EPMA maps unveil the actual chemical variations and crystallisation sequence of pyroxene and plagioclase solidified from a basaltic liquid at variable cooling rates

Crystal-chemical variations of pyroxene (px) and plagioclase (plg) have been analysed by X-ray electron-microprobe (EPMA) mapping to quantify their actual chemical dispersions. These phases were experimentally crystallised from a basaltic liquid (B100, MORB from Iceland) at cooling rates of 1, 7, 60 and 180 °C/h from 1300 °C down to 800 °C. Experiments were run at ambient conditions applying defined temperature paths mirroring characteristic cooling rates from innermost to outermost portions of metre- to centimetre-thick lavas, dikes and bombs emplaced under submarine to subaerial conditions. As the cooling rate increases from 1 to 180 °C/h, the run-products become progressively enriched in pyroxene and depleted in plagioclase, while spinel is invariably low (few area%) and glass is significant only at 180 °C/h. An increase of cooling rate generally leads to enrichment of Al2O3 and depletion of MgO in px, while the opposite behaviour is observed for plg; these trends are mirrored by calculated cations (apfu: atom per formula unit) and components. Average variations as a function of cooling rate are similar to those already observed through classical analysis performed by single point EPMA. However, the actual chemical distributions of CaO versus MgO, Al2O3 and FeOtot oxides unveil the presence of a wider range in pyroxene chemistry. In particular, one px (px-1, CaO-rich, diopsidic type) is present at all the applied cooling rates; a very low CaO-px (px-2, pigeonite or orthopyroxene type) is detected at 1 °C/h; and, finally, once more population of px (px-3, CaO-poor diopsidic type) appears at 60 and 180 °C/h. By contrast, plg analyses yield invariably identical compositions. Textural variations as a function of cooling rate and geothermometric estimations indicate that px-1 crystallised at high-T (or low ΔT), while plg mainly grew in the residual melt produced by the saturation of px. If only textures were evaluated, this order of segregation would like remain unrecognised since px at low cooling rates is smaller than plg. The abundance of phases, their crystal-chemical features, and their order of segregation can be regarded through a theoretical framework of a time-temperature-transformation (TTT) diagram. The most significant chemical variations are displayed by MgO and Al2O3 for both px and plg, which faithfully capture the evolution of cooling conditions. The chemical compositions of px-1 is close to the thermodynamic equilibrium only at 1 °C/h. As the cooling rates increase, the px chemistry indicates disequilibrium conditions. Finally, this study shows that as ΔT/Δt increases, the most abundant px (px-1) and plg are forced towards compositions that become progressively closer to those of the parental liquid

Short-range order and chemical compositions of glasses along the basaltic-rhyolite sub-alkaline join by Raman and FTIR spectroscopies

Six sub-alkaline glasses with compositions progressively shifting from the tholeiitic basalt (B100) end-member to the rhyolite (R100) end-member were investigated and analysed in the same frequency domain by both Raman and FTIR. This approach highlights spectroscopic similarities and differences such as positions, widths and intensities of Raman and FTIR bands, which may also exhibit significant overlapping. Both the Raman and FTIR spectra show several peaks grouped in three main vibrational windows: 200–650 (low frequency region, named F-I in this study), 650–850 (intermediate region, F-II) and 850–1250 cm−1 (high-frequency region, F-III). In line with previous investigations, the F-I interval can be ascribed to vibrational modes involving rings of tetrahedrally coordinated cations linked by bridging oxygens. It can be fitted with three components, whereas F-II involves the motion of Si atoms within its oxygen cage and is adequately represented by two components. Finally, F-III contains different T-O (T = tetrahedrally coordinated network-forming cation) stretching bands that can be tied to the overall degree of polymerization of the glass and are fitted with four components. In some glasses, the three and the two components within F-I and F-II are identifiable in both Raman and FTIR spectra; in cases of strong peak overlap, these peaks can be complementary to one another towards our interpretation of the molecular arrangement(s) in these glasses. Indeed, the positions of the four components in F-III are first constrained in the Raman spectra, which are more identifiable, then further refined using available Raman spectra for corresponding chemically simple silicate systems. The nine fitted components can reproduce the Raman and FTIR spectra extremely well. As a function of the amount of SiO2, the positions and intensities of the three low frequency components progressively shift in both Raman and FTIR. Similarly, the two bands in the F-II intermediate region exhibit a monotonic shifting of their positions. Indeed, the components at high frequency display less significant shifting of their positions as a function of SiO2, while their intensities change more markedly in the Raman spectrum compared to those for FTIR. The vibrational components measured in this study provide a referenced dataset of assignations of the most abundant natural volcanic glasses. Therefore, it provides a diagnostic tool based on the cross-validation of Raman and FTIR spectra to quickly identify the glass chemistry, offering the possibility to expand the applicability of remote investigations

