Boron isotope and B/Ca ratios of planktonic foraminifera

Here a new analytical methodology is described for measuring the isotopic composition of boron in foraminifera using multicollector inductively coupled plasma mass spectrometry (MC-ICPMS). This new approach is fast (~10 samples analysed in duplicate per analytical session) and accurate (to better than 0.25 per mil at 95% confidence) with acceptable sample size requirements (1-3 mg of carbonate). A core top calibration of several common planktic and two benthic species from geographically widespread localities shows a very close agreement between the isotopic composition measured by MC-ICPMS and the isotopic composition of B(OH)-4 in seawater (as predicted using the recently measured isotopic equilibrium factor of 1.0272) at the depth of habitat. A down core and core top investigation of boron concentration (B/Ca ratio) shows that the partition coefficient is influenced by [CO2-3] complicating the application of this proxy. Nevertheless, it is demonstrated that these two proxies can be used to fully constrain the carbonate system of surface water in the Caribbean Sea (ODP Site 999A) over the last 130 kyr. This reconstruction shows that during much of the Holocene and the last interglacial period surface water at Site 999A was in equilibrium with the atmosphere with respect to CO2. During the intervening colder periods although the surface water pCO2 was lower than the Holocene, it was a minor to significant source of CO2 to the atmosphere possibly due to either an expansion of the eastern equatorial Atlantic upwelling zone, or a more local expansion of coastal upwelling in the southern Caribbean. Such reorganisation of the oceanic carbonate system in favour of a larger source of CO2 to the atmosphere from the equatorial ocean may require mechanisms responsible for lowering atmospheric CO2 during glacial periods to be more efficient than previously supposed.

Seawater carbonate chemistry and biological processed during experiments with corals Porites sp. & Stylophora pistillata, 2010

Uptake of anthropogenic CO2 by the oceans is altering seawater chemistry with potentially serious consequences for coral reef ecosystems due to the reduction of seawater pH and aragonite saturation state (omega arag). The objectives of this long-term study were to investigate the viability of two ecologically important reef-building coral species, massive Porites sp. and Stylophora pistilata, exposed to high pCO2(or low pH) conditions and to observe possible changes in physiologically related parameters as well as skeletal isotopic composition. Fragments of Porites sp. and S. pistilata were kept for 6-14 months under controlled aquarium conditions characterized by normal and elevated pCO2 conditions, corresponding to pHTvalues of 8.09, 7.49, and 7.19, respectively. In contrast with shorter, and therefore more transient experiments, the long experimental timescale achieved in this study ensures complete equilibration and steady state with the experimental environment and guarantees that the data provide insights into viable and stably growing corals. During the experiments, all coral fragments survived and added new skeleton, even at seawater omega arag <1, implying that the coral skeleton is formed by mechanisms under strong biological control. Measurements of boron (B), carbon (C) and oxygen (O) isotopic composition of skeleton, C isotopic composition of coral tissue and symbiont zooxanthellae, along with physiological data (such as skeletal growth, tissue biomass, zooxanthellae cell density and chlorophyll concentration) allow for a direct comparison with corals living under normal conditions and sampled simultaneously. Skeletal growth and zooxanthellae density were found to decrease, whereas coral tissue biomass (measured as protein concentration) and zooxanthellae chlorophyll concentrations increased under high pCO2 (low pH) conditions. Both species showed similar trends of delta11B depletion and delta18O enrichment under reduced pH, whereas the delta13C results imply species-specific metabolic response to high pCO2 conditions. The skeletal delta11B values plot above seawater delta11B vs. pH borate fractionation curves calculated using either the theoretically derived deltaB value of 1.0194 (Kakihana et al., Bull. Chem. Soc. Jpn. 50(1977), 158) or the empirical deltaB value of 1.0272 (Klochko et al., EPSL 248 (2006), 261). However, the effective deltaB must be greater than 1.0200 in order to yield calculated coral skeletal delta11B values for pH conditions where omega arag >1. The delta11B vs. pH offset from the literature seawater delta11B vs. pH fractionation curves suggests a change in the ratio of skeletal material laid down during dark and light calcification and/or an internal pH regulation, presumably controlled by ion-transport enzymes. Finally, seawater pH significantly influences skeletal delta13C and delta18O. This must be taken into consideration when reconstructing paleo-environmental conditions from coral skeleton

