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Before the Perseverance rover landing, the acoustic environment of Mars was unknown. Models predicted that: (1) atmospheric turbulence changes at centimetre scales or smaller at the point where molecular viscosity converts kinetic energy into heat1, (2) the speed of sound varies at the surface with frequency2,3 and (3) high-frequency waves are strongly attenuated with distance in CO2 (refs. 2-4). However, theoretical models were uncertain because of a lack of experimental data at low pressure and the difficulty to characterize turbulence or attenuation in a closed environment. Here, using Perseverance microphone recordings, we present the first characterization of the acoustic environment on Mars and pressure fluctuations in the audible range and beyond, from 20 Hz to 50 kHz. We find that atmospheric sounds extend measurements of pressure variations down to 1,000 times smaller scales than ever observed before, showing a dissipative regime extending over five orders of magnitude in energy. Using point sources of sound (Ingenuity rotorcraft, laser-induced sparks), we highlight two distinct values for the speed of sound that are about 10 m s-1 apart below and above 240 Hz, a unique characteristic of low-pressure CO2-dominated atmosphere. We also provide the acoustic attenuation with distance above 2 kHz, allowing us to explain the large contribution of the CO2 vibrational relaxation in the audible range. These results establish a ground truth for the modelling of acoustic processes, which is critical for studies in atmospheres such as those of Mars and Venus.
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The SuperCam instrument, onboard the Perseverance rover (Mars 2020 mission) is designed to perform remote analysis on the Martian surface employing several spectroscopic techniques such as Laser Induced Breakdown Spectroscopy (LIBS), Time-Resolved Raman (TRR), Time-Resolved Fluorescence (TRF) and Visible and Infrared (VISIR) reflectance. In addition, SuperCam also acquires high-resolution images using a color remote micro-imager (RMI) as well as sounds with its microphone. SuperCam has three main subsystems, the Mast Unit (MU) where the laser for chemical analysis and collection optics are housed, the Body Unit (BU) where the different spectrometers are located inside the rover, and the SuperCam Calibration Target (SCCT) located on the rover's deck to facilitate calibration tests at similar ambient conditions as the analyzed samples. To perform adequate calibrations on Mars, the 22 mineral samples included in the complex SCCT assembly must have a very homogeneous distribution of major and minor elements. The analysis and verification of such homogeneity for the 5-6 replicates of the samples included in the SCCT has been the aim of this work. To verify the physic-chemical homogeneity of the calibration targets, micro Energy Dispersive X-ray Fluorescence (EDXRF) imaging was first used on the whole surface of the targets, then the relative abundances of the detected elements were computed on 20 randomly distributed areas of 100 × 100 µm. For those targets showing a positive Raman response, micro-Raman spectroscopy imaging was performed on the whole surface of the targets at a resolution of 100 × 100 µm. The %RSD values (percent of relative standard deviation of mean values) for the major elements measured with EDXRF were compared with similar values obtained by two independent LIBS set-ups at spot sizes of 300 µm in diameter. The statistical analysis showed which elements were homogeneously distributed in the 22 mineral targets of the SCCT, providing their uncertainty values for further calibration. Moreover, nine of the 22 targets showed a good Raman response and their mineral distributions were also studied. Those targets can be also used for calibration purposes of the Raman part of SuperCam using the wavenumbers of their main Raman bands proposed in this work.
