Geochemical fingerprints of glacially eroded bedrock from West Antarctica: Detrital thermochronology, radiogenic isotope systematics and trace element geochemistry in Late Holocene glacial-marine sediments

Geochemical provenance studies of glacial-marine sediments provide a powerful approach to describe subglacial geology, sediment transport pathways, and past ice sheet dynamics. The marine-based West Antarctic Ice Sheet (WAIS) is considered highly vulnerable to ocean warming and sea level rise that is likely to cause its rapid and irreversible retreat. Studies of its past response to climate change are hence essential for projecting its future behaviour. The application of radiogenic and trace element provenance studies for past ice sheet reconstructions requires surveying the geographic variability of geochemical compositions of glaciomarine sediments. In this study, we characterize the provenance of the detrital fraction of 67 Late Holocene marine sediment samples collected off the Pacific margin of West Antarctica (60°W to 160°W), including 40Ar/39Ar ages of individual hornblende and biotite grains (> 150 μm), as well as Sr and Nd isotope and trace element composition of the fine-grained (40Ar/39Ar ages of iceberg-rafted hornblende and biotite grains record primarily Carboniferous to Lates Quaternary ages (~0 to 380 Ma), with a notable age peak of ~100 Ma, associated with plutonic intrusions or deformation events during the mid-Cretaceous. Permian-Jurassic 40Ar/39Ar ages are widespread in the Amundsen Sea sector, marking episodes of large-volume magmatism along the long-lived continental margin. Metasedimentary rocks and Late Cenozoic alkali basalts in West Antarctica cannot be detected using detrital hornblende and biotite 40Ar/39Ar ages due to the absence or small grain-size (i.e. < 150 μm) of these minerals in such rocks. These sources can however be readily recognized by their fine-grained geochemical composition. In addition, geographic trends in the provenance from proximal to distal sites provide insights into major sediment transport pathways. While the transport of fine-grained detritus follows bathymetric cross-shelf troughs, the distribution of iceberg-rafted grains shows influence by transport in the Antarctic Coastal Current. Our study provides the first systematic geochemical characterisation of sediment provenance off West Antarctica, and highlights the importance of combining multiple provenance approaches in different size fractions of glacial-marine sediments, and paves the way to investigate past WAIS dynamics

Ruthenium-cyclopentadienyl bipyridine-biotin based compounds: Synthesis and biological effect

Prospective anticancer metallodrugs should consider target-specific components in their design in order to overcome the limitations of the current chemotherapeutics. The inclusion of vitamins, which receptors are overexpressed in many cancer cell lines, has proven to be a valid strategy. Therefore, in this paper we report the synthesis and characterization of a set of new compounds [Ru(eta(5)-C5H5)(P(C6H4R)(3))(4,4'-R'-2,2'-bpy)](+) (R = F and R' = H, 3; R = F and R' = biotin, 4; R = OCH3 and R' = H, 5; R = OCH3 and R' = biotin, 6), inspired by the exceptional good results recently obtained for the analogue bearing a triphenylphosphane ligand. The precursors for these syntheses were also described following modified literature procedures, [Ru(eta(5)-C5H3)(P(C6H4R)(3))(2)Cl], where R is -F (1) or -OCH3 (2). The structure of all compounds is fully supported by spectroscopic and analytical techniques and by X-ray diffraction studies for compounds 2, 3, and 5. All cationic compounds are cytotoxic in the two breast cancer cell lines tested, MCF7 and MDA-MB-231, and much better than cisplatin under the same experimental conditions. The cytotoxicity of the biotinylated compounds seems to be related with the Ru uptake by the cells expressing biotin receptors, indicating a potential mediated uptake. Indeed, a biotin-avidin study confirmed that the attachment of biotin to the organometallic fragment still allows biotin recognition by the protein. Therefore, the biotinylated compounds might be potent anticancer drugs as they show cytotoxic effect in breast cancer cells at low dose dependent on the compounds' uptake, induce cell death by apoptosis and inhibit the colony formation of cancer cells causing also less severe side effects in zebrafish.This work was financed by the Portuguese Foundation for Science and Technology (Fundacao para a Crencia e Tecnologia, FCT) within the scope of Projects UID/QUI/00100/2019 and PTDC/QUI-QIN/28662/2017. This work was supported by the strategic program UID/BIA/04050/2013 (POCI-01-0145-FEDER-007569) funded by national funds through the FCT I.P. and by the ERDF through the COMPETE2020 -Programa Operacional Competitividade e Intemacionalizacao (POCI). A.V. acknowledges the Investigator FCT2013 Initiative for the Project IF/01302/2013 and CEEC-IND/01974/2017 (acknowledging FCT, as well as POPH and FSE, the European Social Fund). L.C.-R, A.R.B. and A.P. thank FCT for their Ph.D. Grants (SFRH/BD/100515/2014, SFRH/BD/139271/2018, and SFRH/BD/139412/2018, respectively). L.C.-R also acknowledges Fulbright Research Grant 2017/2018 with the support of FCT. Brittany Karas acknowledges NJAES-RutgersNJ01201 and NIEHS Training Grant T32-ES 007148 and B.T.B. and C.D. acknowledge NIH-NIEHS P30 ES005022. K.R.C. acknowledges NJAES Project 01202 (W2045) and NIH ES005022