Adverse events in thyroid surgery: observational study in three surgical units with high volume/year

Background: Thyroid surgery, performed for benign or malignant pathologies, is one of the most frequently performed procedures and its frequency has even been increasing in recent years. Postoperative bleeding, recurrent laryngeal nerve (RLN) palsy, associated to dysphonia, dysphagia, dyspnea, and hypoparathyroidism represent the most fearful and common complications. We conducted a multicenter, observational study of retrospectively collected data in three high-volume referral centers, enrolling all patients undergone to thyroid surgery between January 2016 and December 2017 in Parma University Hospital, Cagliari University Hospital and Ferrara University Hospital. Materials: Patients were divided into five groups, differentiated thyroid carcinoma, medullary thyroid carcinoma, non-toxic benign pathology, hyperfunctioning benign pathology and NIFTP (Non-invasive Follicular Thyroid neoplasm with Papillary-like nuclear features). A follow up at 7 and 30 days was executed, evaluating the onset of paresthesia, dysphonia and dysphagia. A 6-month follow-up was conducted in cases of early complications. Results: Totally, 1252 patients were eligible for the study: 907 female and 345 male, with a female to male ratio of 2.6:1 and an average age of 53.428. Total thyroidectomy was performed in 1022 cases, lobectomy in 230. After 6 months we recorded paresthesia in 0.5%, dysphonia in 1.8% and dysphagia in 0.5%. Conclusion: Our study confirms once again that a share of morbidity escapes the possibilities of prediction and control by the operator, depending on patient anamnestic, pathological or anatomical factors

Medication use, renin-angiotensin system inhibitors, and acute care utilization after hospitalization in patients with chronic kidney disease.

OBJECTIVES: The aims of this secondary analysis were to: (a) characterize medication use following hospital discharge for patients with chronic kidney disease (CKD), and (b) investigate relationships of medication use with the primary composite outcome of acute care utilization 90 days after hospitalization. METHODS: The CKD-Medication Intervention Trial (CKD-MIT) enrolled acutely ill hospitalized patients with CKD stages 3-5 not dialyzed (CKD 3-5 ND). In this post hoc analysis, data for medication use were characterized, and the relationship of medication use with the primary outcome was evaluated using Cox proportional hazards models. RESULTS: Participants were taking a mean of 12.6 (standard deviation=5.1) medications, including medications from a wide variety of medication classes. Nearly half of study participants were taking angiotensin-converting enzyme (ACE) inhibitors or angiotensin II receptor blockers (ARB). ACE inhibitor/ARB use was associated with decreased risk of the primary outcome (hazard ratio=0.51; 95% confidence interval 0.28-0.95; CONCLUSIONS: A large number, variety, and complexity of medications were used by hospitalized patients with CKD 3-5 ND. ACE inhibitor or ARB use at hospital discharge was associated with a decreased risk of 90-day acute care utilization

Characterizing the Near-infrared Spectra of Flares from TRAPPIST-1 During JWST Transit Spectroscopy Observations