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Meio Ambiente Extraterreno , Marte , Calibragem , Meio Ambiente Extraterreno/química , Minerais/análise , Análise Espectral Raman/métodosRESUMO
In general, any standoff sensor for the effective detection of explosives must meet two basic requirements: first, a capacity to detect the response generated from only a small amount of material located at a distance of several meters (high sensitivity) and second, the ability to provide easily distinguishable responses for different materials (high specificity). Raman spectroscopy and laser-induced breakdown spectroscopy (LIBS) are two analytical techniques which share similar instrumentation and, at the same time, generate complementary data. These factors have been taken into account recently for the design of sensors used in the detection of explosives. Similarly, research on the proper integration of both techniques has been around for a while. A priori, the different operational conditions required by the two techniques oblige the acquisition of the response for each sensor through sequential analysis, previously necessary to define the proper hierarchy of actuation. However, such an approach does not guarantee that Raman and LIBS responses obtained may relate to each other. Nonetheless, the possible advantages arising from the integration of the molecular and elemental spectroscopic information come with an obvious underlying requirement, simultaneous data acquisition. In the present paper, strong and weak points of Raman spectroscopy and LIBS for solving explosives detection problems, in terms of selectivity, sensitivity, and throughput, are critically examined, discussed, and compared for assessing the ensuing options on the fusion of the responses of both sensing technologies.
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The enormous possibilities offered by near-infrared (NIR) spectroscopy for the (on/in/at-line) quality control process of olive fruits, pastes, and oils are summarized throughout this paper. Special attention has been paid to the combination of NIR and chemometric treatments for the on-line analysis of olive fruits and also for the quality parameters evaluation on olive oils and pastes which can enhance the production of a high quality olive oil and the selection of olive fruit with superior properties. The implementation of NIR sensors in olive mills with successful results has also been reviewed and the commercial olive fruit and oil analyzers highlighted.
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Indústria Alimentícia/métodos , Óleos de Plantas/química , Espectroscopia de Luz Próxima ao Infravermelho , Ácidos Graxos/análise , Contaminação de Alimentos/análise , Indústria Alimentícia/instrumentação , Frutas/química , Olea/química , Azeite de Oliva , Óleos de Plantas/classificação , Espectroscopia de Luz Próxima ao Infravermelho/métodos , Água/análiseRESUMO
SuperCam is a highly integrated remote-sensing instrumental suite for NASA's Mars 2020 mission. It consists of a co-aligned combination of Laser-Induced Breakdown Spectroscopy (LIBS), Time-Resolved Raman and Luminescence (TRR/L), Visible and Infrared Spectroscopy (VISIR), together with sound recording (MIC) and high-magnification imaging techniques (RMI). They provide information on the mineralogy, geochemistry and mineral context around the Perseverance Rover. The calibration of this complex suite is a major challenge. Not only does each technique require its own standards or references, their combination also introduces new requirements to obtain optimal scientific output. Elemental composition, molecular vibrational features, fluorescence, morphology and texture provide a full picture of the sample with spectral information that needs to be co-aligned, correlated, and individually calibrated. The resulting hardware includes different kinds of targets, each one covering different needs of the instrument. Standards for imaging calibration, geological samples for mineral identification and chemometric calculations or spectral references to calibrate and evaluate the health of the instrument, are all included in the SuperCam Calibration Target (SCCT). The system also includes a specifically designed assembly in which the samples are mounted. This hardware allows the targets to survive the harsh environmental conditions of the launch, cruise, landing and operation on Mars during the whole mission. Here we summarize the design, development, integration, verification and functional testing of the SCCT. This work includes some key results obtained to verify the scientific outcome of the SuperCam system.
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In this paper, the ability of chrome shavings to remove motor oils, oily wastes and hydrocarbons from water has been studied. To determine amount of hydrocarbons sorbed on tanned wastes, a FT-NIR methodology was used and a multivariate calibration based on partial least squares (PLS) was employed for data treatment. The light density, porous tanned waste granules float on the surface of water and remove hydrocarbons and oil films. Wastes fibers from tannery industry have high sorption capacity. These tanned solid wastes are capable of absorbing many times their weight in oil or hydrocarbons (6.5-7.6g of oil and 6.3g of hydrocarbons per gram of chrome shavings). The removal efficiency of the pollutants from water is complete. The sorption of pollutants is a quasi-instantaneous process.