Multi-stage evolution of the lithospheric mantle in the West Antarctic Rift System - a mantle xenolith study

Mantle xenoliths allow us to investigate the geochemical and dynamic evolution of the mantle beneath the western margin of Antarctica and reconstruct a timeline of geologic events that are obscured on the surface. For this study, mantle xenoliths, brought to the surface by recent volcanism, were collected along a transect from the rift shoulder and into the rift basin in the western margin of the West Antarctic Rift System (WARS), thus providing a recent snapshot of the lithospheric mantle after major episodes of rifting. The second chapter of my thesis focuses on determining the age and persistence of the mantle within the rift. The rhenium-osmium (Re-Os) isotope system has proven to be an invaluable tracer of the tectonic history of the lithospheric mantle and can constrain the age of melt extraction and subsequent stabilization of the lithospheric mantle. This allowed us to track the age of the lithospheric mantle across this rifted margin. Os isotopes, combined with major element compositions, reveal widespread Paleoproterozoic (1.7-2.4 Ga) stabilization of the lithosphere and subsequent preservation, suggesting the lithosphere has dynamically thinned in response to rifting. Major element data allowed us to place temperature (T) constraints on the mantle and characterize the thermal history in the WARS. This study also revealed the oldest lithosphere ages recorded in Antarctica (3.3 Ga) and is the first to report ages that coincide with adjacent crustal ages, thus confirming the coupled relationship between the lithospheric mantle and continental crust. An integral factor controlling the composition of magmas generated at Earth’s surface is the composition of the SCLM. Magmas generated at depth must pass through it, and subsequently may take on geochemical signatures of the lithosphere, or may leave behind geochemical imprints of the migrating magma in the SCLM. Trace elements provide a means to investigate both the depletion and re-enrichment history of the SCLM. The third chapter of my thesis investigates the metasomatic overprinting of the Paleoproterozoic SCLM. Metasomatism, which is the chemical alteration of a rock by a migrating melt and/or fluid, leaves behind diagnostic signatures of the metasomatizing agent (e.g. subduction related fluids or carbonated melts). This can occur cryptically, where a melt percolates through the rock, changing the composition of the rock, but not the lithology. Modal metasomatism produces new mineral phases that are not typically expected in the rock. In xenoliths, trace elements enable us to decode geochemical signatures, and determine the sources of metasomatism. The WARS lithosphere has experienced varying degrees of re-enrichment, broadly characterized by low high field strength element (HFSE) abundances and rare earth element (REE) enrichments that correspond with carbonatite metasomatism. In addition, the presence of secondary hydrous phases (e.g. amphibole and phlogopite) imparted distinct geochemical signatures, revealing that the SCLM beneath the WARS was modified by reactive porous flow with an evolving metasomatic fluid/melt. Widespread Cenozoic rift-related volcanism (<20 Ma) is observed throughout the western margin of the East Antarctic Craton. It has been proposed that the Cenozoic basaltic volcanism in the region of our study site originated from a SCLM source that had been metasomatized during subduction along the paleo-Pacific margin of Gondwana, and subsequent extension in the WARS during the Late Cretaceous (~90 Ma). The fourth chapter of my thesis utilizes strontium (Sr), neodymium (Nd), and hafnium (Hf) isotopes to date depletion and refertilization events in the lithosphere, as well as understand the role of the SCLM in the formation of WARS volcanism. Together with lithologic features (e.g. presence of hydrous phase additions), Sr and Nd isotopic ratios in WARS xenoliths provide a geochemical link to the Cenozoic rift-related magmatism, and supports the SCLM’s role in the formation of diffuse alkaline magmatism throughout the region. Lu-Hf isotope model ages add a constraint on the timing of melt depletion, and establish a relationship between depleted and refertilized domains. Sr isotopes constrain a genetic link between the metasomatized Archean lithosphere sampled on the rift shoulder and the highly radiogenic character of the Ferrar flood basalts, and indicate long-term storage of subduction modified mantle domains in the SCLM. The Sm-Nd isotope system is variably overprinted by metasomatism throughout the WARS. The most highly metasomatized location produces a well-correlated isochron that indicates that the SCLM acquired its trace element metasomatic signature about 130 Ma ago, during the late stages of subduction along the paleo-Pacific margin of Gondwana