We present the first analysis of JWST near-infrared spectroscopy of stellar flares from TRAPPIST-1 during transits of rocky exoplanets. Four flares were observed from 0.6--2.8 $\mu$m with NIRISS and 0.6--3.5 $\mu$m with NIRSpec during transits of TRAPPIST-1b, f, and g. We discover P$\alpha$ and Br$\beta$ line emission and characterize flare continuum at wavelengths from 1--3.5 $\mu$m for the first time. Observed lines include H$\alpha$, P$\alpha$-P$\epsilon$, Br$\beta$, He I $\lambda$0.7062$\mu$m, two Ca II infrared triplet (IRT) lines, and the He I IRT. We observe a reversed Paschen decrement from P$\alpha$-P$\gamma$ alongside changes in the light curve shapes of these lines. The continuum of all four flares is well-described by blackbody emission with an effective temperature below 5300 K, lower than temperatures typically observed at optical wavelengths. The 0.6--1 $\mu$m spectra were convolved with the TESS response, enabling us to measure the flare rate of TRAPPIST-1 in the TESS bandpass. We find flares of 10$^{30}$ erg large enough to impact transit spectra occur at a rate of 3.6$\substack{+2.1 \\ -1.3}$ flare d$^{-1}$, $\sim$10$\times$ higher than previous predictions from K2. We measure the amount of flare contamination at 2 $\mu$m for the TRAPPIST-1b and f transits to be 500$\pm$450 and 2100$\pm$400 ppm, respectively. We find up to 80% of flare contamination can be removed, with mitigation most effective from 1.0--2.4 $\mu$m. These results suggest transits affected by flares may still be useful for atmospheric characterization efforts.Comment: 29 pages, 17 figures, 3 tables, accepted to The Astrophysical Journa

ATOCA: an algorithm to treat order contamination. Application to the NIRISS SOSS mode

After a successful launch, the James Webb Space Telescope is preparing to undertake one of its principal missions, the characterization of the atmospheres of exoplanets. The Single Object Slitless Spectroscopy (SOSS) mode of the Near Infrared Imager and Slitless Spectrograph (NIRISS) is the only observing mode that has been specifically designed for this objective. It features a wide simultaneous spectral range (0.6--2.8\,\micron) through two spectral diffraction orders. However, due to mechanical constraints, these two orders overlap slightly over a short range, potentially introducing a ``contamination'' signal in the extracted spectrum. We show that for a typical box extraction, this contaminating signal amounts to 1\% or less over the 1.6--2.8\,\micron\ range (order 1), and up to 1\% over the 0.85--0.95\,\micron\ range (order 2). For observations of exoplanet atmospheres (transits, eclipses or phase curves) where only temporal variations in flux matter, the contamination signal typically biases the results by order of 1\% of the planetary atmosphere spectral features strength. To address this problem, we developed the Algorithm to Treat Order ContAmination (ATOCA). By constructing a linear model of each pixel on the detector, treating the underlying incident spectrum as a free variable, ATOCA is able to perform a simultaneous extraction of both orders. We show that, given appropriate estimates of the spatial trace profiles, the throughputs, the wavelength solutions, as well as the spectral resolution kernels for each order, it is possible to obtain an extracted spectrum accurate to within 10\,ppm over the full spectral range.Comment: Submitted to PASP. 22 pages, 12 figure

Atmospheric Reconnaissance of TRAPPIST-1 b with JWST/NIRISS: Evidence for Strong Stellar Contamination in the Transmission Spectra

TRAPPIST-1 is a nearby system of seven Earth-sized, temperate, rocky exoplanets transiting a Jupiter-sized M8.5V star, ideally suited for in-depth atmospheric studies. Each TRAPPIST-1 planet has been observed in transmission both from space and from the ground, confidently rejecting cloud-free, hydrogen-rich atmospheres. Secondary eclipse observations of TRAPPIST-1 b with JWST/MIRI are consistent with little to no atmosphere given the lack of heat redistribution. Here we present the first transmission spectra of TRAPPIST-1 b obtained with JWST/NIRISS over two visits. The two transmission spectra show moderate to strong evidence of contamination from unocculted stellar heterogeneities, which dominates the signal in both visits. The transmission spectrum of the first visit is consistent with unocculted starspots and the second visit exhibits signatures of unocculted faculae. Fitting the stellar contamination and planetary atmosphere either sequentially or simultaneously, we confirm the absence of cloud-free hydrogen-rich atmospheres, but cannot assess the presence of secondary atmospheres. We find that the uncertainties associated with the lack of stellar model fidelity are one order of magnitude above the observation precision of 89 ppm (combining the two visits). Without affecting the conclusion regarding the atmosphere of TRAPPIST-1 b, this highlights an important caveat for future explorations, which calls for additional observations to characterize stellar heterogeneities empirically and/or theoretical works to improve model fidelity for such cool stars. This need is all the more justified as stellar contamination can affect the search for atmospheres around the outer, cooler TRAPPIST-1 planets for which transmission spectroscopy is currently the most efficient technique.Comment: 26 pages, 11 figures, accepted for publication in The Astrophysical Journal Letter

