Differential Membrane Lipid Profiles and Vibrational Spectra of Three Edaphic Algae and One Cyanobacterium.

The membrane glycerolipids of four phototrophs that were isolated from an edaphic assemblage were determined by UPLC-MS after cultivation in a laboratory growth chamber. Identification was carried out by 18S and 16S rDNA sequencing. The algal species were Klebsormidium flaccidum (Charophyta), Oocystis sp. (Chlorophyta), and Haslea spicula (Bacillariophyta), and the cyanobacterium was Microcoleus vaginatus (Cyanobacteria). The glycerolipid profile of Oocystis sp. was dominated by monogalactosyldiacylglycerol (MGDG) species, with MGDG(18:3/16:4) accounting for 68.6%, whereas MGDG(18:3/16:3) was the most abundant glycerolipid in K. flaccidum (50.1%). A ratio of digalactosyldiacylglycerol (DGDG) species to MGDG species (DGDG/MGDG) was shown to be higher in K. flaccidum (0.26) than in Oocystis sp. (0.14). This ratio increased under high light (HL) as compared to low light (LL) in all the organisms, with its highest value being shown in cyanobacterium (0.38-0.58, LL-HL). High contents of eicosapentaenoic acid (EPA, C20:5) and hexadecenoic acid were observed in the glycerolipids of H. spicula. Similar Fourier transform infrared (FTIR) and Raman spectra were found for K. flaccidum and Oocystis sp. Specific bands at 1629.06 and 1582.78 cm-1 were shown by M. vaginatus in the Raman spectra. Conversely, specific bands in the FTIR spectrum were observed for H. spicula at 1143 and 1744 cm-1. The results of this study point out differences in the membrane lipid composition between species, which likely reflects their different morphology and evolutionary patterns.

ACUTE RETINAL DAMAGE AFTER USING A TOXIC PERFLUORO-OCTANE FOR VITREO-RETINAL SURGERY.

PURPOSE: To describe a series of retinal acute toxicity cases with severe visual loss after intraocular use of a toxic perfluoro-octane (PFO). The clinical presentation is described, and the likely causes are analyzed. New biological methods for testing safety of intraocular medical devices are proposed. METHODS: Information regarding a series of eyes suffering acute severe events after intraocular use of a toxic PFO was analyzed. Four types of spectroscopy, nuclear magnetic resonance, and chromatography were used to identify the potential PFO contaminants. Cultures of human retinal pigment epithelial cells (ARPE-19) and porcine neuroretina were used to quantify the toxicity of the suspect PFO lots. RESULTS: Of 117 cases of intraocular toxicity, 96 were considered clearly related to the use of PFO. Fifty-three cases had no light perception, and 97 had no measurable visual acuity. Retinal necrosis (n = 38) and vascular occlusion (n = 33) were the most characteristic findings. Two hydroxyl compounds, perfluorooctanoic acid and dodecafluoro-1-heptanol, and benzene derivatives were identified as the suspected toxic agents. While existing toxicity testing failed, we proposed new tests that demonstrated clear toxicity. CONCLUSION: Protocols to determine cytotoxicity of intraocular medical devices should be revised to assure safety. Acute toxic events should be reported to health authorities and scientific media.

Dark microbiome and extremely low organics in Atacama fossil delta unveil Mars life detection limits.

Identifying unequivocal signs of life on Mars is one of the most important objectives for sending missions to the red planet. Here we report Red Stone, a 163-100 My alluvial fan-fan delta that formed under arid conditions in the Atacama Desert, rich in hematite and mudstones containing clays such as vermiculite and smectites, and therefore geologically analogous to Mars. We show that Red Stone samples display an important number of microorganisms with an unusual high rate of phylogenetic indeterminacy, what we refer to as "dark microbiome", and a mix of biosignatures from extant and ancient microorganisms that can be barely detected with state-of-the-art laboratory equipment. Our analyses by testbed instruments that are on or will be sent to Mars unveil that although the mineralogy of Red Stone matches that detected by ground-based instruments on the red planet, similarly low levels of organics will be hard, if not impossible to detect in Martian rocks depending on the instrument and technique used. Our results stress the importance in returning samples to Earth for conclusively addressing whether life ever existed on Mars.