Moving toward a Handheld “Plasma” Spectrometer for Elemental Analysis, Putting the Power of the Atom (Ion) in the Palm of Your Hand

Many of the current innovations in instrument design have been focused on making them smaller, more rugged, and eventually field transportable. The ultimate application is obvious, carrying the instrument to the field for real time sample analysis without the need for a support laboratory. Real time data are priceless when screening either biological or environmental samples, as mitigation strategies can be initiated immediately upon the discovery that contaminant metals are present in a location they were not intended to be. Additionally, smaller “handheld” instruments generally require less sample for analysis, possibly increasing sensitivity, another advantage to instrument miniaturization. While many other instruments can be made smaller just by using available micro-technologies (e.g., eNose), shrinking an ICP-MS or AES to something someone might carry in a backpack or pocket is now closer to reality than in the past, and can be traced to its origins based on a component-by-component evaluation. While the optical and mass spectrometers continue to shrink in size, the ion/excitation source remains a challenge as a tradeoff exists between excitation capabilities and the power requirements for the plasma’s generation. Other supporting elements have only recently become small enough for transport. A systematic review of both where the plasma spectrometer started and the evolution of technologies currently available may provide the roadmap necessary to miniaturize the spectrometer. We identify criteria on a component-by-component basis that need to be addressed in designing a miniaturized device and recognize components (e.g., source) that probably require further optimization. For example, the excitation/ionization source must be energetic enough to take a metal from a solid state to its ionic state. Previously, a plasma required a radio frequency generator or high-power DC source, but excitation can now be accomplished with non-thermal (cold) plasma sources. Sample introduction, for solids, liquids, and gasses, presents challenges for all sources in a field instrument. Next, the interface between source and a mass detector usually requires pressure reduction techniques to get an ion from plasma to the spectrometer. Currently, plasma mass spectrometers are field ready but not necessarily handheld. Optical emission spectrometers are already capable of getting photons to the detector but could eventually be connected to your phone. Inert plasma gas generation is close to field ready if nitrogen generators can be miniaturized. Many of these components are already commercially available or at least have been reported in the literature. Comparisons to other “handheld” elemental analysis devices that employ XRF, LIBS, and electrochemical methods (and their limitations) demonstrate that a “cold” plasma-based spectrometer can be more than competitive. Migrating the cold plasma from an emission only source to a mass spectrometer source, would allow both analyte identification and potentially source apportionment through isotopic fingerprinting, and may be the last major hurdle to overcome. Finally, we offer a possible design to aid in making the cold plasma source more applicable to a field deployment

Unprecedented inhibition of P-gp activity by a novel ruthenium-cyclopentadienyl compound bearing a bipyridine-biotin ligand

International audienceTwo new ruthenium complexes, [Ru(h 5-Cp)(PPh 3)(2,2'-bipy-4,4'-R)] þ with R ¼-CH 2 OH (Ru1) or dibiotin ester (Ru2) were synthesized and fully characterized. Both compounds were tested against two types of breast cancer cells (MCF7 and MDA-MB-231), showing better cytotoxicity than cisplatin in the same experimental conditions. Since multidrug resistance (MDR) is one of the main problems in cancer chemotherapy, we have assessed the potential of these compounds to overcome resistance to treatments. Ru2 showed exceptional selectivity as P-gp inhibitor, while Ru1 is possibly a substrate. In vivo studies in zebrafish showed that Ru2 is well tolerated up to 1.17 mg/L, presenting a LC 50 of 5.73 mg/L at 5 days post fertilization

The geochemical and mineralogical fingerprint of West Antarctica's weak underbelly: Pine Island and Thwaites glaciers

The marine-based West Antarctic Ice Sheet (WAIS) is considered the most unstable part of the Antarctic Ice Sheet, with particular vulnerability in the Amundsen Sea sector where glaciers are melting at an alarming rate. Far-field sea-level data and ice-sheet models have pointed towards at least one major WAIS disintegration during the Late Quaternary, but direct evidence for past collapse(s) from ice-proximal geological archives remains elusive. In order to facilitate geochemical and mineralogical tracing of the two most important glaciers draining into the Amundsen Sea, i.e. Pine Island Glacier (PIG) and Thwaites Glacier (TG), we here provide the first multi-proxy provenance analysis of 26 seafloor surface sediment samples from Pine Island Bay