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Hidrocarbonetos/isolamento & purificação , Óleos Industriais/análise , Resíduos Industriais , Manufaturas , Poluentes Químicos da Água/isolamento & purificação , Purificação da Água/métodos , Adsorção , Hidrocarbonetos/análise , Curtume , Poluentes Químicos da Água/análiseRESUMO
The population studied in this paper is composed of 10 patients under hemodialysis, who have underwent a general exploration, a stress test, a spirometry, an analytic control and assessment of exercise their psychological situation, before and after the programme. At the end of the training programme there is an important increase in the SVC and the FVC, as well as the power and time of the stress test. The psychological state improves as well as the anaemia.
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Exercício Físico , Falência Renal Crônica/fisiopatologia , Idoso , Anemia/etiologia , Anemia/terapia , Teste de Esforço , Frequência Cardíaca , Humanos , Falência Renal Crônica/sangue , Falência Renal Crônica/psicologia , Falência Renal Crônica/terapia , Diálise RenalRESUMO
During recent years laser-induced breakdown spectroscopy (LIBS) has been considered one of the techniques with larger ability for trace detection of explosives. However, despite of the high sensitivity exhibited for this application, LIBS suffers from a limited selectivity due to difficulties in assigning the molecular origin of the spectral emissions observed. This circumstance makes the recognition of fingerprints a latent challenging problem. In the present manuscript the sorting of six explosives (chloratite, ammonal, DNT, TNT, RDX and PETN) against a broad list of potential harmless interferents (butter, fuel oil, hand cream, olive oil, ), all of them in the form of fingerprints deposited on the surfaces of objects for courier services, has been carried out. When LIBS information is processed through a multi-stage architecture algorithm built from a suitable combination of 3 learning classifiers, an unknown fingerprint may be labeled into a particular class. Neural network classifiers trained by the Levenberg-Marquardt rule were decided within 3D scatter plots projected onto the subspace of the most useful features extracted from the LIBS spectra. Experimental results demonstrate that the presented algorithm sorts fingerprints according to their hazardous character, although its spectral information is virtually identical in appearance, with rates of false negatives and false positives not beyond of 10%. These reported achievements mean a step forward in the technology readiness level of LIBS for this complex application related to defense, homeland security and force protection.
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Inteligência Artificial , Substâncias Explosivas , Análise Espectral/métodos , Árvores de DecisõesRESUMO
Univariate (zero-order), multivariate (first-order) and multiway (second-order) calibrations were assayed for the determination of vinegar acidity using a mechanized procedure based upon vibrational spectroscopy and the emerging multicommutation methodology. The second-order methodology relies on the use of a flow system based on multicommutation and binary sampling. The flow network comprises a set of three-way solenoid valves, computer-controlled to provide facilities to handle the sample and to generate a time-dependent pH gradient using two carrier solutions. The procedure is based on the volumetric fraction variation approach that maintains the same volume of sample solution and dynamically varies its pH. The analysis of second-order absorbance-pH matrices was performed using parallel factor analysis (PARAFAC). Results were compared with first-order absorbance data analyzed with linear calibration and partial least squares regression (PLS) and they were employed for a discussion of the relative advantages of the applied chemometric tools. As excellent accuracy is obtained without the need of any sample pre-treatment, the procedure can be fully mechanized (i.e., by means of an auto-sampler device). Accuracy of the different strategies assayed was assessed by comparing the results achieved with those obtained by titration reference procedure.
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Ácido Acético/química , Concentração de Íons de Hidrogênio , Espectrofotometria Infravermelho/métodos , Análise FatorialRESUMO
It has been evaluated the potential of near-infrared (NIR) diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) as a way for non-destructive measurement of trace elements at microg kg(-1) level in foods, with neither physical nor chemical pre-treatment. Predictive models were developed using partial least-square (PLS) multivariate approaches based on first-order derivative spectra. A critical comparison of two spectral pre-treatments, multiplicative signal correction (MSC) and standard normal variate (SNV) was also made. The PLS models built after using SNV provided the best prediction results for the determination of arsenic and lead in powdered red paprika samples. Relative root-mean-square error of prediction (RRMSEP) of 23% for both metals, arsenic and lead, were found in this study using 20 well characterized samples for calibration and 13 additional samples as validation set. Results derived from this study showed that NIR diffuse reflectance spectroscopy combined with the appropriate chemometric tools could be considered as an useful screening tool for a rapid determination of As and Pb at concentration level of the order of hundred microg kg(-1).