Boron isotope composition and seawater characteristics of cold water scleratinian corals

The boron isotope systematics has been determined for azooxanthellate scleractinian corals from a wide range of both deep-sea and shallow-water environments. The aragonitic coral species, Caryophyllia smithii, Desmophyllum dianthus, Enallopsammia rostrata, Lophelia pertusa, and Madrepora oculata, are all found to have relatively high d11B compositions ranging from 23.2 per mil to 28.7 per mil. These values lie substantially above the pH-dependent inorganic seawater borate equilibrium curve, indicative of strong up-regulation of pH of the internal calcifying fluid (pH(cf)), being elevated by ~0.6-0.8 units (Delta pH) relative to ambient seawater. In contrast, the deep-sea calcitic coral Corallium sp. has a significantly lower d11B composition of 15.5 per mil, with a corresponding lower Delta pH value of ~0.3 units, reflecting the importance of mineralogical control on biological pH up-regulation. The solitary coral D. dianthus was sampled over a wide range of seawater pH(T) and shows an approximate linear correlation with Delta pH(Desmo) = 6.43 - 0.71 pH(T) (r**2 = 0.79). An improved correlation is however found with the closely related parameter of seawater aragonite saturation state, where Delta pH(Desmo) = 1.09 - 0.14 Omega(arag) (r**2 = 0.95), indicating the important control that carbonate saturation state has on calcification. The ability to up-regulate internal pH(cf), and consequently Omega(cf), of the calcifying fluid is therefore a process present in both azooxanthellate and zooxanthellate aragonitic corals, and is attributed to the action of Ca2+ -ATPase in modulating the proton gradient between seawater and the site of calcification. These findings also show that the boron isotopic compositions (d11Bcarb) of aragonitic corals are highly systematic and consistent with direct uptake of the borate species within the biologically controlled extracellular calcifying medium.

The Provenance and Geochemical Alteration of Bermudan Eolianites

Large calcareous eolianites cover the remote island of Bermuda, accounting for more than 90% of the limestone bedrock. This study examines the sedimentology and geochemistry of these eolianites to better understand Pleistocene oceanography and the meteoric alteration of subtropical carbonate sediments. Cluster analyses reveal that the eolian carbonate sediments fall into two natural groups that represent lagoonal and reefal end members of marine sediment production. Coral fragments are uncharacteristically absent, possibly destroyed prior to their incorporation into eolian deposits by endolithic microboring organisms or broken up during transport. Sediment assemblages lead to the following interpretations of the Bermudan offshore environment: (1) the Ledge Flats reef system along the southwestern coast has been active since MIS 11, contributing coralline algal-rich sediment to the northern beaches of Sandy’s Parish and acting as an energy barrier in the south, allowing for low energy sedimentation in the quiet back- reef region; (2) on the northeastern coast, the low energy back-reef region landward of the Ledge Flats has thrived since MIS 11; (3) during MIS 5e, slightly warmer water temperatures led to the hindrance of coralline algal growth along the southern coast and in the North Lagoon. These are the first interpretations of Pleistocene marine assemblages on Bermuda. Meteoric fluids progressively transformed the pristine carbonate sediments into hardened limestones in a predictable solubility-dependent manner. The progressive alteration is coincident with: (1) divergence of δ18O and δ13C values from those similar to unaltered sediment towards those of calcrete, due to interaction with CO2-charged meteoric fluids; (2) depletion of elements with low partitioning coefficients and low meteoric concentrations, such as barium, boron, magnesium, potassium, sodium, strontium, and uranium; (3) enrichment of iron from Terra Rossa-hosted iron oxides; (4) enrichment of aluminum via detrital minerals sourced from protosol horizons; and (5) manganese concentrations that remain uncharacteristically low, owing to the lack of a consistent manganese source. Elemental correlations are useful for characterizing meteoric diagenesis, assuming the primary mineralogy is recognized, all components have been fully altered, and inter-particle cements are ubiquitous.