Near-Infrared Transmission Spectroscopy of HAT-P-18 \,b with NIRISS: Disentangling Planetary and Stellar Features in the Era of JWST

The JWST Early Release Observations (ERO) included a NIRISS/SOSS (0.6-2.8$\,\mu$m) transit of the $\sim\,$850$\,$K Saturn-mass exoplanet HAT-P-18$\,$b. Initial analysis of these data reported detections of water, escaping helium, and haze. However, active K dwarfs like HAT-P-18 possess surface heterogeneities $-$ starspots and faculae $-$ that can complicate the interpretation of transmission spectra, and indeed, a spot-crossing event is present in HAT-P-18$\,$b's NIRISS/SOSS light curves. Here, we present an extensive reanalysis and interpretation of the JWST ERO transmission spectrum of HAT-P-18$\,$b, as well as HST/WFC3 and $\textit{Spitzer}$/IRAC transit observations. We detect H$_2$O (12.5$\,\sigma$), CO$_2$ (7.3$\,\sigma$), a cloud deck (7.4$\,\sigma$), and unocculted starspots (5.8$\,\sigma$), alongside hints of Na (2.7$\,\sigma$). We do not detect the previously reported CH$_4$ ($\log$ CH$_4$ $<$ -6 to 2$\,\sigma$). We obtain excellent agreement between three independent retrieval codes, which find a sub-solar H$_2$O abundance ($\log$ H$_2$O $\approx -4.4 \pm 0.3$). However, the inferred CO$_2$ abundance ($\log$ CO$_2$ $\approx -4.8 \pm 0.4$) is significantly super-solar and requires further investigation into its origin. We also introduce new stellar heterogeneity considerations by fitting for the active regions' surface gravities $-$ a proxy for the effects of magnetic pressure. Finally, we compare our JWST inferences to those from HST/WFC3 and $\textit{Spitzer}$/IRAC. Our results highlight the exceptional promise of simultaneous planetary atmosphere and stellar heterogeneity constraints in the era of JWST and demonstrate that JWST transmission spectra may warrant more complex treatments of the transit light source effect

Homogeneous search for helium in the atmosphere of 11 gas giant exoplanets with SPIRou

The metastable helium triplet in the near-infrared (10833{\AA}) is among the most important probes of exoplanet atmospheres. It can trace their extended outer layers and constrain mass-loss. We use the near-infrared high-resolution spectropolarimeter SPIRou on the CFHT to search for the spectrally resolved helium triplet in the atmospheres of eleven exoplanets, ranging from warm mini-Neptunes to hot Jupiters and orbiting G, K, and M dwarfs. Observations were obtained as part of the SPIRou Legacy Survey and complementary open-time programs. We apply a homogeneous data reduction to all datasets and set constraints on the presence of metastable helium, despite the presence of systematics in the data. We confirm published detections for HAT-P-11b, HD189733b, and WASP-69b and set upper limits for the other planets. We apply the p-winds open source code to set upper limits on the mass-loss rate for the non-detections and to constrain the thermosphere temperature, mass-loss rate, line-of-sight velocity, and the altitude of the thermosphere for the detections. We confirm that the presence of metastable helium correlates with the stellar mass and the XUV flux received by the planets. We investigated the correlation between the mass-loss rate and the presence of metastable helium, but it remains difficult to draw definitive conclusions. Finally, some of our results are in contradiction with previous results in the literature, therefore we stress the importance of repeatable, homogeneous, and larger-scale analyses of the helium triplet to obtain robust statistics, study temporal variability, and better understand how the helium triplet can be used to explore the evolution of exoplanets.Comment: 28 pages, 13 figures, Accepted in A&A for publicatio