used as reference methods to validate the estimates of body composition by simple field techniques; however, very few studies have compared these two methods. We compared the estimates of body composition by DXA and isotope dilution (18O) technique in apparently healthy Indian men and women (aged 19–70 years, n 152, 48 % men) with a wide range of BMI (14–40 kg/m2). Isotopic enrichment was assessed by isotope ratio mass spectroscopy. The agreement between the estimates of body composition measured by the two techniques was assessed by the Bland–Altman method. The mean age and BMI were 37 (SD 15) years and 23·3 (SD 5·1) kg/m2, respectively, for men and 37 (SD 14) years and 24·1 (SD 5·8) kg/m2, respectively, for women. The estimates of fat-free mass were higher by about 7 (95 % CI 6, 9) %, those of fat mass were lower by about 21 (95 % CI 218,223) %, and those of body fat percentage (BF%) were lower by about 7·4 (95 % CI 28·2, 26·6) % as obtained by DXA compared with the isotope dilution technique. The Bland–Altman analysis showed wide limits of agreement that indicated poor agreement between the methods. The bias in the estimates of BF% was higher at the lower values of BF%. Thus, the two commonly used reference methods showed substantial differences in the estimates of body composition with wide limits of agreement. As the estimates of body composition are method-dependent, the two methods cannot be used interchangeably

Calculation of the oxygen isotope discrimination factor for studying plant respiration

Measurement of discrimination against 18O during dark respiration in plants is currently accepted as the only reliable method of estimating the partitioning of electrons between the cytochrome and alternative pathways. In this paper, we review the theory of the technique and its application to a gas-phase system. We extend it to include sampling effects and show that the isotope discrimination factor, D, is calculated as –dln(1 + δ)/dlnO*, where δ is isotopic composition of the substrate oxygen and O*=[O2]/[N2] in a closed chamber containing tissue respiring in the dark. It is not necessary to integrate the expression but, if the integrated form is used, the resultant regression should not be constrained through the origin. This is important since any error in D will have significant effects on the estimation of the flux of electrons through the two pathways.

Coherent phonon decay and the boron isotope effect for MgB2

Ab-initio DFT calculations for the phonon dispersion (PD) and the Phonon Density Of States (PDOS) of the two isotopic forms (10B and 11B) of MgB2 demonstrate that use of a reduced symmetry super-lattice provides an improved approximation to the dynamical, phonon-distorted P6/mmm crystal structure. Construction of phonon frequency plots using calculated values for these isotopic forms gives linear trends with integer multiples of a base frequency that change in slope in a manner consistent with the isotope effect (IE). Spectral parameters inferred from this method are similar to that determined experimentally for the pure isotopic forms of MgB2. Comparison with AlB2 demonstrates that a coherent phonon decay down to acoustic modes is not possible for this metal. Coherent acoustic phonon decay may be an important contributor to superconductivity for MgB2.

Multiple sulfur isotope analyses support a magmatic model for the volcanogenic massive sulfide deposits of the Teutonic Bore volcanic complex, Yilgarn Craton, Western Australia

We report sensitive high mass resolution ion microprobe, stable isotopes (SHRIMP SI) multiple sulfur isotope analyses (32S, 33S, 34S) to constrain the sources of sulfur in three Archean VMS deposits—Teutonic Bore, Bentley, and Jaguar—from the Teutonic Bore volcanic complex of the Yilgarn Craton, Western Australia, together with sedimentary pyrites from associated black shales and interpillow pyrites. The pyrites from VMS mineralization are dominated by mantle sulfur but include a small amount of slightly negative mass-independent fractionation (MIF) anomalies, whereas sulfur from the pyrites in the sedimentary rocks has pronounced positive MIF, with ∆33S values that lie between 0.19 and 6.20‰ (with one outlier at −1.62‰). The wall rocks to the mineralization include sedimentary rocks that have contributed no detectable positive MIF sulfur to the VMS deposits, which is difficult to reconcile with the leaching model for the formation of these deposits. The sulfur isotope data are best explained by mixing between sulfur derived from a magmatic-hydrothermal fluid and seawater sulfur as represented by the interpillow pyrites. The massive sulfide lens pyrites have a weighted mean ∆33S value of −0.27 ± 0.05‰ (MSWD = 1.6) nearly identical with −0.31 ± 0.08‰ (MSWD = 2.4) for pyrites from the stringer zone, which requires mixing to have occurred below the sea floor. We employed a two-component mixing model to estimate the contribution of seawater sulfur to the total sulfur budget of the two Teutonic Bore volcanic complex VMS deposits. The results are 15 to 18% for both Teutonic Bore and Bentley, much higher than the 3% obtained by Jamieson et al. (2013) for the giant Kidd Creek deposit. Similar calculations, carried out for other Neoarchean VMS deposits give value between 2% and 30%, which are similar to modern hydrothermal VMS deposits. We suggest that multiple sulfur isotope analyses may be used to predict the size of Archean VMS deposits and to provide a vector to ore deposit but further studies are needed to test these suggestions.

Geochronological (U–Pb, U–Th–total Pb, Sm–Nd) and geochemical (REE, 87Sr/86Sr, δ18O, δ13C) tracing of intraplate tectonism and associated fluid flow in the Warburton Basin, Australia

The Warburton Basin of central Australia has experienced a complex tectonic and fluid-flow history, resulting in the formation of various authigenic minerals. Geochemical and geochronological analyses were undertaken on vein carbonates from core samples of clastic sediments. Results were then integrated with zircon U–Pb dating and uraninite U–Th–total Pb dating from the underlying granite. Stable and radiogenic isotopes (δ18O, Sr and εNd), as well as trace element data of carbonate veins indicate that >200 °C basinal fluids of evolved meteoric origin circulated through the Warburton Basin. Almost coincidental ages of these carbonates (Sm–Nd; 432 ± 12 Ma) with primary zircon (421 ± 3.8 Ma) and uraninite (407 ± 16 Ma) ages from the granitic intrusion point towards a substantial period of active tectonism and an elevated thermal regime during the mid Silurian. We hypothesise that such a thermal regime may have resulted from extensional tectonism and concomitant magmatic activity following regional orogenesis. This study shows that the combined application of geochemical and geochronological analyses of both primary and secondary species may constrain the timing of tectonomagmatic events and associated fluid flow in intraplate sedimentary basins. Furthermore, this work suggests that the Sm–Nd-isotopic system is surprisingly robust and can record geologically meaningful age data from hydrothermal mineral species.