Spectroscopic study of terrestrial analogues to support rover missions to Mars - A Raman-centred review.

The 2020s could be called, with little doubt, the "Mars decade". No other period in space exploration history has experienced such interest in placing orbiters, rovers and landers on the Red Planet. In 2021 alone, the Emirates' first Mars Mission (the Hope orbiter), the Chinese Tianwen-1 mission (orbiter, lander and rover), and NASA's Mars 2020 Perseverance rover reached Mars. The ExoMars mission Rosalind Franklin rover is scheduled for launch in 2022. Beyond that, several other missions are proposed or under development. Among these, MMX to Phobos and the very important Mars Sample Return can be cited. One of the key mission objectives of the Mars 2020 and ExoMars 2022 missions is the detection of traces of potential past or present life. This detection relies to a great extent on the analytical results provided by complementary spectroscopic techniques. The development of these novel instruments has been carried out in step with the analytical study of terrestrial analogue sites and materials, which serve to test the scientific capabilities of spectroscopic prototypes while providing crucial information to better understand the geological processes that could have occurred on Mars. Being directly involved in the development of three of the first Raman spectrometers to be validated for space exploration missions (Mars 2020/SuperCam, ExoMars/RLS and RAX/MMX), the present review summarizes some of the most relevant spectroscopy-based analyses of terrestrial analogues carried out over the past two decades. Therefore, the present work describes the analytical results gathered from the study of some of the most distinctive terrestrial analogues of Martian geological contexts, as well as the lessons learned mainly from ExoMars mission simulations conducted at representative analogue sites. Learning from the experience gained in the described studies, a general overview of the scientific outcome expected from the spectroscopic system developed for current and forthcoming planetary missions is provided.

ExoFiT trial at the Atacama Desert (Chile): Raman detection of biomarkers by representative prototypes of the ExoMars/Raman Laser Spectrometer.

In this work, the analytical research performed by the Raman Laser Spectrometer (RLS) team during the ExoFiT trial is presented. During this test, an emulator of the Rosalind Franklin rover was remotely operated at the Atacama Desert in a Mars-like sequence of scientific operations that ended with the collection and the analysis of two drilled cores. The in-situ Raman characterization of the samples was performed through a portable technology demonstrator of RLS (RAD1 system). The results were later complemented in the laboratory using a bench top RLS operation simulator and a X-Ray diffractometer (XRD). By simulating the operational and analytical constraints of the ExoMars mission, the two RLS representative instruments effectively disclosed the mineralogical composition of the drilled cores (k-feldspar, plagioclase, quartz, muscovite and rutile as main components), reaching the detection of minor phases (e.g., additional phyllosilicate and calcite) whose concentration was below the detection limit of XRD. Furthermore, Raman systems detected many organic functional groups (-C≡N, -NH2 and C-(NO2)), suggesting the presence of nitrogen-fixing microorganisms in the samples. The Raman detection of organic material in the subsurface of a Martian analogue site presenting representative environmental conditions (high UV radiation, extreme aridity), supports the idea that the RLS could play a key role in the fulfilment of the ExoMars main mission objective: to search for signs of life on Mars.

ExoMars Raman Laser Spectrometer: A Tool to Semiquantify the Serpentinization Degree of Olivine-Rich Rocks on Mars.

