Reconciling diverse lacustrine and terrestrial system response to penultimate deglacial warming in southern Europe

Unlike the most recent deglaciation, the regional expression of climate changes during the penultimate deglaciation remains understudied, even though it led into a period of excess warmth with estimates of global average temperature 1–2 °C, and sea level ∼6 m, above pre-industrial values. We present the first complete high-resolution southern European diatom record capturing the penultimate glacial-interglacial transition, from Lake Ioannina (northwest Greece). It forms part of a suite of proxies selected to assess the character and phase relationships of terrestrial and aquatic ecosystem response to rapid climate warming, and to resolve apparent conflicts in proxy evidence for regional paleohydrology. The diatom data suggest a complex penultimate deglaciation driven primarily by multiple oscillations in lake level, and provide firm evidence for the regional influence of abrupt changes in North Atlantic conditions. There is diachroneity in lake and terrestrial ecosystem response to warming at the onset of the last interglacial, with an abrupt increase in lake level occurring ∼2.7 k.y. prior to sustained forest expansion with peak precipitation. We identify the potentially important role of direct input of snow melt and glacial meltwater transfer to the subterranean karst system in response to warming, which would cause rising regional groundwater levels. This explanation, and the greater sensitivity of diatoms to subtle changes in temperature, reconciles the divergent lacustrine and terrestrial proxy evidence and highlights the sensitivity of lakes situated in mountainous karstic environments to past climate warming

Ultrasound delivery of Surface Enhanced InfraRed Absorption active gold-nanoprobes into fibroblast cells: a biological study via Synchrotron-based InfraRed microanalysis at single cell level

Ultrasound (US) induced transient membrane permeabilisation has emerged as a hugely promising tool for the delivery of exogenous vectors through the cytoplasmic membrane, paving the way to the design of novel anticancer strategies by targeting functional nanomaterials to specific biological sites. An essential step towards this end is the detailed recognition of suitably marked nanoparticles in sonoporated cells and the investigation of the potential related biological effects. By taking advantage of Synchrotron Radiation fourier transform infrared micro-spectroscopy (SR-microftiR) in providing highly sensitive analysis at the single cell level, we studied the internalisation of a nanoprobe within fibroblasts (NIH-3T3) promoted by low-intensity US. To this aim we employed 20 nm gold nanoparticles conjugated with the IR marker 4-aminothiophenol. The significant Surface Enhanced Infrared Absorption provided by the nanoprobes, with an absorbance increase up to two orders of magnitude, allowed us to efficiently recognise their inclusion within cells. Notably, the selective and stable SR- microftiR detection from single cells that have internalised the nanoprobe exhibited clear changes in both shape and intensity of the spectral profile, highlighting the occurrence of biological effects. Flow cytometry, immunofluorescence and murine cytokinesis-block micronucleus assays confirmed the presence of slight but significant cytotoxic and genotoxic events associated with the US-nanoprobe combined treatments. our results can provide novel hints towards US and nanomedicine combined strategies for cell spectral imaging as well as drug delivery-based therapies

Towards microfluidic reactors for in situ synchrotron infrared studies

Anodically bonded etched silicon microfluidic devices that allow infrared spectroscopic measurement of solutions are reported. These extend spatially well-resolved in situ infrared measurement to higher temperatures and pressures than previously reported, making them useful for effectively time-resolved measurement of realistic catalytic processes. A data processing technique necessary for the mitigation of interference fringes caused by multiple reflections of the probe beam is also describe

Coherent control of ac Stark allowed transition in Λ\Lambda system

We show that quantum-interference-related phenomena, such as electromagnetically induced transparency, gain without inversion and enhanced refractive index may occur on electric-dipole forbidden transitions. Gain/dispersion characteristics of such transitions strongly depend upon the relative phase between the driving and probe fields. Unlike allowed transitions, gain/absorption behavior of forbidden transitions exhibit antisymmetric feature on the Rabi sidebands. Absorption/gain spectra possess extremely narrow sub-natural resonances.Comment: 5 pages, 5 figure