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Arsênio/análise , Capsicum/química , Chumbo/análise , Espectroscopia de Luz Próxima ao Infravermelho/métodos , CalibragemRESUMO
Two vibrational spectroscopy procedures have been developed and compared for the direct and simultaneous determination of piperonyl butoxide and tetramethrin, the active ingredients of alcoholic capillary lotions, for hair pediculosis diseases. Nine lotions, purchased from the Spanish market, were analyzed using both, attenuated total reflectance (ATR) and transmission FT-IR measurements, and based on the use of partial least squares (PLS) multivariate calibration. A reduced set of 15 matched standards (11 for calibration and 4 for validation) was employed using both measurement modes. The spectral wave number ranges between 1757 and 1712 cm(-1) was selected to determine tetramethrin by both, transmittance and reflectance measurements. For the analysis of piperonyl butoxide the 1513-1479 cm(-1) and 1576-1479 cm(-1) regions were selected for ATR and transmission measurements, respectively. Results found for commercial samples compared well with those obtained by a liquid chromatography reference method that evidenced the applicability of the proposed strategy for the analysis of commercial formulations.
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Infestações por Piolhos/tratamento farmacológico , Ftirápteros/efeitos dos fármacos , Butóxido de Piperonila/química , Piretrinas/química , Espectroscopia de Infravermelho com Transformada de Fourier/métodos , Administração Tópica , Animais , Análise dos Mínimos Quadrados , Butóxido de Piperonila/administração & dosagem , Butóxido de Piperonila/uso terapêutico , Piretrinas/administração & dosagem , Piretrinas/uso terapêutico , Controle de QualidadeRESUMO
It has been made a critical evaluation of the application of near infrared Fourier transform-Raman spectroscopy for the simultaneous determination of the most important nutritional parameters such as energetic value, carbohydrate, protein and fat contents of infant formula and powdered milk samples based on the use of partial least squares (PLS) regression analysis. A highly heterogeneous population of 23 samples, covering a wide range of infant food formula and powdered milk, were obtained from the Spanish market. Raman spectra, obtained by excitation with a Nd:YAG laser at 1064 nm, show no disturbing fluorescence effects; therefore sample spectra can be recorded without any previous preparation step. After correcting the spectra, hierarchical cluster analysis was performed in order to select a representative calibration set and the corresponding validation sample set. Different PLS models and several spectral windows were tested in order to evaluate their prediction capabilities for the validation set. Considering a calibration set comprised of three replicate spectra of 15 samples and a validation data set of eight samples, the procedure developed provided figures of merit which complied with the statutory values declared by the United States Food and Drug Administration (US FDA).
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Análise de Alimentos/métodos , Alimentos , Fórmulas Infantis/química , Leite/química , Análise Espectral Raman/métodos , Animais , Calibragem , Carboidratos/análise , Gorduras/análise , Humanos , Lactente , Recém-Nascido , Proteínas/análiseRESUMO
A rapid and non-destructive method has been developed for the characterization of chocolate samples based on diffuse reflectance near-infrared Fourier transform spectroscopy (DRIFTS) and artificial neural networks (ANNs). This methodology provides a potentially useful alternative to time-consuming chemical methods of analysis. To assess its utility, 36 chocolate samples purchased from the Spanish market were analyzed for the determination of the main nutritional parameters like carbohydrates, fat, proteins, energetic value and cocoa content. Direct triplicate measurements of each sample were carried out by DRIFTS. Cluster hierarchical analysis was used for selecting calibration and validation data sets, resulting in a calibration set comprised of 19 samples and a validation data set of 17 samples. As it is common the presence of non-linear effect in reflectance spectroscopy, ANNs was chosen for data pretreatment. The root-mean-square error of prediction (RMSEP) values obtained for carbohydrates, fat, energetic value and cocoa were 1.0% (w/w), 1.0% (w/w), 50 kJ (100 g)(-1) and 1.4%, respectively. The mean difference (d(x-y)) and standard deviation of mean differences (s(x-y)) of the carbohydrates, fat, proteins content, energetic value and cocoa content were 0.9 and 2.4% (w/w), 0.2 and 1.0% (w/w), 9.1 and 50 kJ (100 g)(-1), and -0.5 and 1.4%, respectively. The maximum relative error for the prediction (QC) of any of these parameters for a new sample did not exceed 5.2%.