Dielectric screening in atomically thin boron nitride nanosheets

Two-dimensional (2D) hexagonal boron nitride (BN) nanosheets are excellent dielectric substrate for graphene, molybdenum disulfide, and many other 2D nanomaterial-based electronic and photonic devices. To optimize the performance of these 2D devices, it is essential to understand the dielectric screening properties of BN nanosheets as a function of the thickness. Here, electric force microscopy along with theoretical calculations based on both state-of-the-art first-principles calculations with van der Waals interactions under consideration, and nonlinear Thomas-Fermi theory models are used to investigate the dielectric screening in high-quality BN nanosheets of different thicknesses. It is found that atomically thin BN nanosheets are less effective in electric field screening, but the screening capability of BN shows a relatively weak dependence on the layer thickness.

A boron nitride - graphene - C60 heterostructure

We have fabricated a new van-der-Waals heterostructure composed by BN/graphene/C60. We performed transport measurements on the preliminary BN/graphene device finding a sharp Dirac point at the neutrality point. After the deposition of a C60 thin film by thermal evaporation, we have observed a significant n-doping of the heterostructure. This suggests an unusual electron transfer from C60 into the BN/graphene structure. This BN/graphene/C60 heterostructure can be of interest in photovoltaic applications. It can be used to build devices like p-n junctions, where C60 can be easily deposited in defined regions of a graphene junction by the use of a shadow mask. Our results are contrasted with theoretical calculations.

Boron uptake in normal melanocytes and melanoma cells and boron biodistribution study in mice bearing B16F10 melanoma for boron neutron capture therapy

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

In situ Lithium and Boron isotope determinations in mica, pyroxene, and serpentine by LA-MC-ICP-MS

Boron and Li are light, incompatible elements that preferentially partition into the liquid phase, whether melt or aqueous fluid, and thus are useful for tracking fluid-related processes in rocks. Most of the Li isotopic data presently available on subduction-related rocks are from whole-rock analyses; and the B isotopic analyses of subduction material have been carried out either on whole-rocks or in-situ on an accessory phase, such as tourmaline. The new method presented here couples an ESI New Wave UP-193-FX ArF* (193 nm) excimer laser-ablation microscope with a Neptune Plus (Thermo Scientific) MC-ICP-MS aiming to measure both Li and B isotopes in situ with good spatial resolution (metamorphic minerals are commonly chemically zoned, and whole-rock analyses lose this detail). The data thus obtained are compared with SIMS analyses on the same mineral samples for B, and with MC-ICP-MS analyses on whole-rock or mineral separates from the same sample for Li. Additionally, data acquired on tourmaline standards were compared to SIMS values. The results show that for B concentrations above 5 μg/g, the data obtained by LA-MC-ICP-MS and by SIMS are identical within error, for mica (phengitic muscovite), pyroxene (jadeite), serpentine (antigorite), and tourmaline. For Li concentrations above 10 μg/g, the data obtained by LA-MC-ICP-MS and by MC-ICP-MS are also identical, within error, for mica (phengitic muscovite), and pyroxene (jadeite). However, analyses of tourmaline standards have shown significant differences with reference values, so LA-MC-ICP-MS does not yet appear to be an appropriate method to analyze Li isotopes in tourmalines. Thus, LA-MC-ICP-MS is a suitable method to measure Li and B isotopes with good spatial resolution in major rock-forming silicates from subduction-related rocks where concentrations exceed 10 μg/g and 5 μg/g, respectively, with an error on individual measurements equal to or less than previously used methods, but obtainable in a significantly shorter amount of time. The external reproducibility is ± 2.88 to 3.31 ‰ for B and ± 1.50 to 1.75 for Li, which is lower than or equal to the variations encountered within a given chemically zoned sample (up to 10 ‰ of variation within a given natural sample).