Persistent millennial-scale climate variability in Southern Europe during Marine Isotope Stage 6

Exploring the mode and tempo of millennial-scale climate variability under evolving boundary conditions can provide insights into tipping points in different parts of the Earth system, and can facilitate a more detailed understanding of climate teleconnections and phase relationships between different Earth system components. Here we use fossil diatom and stable carbon and oxygen isotope analysis of lake sediment deposits (core I-284) from the Ioannina basin, NW Greece, to explore in further detail millennial-scale climate instability in southern Europe during Marine Isotope Stage 6 (MIS 6; ca. 185‒130 ka). This interval correlates with the Vlasian Stage in Greece and the Late Saalian Substage in northern Europe, which were both characterised by extensive glaciations. The new dataset resolves at least 18 discrete warmer/wetter intervals, many of which were associated with strong Asian Monsoon events and North Atlantic interstadials. A number of cooler/drier intervals are also identified in the I-284 record, which are typically associated with weaker Asian Monsoon events and North Atlantic stadials, consistent with a variable Atlantic Meridional Overturning Circulation. Unlike the subdued changes in tree populations that are observed at Ioannina during mid-to-late MIS 6, the diatom record contains frequent high-amplitude oscillations in species assemblages, pointing to its sensitivity at a time when the lake system must have been close to environmental thresholds. Millennial-scale variability in diatom species assemblages continues into late MIS 6 at Ioannina, contributing important evidence for an emerging picture of frequent and persistent climate instability even at times of high global ice volume

Elucidating the significance of copper and nitrate speciation in Cu-SSZ-13 for N2O formation during NH3-SCR

Unwanted N2O formation is a problem that has been noted in selective catalytic reduction (SCR) where copper zeolite catalysts are utilized. With its immense global warming potential and long-term stability, elevated atmospheric N2O has already been identified as a future challenge in the war on climate change. This paper explores the phenomenon of N2O formation during NH3-SCR over Cu-SSZ-13 catalysts, which are currently commercialized in automotive emissions control systems, and proposes a link between N2O production and the local copper environment found within the zeolite. To achieve this, a comparison is made between two Cu-SSZ-13 samples with different copper co-ordinations produced via different synthesis methods. A combination of synchrotron X-ray absorption near-edge spectroscopy, UV–vis, Raman, and density functional theory (DFT) is used to characterize the nature of copper species present within each sample. Synchrotron IR microspectroscopy is then used to compare their behavior during SCR under operando conditions and monitor the evolution of nitrate intermediates, which, along with further DFT, informs a mechanistic model for nitrate decomposition pathways. Increased N2O production is seen in the Cu-SSZ-13 sample postulated to contain a linear Cu species, providing an important correlation between the catalytic behavior of Cu-zeolites and the nature of their metal ion loading and speciation

Refinement of pore size at sub-angstrom precision in robust metal-organic frameworks for separation of xylenes

The demand for xylenes is projected to increase over the coming decades. The separation of xylene isomers, particularly p- and m-xylenes, is vital for the production of numerous polymers and materials. However, current state-of-the-art separation is based upon fractional crystallisation at 220 K which is highly energy intensive. Here, we report the discrimination of xylene isomers via refinement of the pore size in a series of porous metal–organic frameworks, MFM-300, at sub-angstrom precision leading to the optimal kinetic separation of all three xylene isomers at room temperature. The exceptional performance of MFM-300 for xylene separation is confirmed by dynamic ternary breakthrough experiments. In-depth structural and vibrational investigations using synchrotron X-ray diffraction and terahertz spectroscopy define the underlying host–guest interactions that give rise to the observed selectivity (p-xylene < o-xylene < m-xylene) and separation factors of 4.6–18 for p- and m-xylenes