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Cacau/química , Rede Nervosa , Avaliação Nutricional , Animais , Calorimetria , Carboidratos/análise , Manipulação de Alimentos , Leite/química , Espectroscopia de Infravermelho com Transformada de Fourier/métodosRESUMO
A critical evaluation of the application of attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) and partial least squares (PLS) to the determination of several nutritional parameters, such as the energetic value and the carbohydrate, protein and calcium contents, in commercially available yogurt samples was carried out. To this end, a highly heterogeneous population of 48 samples covering a wide range of yogurts obtained from the Spanish market was used. After correcting the spectra, hierarchical cluster analysis was performed in order to select a representative calibration set and the corresponding validation sample set. Different PLS models and several spectral windows were tested in order to evaluate their prediction capabilities for the validation set. For all nutritional parameters, with the exception of fat content, the procedure developed here provided good precision; the values obtained complied with the statutory values declared by the US FDA.
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Espectroscopia de Infravermelho com Transformada de Fourier/métodos , Iogurte/análise , Cálcio/química , Calibragem , Carboidratos/química , Gorduras/química , Proteínas/química , Iogurte/classificaçãoRESUMO
A new procedure has been developed for the determination of hydrocarbons retained in solid tanned wastes from polluted waters. The method uses near-infrared (NIR) transmission spectra obtained from leachates of the hydrocarbons with CCl4 using a partial least-squares (PLS) calibration model based on the use of mixtures of n-hexane, isooctane, and toluene diluted with CCl4. This methodology was applied to the evaluation of the absorption capacity of chrome shavings in water samples polluted with hydrocarbons, resulting in a maximum absorption capacity of 6.30 g hydrocarbons per g solid waste.
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We report the results of an intervention trial comparing the counseling (group A) of the general practitioner to encourage to quit smoking in dissonant smokers and an intervention based on counseling and offer of follow up at 2 and 3 weeks and at 3 and 6 months (group B). Both interventions were globally evaluated to assess the influence of the smoking habits of health professionals on the results. In the 93 group B patients there was a higher quitting rate than in group A. The rates of success after one year follow up were 26.9% and 11.9% (p less than 0.05). Forty-seven of the 152 patients were counseled by smoking physicians and 105 by non-smoking physicians; at one-year follow-up, the verified quitting rates were 10.6% and 25.7%, although the difference was not significant. It was concluded that the reinforcement of counseling by follow-up may increase the rate of quitting smoking in dissonant smokers in a primary care setting, and that the influence of the habit of the health professional can be limited through more systematic interventions.
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Médicos , Prevenção do Hábito de Fumar , Adulto , Atitude do Pessoal de Saúde , Aconselhamento , Feminino , Seguimentos , Humanos , Masculino , Pessoa de Meia-Idade , Inquéritos e QuestionáriosRESUMO
The utility of two tests for the early detection of alcoholism (CBA and CAGE) is studied in a group of 247 adult patients of both sexes at the primary care environment. For the definition of the "problem drinker case", the Münchner alkoholismus test (MALT) protocol is used as "gold standard". A sensitiveness of 79 and 75% is obtained for the CBA and CAGE respectively, a specifity of 94 and 96%, and predictive positive value of 63 and 73%, with a prevalence of "problematic drinkers" of 12%. Both questionnaires are shown as efficient instruments for the secundary prevention of alcoholism in the primary care consulting rooms.