The mechanisms of hazardous silicic eruptions are controlled by complex, poorly-understood conduit processes. Observations of recent Chilean rhyolite eruptions have revealed the importance of hybrid activity, involving simultaneous explosive and effusive emissions from a common vent. Such behavior hinges upon the ability of gas to decouple from magma in the shallow conduit. Tuffisite veins are increasingly suspected to be a key facilitator of outgassing, as they repeatedly provide a transient permeable escape route for volcanic gases. Intersection of foam domains by tuffisite veins appears critical to efficient outgassing. However, knowledge is currently lacking into textural heterogeneities within shallow conduits, their relationship with tuffisite vein propagation, and the implications for fragmentation and degassing processes. Similarly, the magmatic vesiculation response to upper conduit pressure perturbations, such as those related to the slip of dense magma plugs, remains largely undefined. Here we provide a detailed characterization of an exceptionally large tuffisite vein within a rhyolitic obsidian bomb ejected during transitional explosive-effusive activity at Chaitén, Chile in May 2008. Vein textures and chemistry provide a time-integrated record of the invasion of a dense upper conduit plug by deeper fragmented magma. Quantitative textural analysis reveals diverse vesiculation histories of various juvenile clast types. Using vesicle size distributions, bubble number densities, zones of diffusive water depletion, and glass H 2 O concentrations, we propose a multi-step degassing/fragmentation history, spanning deep degassing to explosive bomb ejection. Rapid decompression events of ∼3-4 MPa are associated with fragmentation of foam and dense magma at ∼200-360 m depth in the conduit, permitting vertical gas and pyroclast mobility over hundreds of meters. Permeable pathway occlusion in the dense conduit plug by pyroclast accumulation and sintering preceded ultimate bomb ejection, which then triggered a final bubble nucleation event. Our results highlight how the vesiculation response of magma to decompression events is highly sensitive to the local melt volatile concentration, which is strongly spatially Saubin et al.Chaitén Tuffisites Record Conduit Processes heterogeneous. Repeated opening of pervasive tuffisite vein networks promotes this heterogeneity, allowing juxtaposition of variably volatile-rich magma fragments that are derived from a wide range of depths in the conduit. This process enables efficient but explosive removal of gas from rhyolitic magma and creates a complex textural collage within dense rhyolitic lava, in which neighboring fused clasts may have experienced vastly different degassing histories.

FTIR absorption micro-spectroscopy is a widely used, powerful technique for analysing biological materials. In principle it is a straightforward linear absorption spectroscopy, but it can be affected by artefacts that complicate the interpretation of the data. In this article, artefacts produced by the electric-field standing-wave (EFSW) in micro-reflection-absorption (transflection) spectroscopy are investigated. An EFSW is present at reflective metallic surfaces due to the interference of incident and reflected light. The period of this standing wave is dependent on the wavelength of the radiation and can produce non-linear changes in absorbance with increasing sample thickness (non-Beer-Lambert like behaviour). A protein micro-structure was produced as a simple experimental model for a biological cell and used to evaluate the differences between FTIR spectra collected in transmission and transflection. By varying the thickness of the protein samples, the relationship between the absorbance and sample thickness in transflection was determined, and shown to be consistent with optical interference due to the EFSW coupled with internal reflection from the sample top surface. FTIR spectral image data from MCF 7 breast adenocarcinoma cells was then analysed to determine the severity of the EFSW artefact in data from a real sample. The results from these measurements confirmed that the EFSW artefact has a profound effect on transflection spectra, and in this case the main spectral variations were related to the sample thickness rather than any biochemical differences.

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Studies of drug-cell interactions in cancer model systems are essential in the preclinical stage of rational drug design, which relies on a thorough understanding of the mechanisms underlying cytotoxic activity and biological effects, at a molecular level.This study aimed at applying complementary vibrational spectroscopy methods to evaluate the cellular impact of two Pt(II) and Pd(II) dinuclear chelates with spermine (Pt 2 Spm and Pd 2 Spm), using cisplatin (cis-Pt(NH 3 ) 2 Cl 2 ) as a reference compound. Their effects on cellular metabolism were monitored in a human triple-negative metastatic breast cancer cell line (MDA-MB-231) by Raman and synchrotron-radiation infrared microspectroscopies, for different drug concentrations (2-8 mM) at 48 h exposure.Multivariate data analysis was applied (unsupervised PCA), unveiling drug-and concentration-dependent effects: apart from discrimination between control and drugtreated cells, a clear separation was obtained for the different agents studiedmononuclear vs. polynuclear, and Pt(II) vs. Pd(II). Spectral biomarkers of drug action were identified, as well as the cellular response to the chemotherapeutic insult. The main effect of the tested compounds was found to be on DNA, lipids and proteins, the Pd(II) agent having a more significant impact on proteins while its Pt(II) homologue affected the cellular lipid content at lower concentrations, which suggests the occurrence of distinct and unconventional pathways of cytotoxicity for these dinuclear polyamine complexes. Raman and FTIR microspectroscopies were confirmed as powerful non-invasive techniques to obtain unique spectral signatures of the biochemical impact and physiological reaction of cells to anticancer agents.