We evaluated the effectiveness of the ExoMars Raman laser spectrometer (RLS) to determine the degree of serpentinization of olivine-rich units on Mars. We selected terrestrial analogs of martian ultramafic rocks from the Leka Ophiolite Complex (LOC) and analyzed them with both laboratory and flight-like analytical instruments. We first studied the mineralogical composition of the samples (mostly olivine and serpentine) with state-of-the-art diffractometric (X-ray diffractometry [XRD]) and spectroscopic (Raman, near-infrared spectroscopy [NIR]) laboratory systems. We compared these results with those obtained using our RLS ExoMars Simulator. Our work shows that the RLS ExoMars Simulator successfully identified all major phases. Moreover, when emulating the automatic operating mode of the flight instrument, the RLS ExoMars Simulator also detected several minor compounds (pyroxene and brucite), some of which were not observed by NIR and XRD (e.g., calcite). Thereafter, we produced RLS-dedicated calibration curves (R2 between 0.9993 and 0.9995 with an uncertainty between ±3.0% and ±5.2% with a confidence interval of 95%) to estimate the relative content of olivine and serpentine in the samples. Our results show that RLS can be very effective in identifying serpentine, a scientific target of primary importance for the potential detection of biosignatures on Mars-the main objective of the ExoMars rover mission.

ExoMars Raman Laser Spectrometer (RLS): development of chemometric tools to classify ultramafic igneous rocks on Mars.

This work aims to evaluate whether the multi-point analysis the ExoMars Raman Laser Spectrometer (RLS) will perform on powdered samples could serve to classify ultramafic rocks on Mars. To do so, the RLS ExoMars Simulator was used to study terrestrial analogues of Martian peridotites and pyroxenites by applying the operational constraints of the Raman spectrometer onboard the Rosalind Franklin rover. Besides qualitative analysis, RLS-dedicated calibration curves have been built to estimate the relative content of olivine and pyroxenes in the samples. These semi-quantitative results, combined with a rough estimate of the concentration ratio between clino- and ortho-pyroxene mineral phases, were used to classify the terrestrial analogues. XRD data were finally employed as reference to validate Raman results. As this preliminary work suggests, ultramafic rocks on Mars could be effectively classified through the chemometric analysis of RLS data sets. After optimization, the proposed chemometric tools could be applied to the study of the volcanic geological areas detected at the ExoMars landing site (Oxia Planum), whose mineralogical composition and geological evolution have not been fully understood.

Effect of Different Broad Waveband Lights on Membrane Lipids of a Cyanobacterium, Synechococcus sp., as Determined by UPLC-QToF-MS and Vibrational Spectroscopy.

Differential profile of membrane lipids and pigments of a Synechococcus sp. cyanobacterial strain cells exposed to blue, green, red and white light are determined by means of liquid chromatography and mass spectrometry or diode array detection. Raman and ATR-IR spectra of intact cells under the diverse light wavebands are also reported. Blue light cells exhibited an increased content of photosynthetic pigments as well as specific species of membrane glycerolipids as compared to cells exposed to other wavebands. The A630/A680 ratio indicated an increased content of phycobilisomes (PBS) in the blue light-exposed cells. Some differences in the protein conformation between the four light waveband-exposed cells were deduced from the variable absorbance at specific wavenumbers in the FT-Raman and ATR-FTIR spectra, in particular bands assigned to amide I and amide II. Bands from 1180 to 950 cm(-1) in the ATR-FTIR spectrum suggest degraded outer membrane polysaccharide in the blue light-exposed cells.

Linking groundwater pollution to the decay of 15th-century sculptures in Burgos Cathedral (northern Spain).

Precipitation of salts-mainly hydrated Mg-Na sulfates-in building materials is rated as one of the most severe threats to the preservation of our architectural and cultural heritage. Nevertheless, the origin of this pathology is still unknown in many cases. Proper identification of the cause of damage is crucial for correct planning of future restoration actions. The goal of this study is to identify the source of the degradation compounds that are affecting the 15th-century limestone sculptures that decorate the retro-choir of Burgos Cathedral (northern Spain). To this end, detailed characterization of minerals by in situ (Raman spectroscopy) and laboratory techniques (XRD, Raman and FTIR) was followed by major elements (ICP and IC) and isotopic analysis (δ(34)S and δ(15)N) of both the mineral phases precipitated on the retro-choir and the dissolved salts in groundwater in the vicinity of the cathedral. The results reveal unequivocal connection between the damage observed and capillary rise of salts-bearing water from the subsoil. The multianalytical methodology used is widely applicable to identify the origin of common affections suffered by historical buildings and masterpieces.