Understanding the compositional changes of organic matter in torrefied olive mill pomace compost using infrared spectroscopy and chemometrics.

Composting olive mill pomace (OMP), the major by-product of the olive oil industry, is an attractive waste management practice in the context of sustainable food production. Thermal treatment of compost at mild temperatures (torrefaction) can aid to improve its characteristics as a soil amendment. This study aims to understand the chemical changes occurring during torrefaction of olive mill pomace-based (OMP) compost, as well as to evaluate the treatment effects on compost at different stages of maturation. Here, treatments at different temperatures (175, 225, and 275 °C) and duration (from 1 to 5 h) have been employed to obtain a sort of torrefied samples. In general, the H/C and O/C atomic ratios of compost samples decreased with torrefaction temperatures, which suggests an incipient coalification of the organic matter. Furthermore, the results showed that a combination of FT-NIR and FT-MIR spectroscopy using a low-level data fusion strategy is very sensitive to the molecular changes occurring both in the composting process and during heating. Principal Component Analysis (PCA) of the merged spectra revealed that the changes at 175 °C are mainly the loss of water (O-H contributions at 3300 and 5169 cm-1) together with the degradation of proteins (observed in the decrease of amide I and II characteristic bands). Furthermore, the samples heated at this temperature can still be differentiated by their initial maturation stage. On the other hand, thermochemical changes occurring at higher temperatures are more intense and make the samples more alike, independently of the composting time. When heating above 225 °C, the loss of O-H happens together with the decrease of aliphatic moieties, reflected in the bands 2920 and 2850 cm-1 (FT-MIR) and 4258, 4323, 5665, and 5781 cm-1 (FT-MIR). This can be attributed to the thermal degradation of cellulosic materials and, additionally, to the degradation of the residual oil in the case of poorly composted samples. Heated samples are characterized by the presence of carbonyl groups (1709 cm-1) and humic-like complex and polymerized aromatic structures (1579 cm-1). Since the characteristics of the torrefied compost at 275 °C are very similar regardless of the initial maturation stage, torrefaction may be a very interesting way to reduce the composting time of olive mill pomace to obtain a high-quality organic amendment for soil application.

Characterization of Wall Paintings of the Harem Court in the Alhambra Monumental Ensemble: Advantages and Limitations of In Situ Analysis.

Non-invasive techniques (X-ray fluorescence, XRF, and Raman spectroscopy) were used for the study of the Hispano Muslim wall paintings. Principal component analysis (PCA) was performed on the semi-quantitative XRF results directly provided by the in-built factory calibrations with minimum user manipulation. The results obtained were satisfactory and highlighted differences and similarities among the measurement points. In this way, it was possible to differentiate the decorations carried out on gypsum plasterwork and the wall paintings over lime plaster. The color palette, revealed by combining the results from XRF and Raman spectroscopies, comprised the pigments hematite, lapis lazuli, cinnabar (in poor conservation state), and possibly, carbon. Evidence of past interventions was also provided by PCA on XRF data, which detected the presence of Pb, Ba, and Zn in some areas. Furthermore, the preparation layers have been studied in detail on cross-sections of two microsamples. Several layers of lime plaster with a compact microstructure have been observed. The characteristic of the pictorial layer and the identification of calcium oxalate point to the use of a secco-technique. The main alteration identified was a gypsum surface layer covering the painting and signs of plaster deterioration due to gypsum migration to more internal areas. Finally, the comparison with the observations made by restorers in previous interventions on these paintings revealed the importance of the representativeness gained with the in situ study, which enabled the analysis of a high number of areas.

Comparing mapping and direct hyperspectral imaging in stand-off Raman spectroscopy for remote material identification.

Stand-off Raman spectroscopy offers a highly selective technique to probe unknown substances from a safe distance. Often, it is necessary to scan large areas of interest. This can be done by pointwise imaging (PI), that is, spectra are sequentially acquired from an array of points over the region of interest (point-by-point mapping). Alternatively, in this paper a direct hyperspectral Raman imager is presented, where a defocused laser beam illuminates a wide area of the sample and the Raman scattered light is collected from the whole field of view (FOV) at once as a spectral snapshot filtered by a liquid crystal tunable filter to select a specific Raman shift. Both techniques are compared in terms of achievable FOV, spectral resolution, signal-to-noise performance, and time consumption during a measurement at stand-off distance of 15 m. The HSRI showed superior spectral resolution and signal-to-noise ratio, while more than doubling the FOV of the PI at laser power densities reduced by a factor of 277 at the target. Further, the output hyperspectral image data cube can be processed with state of the art chemometric algorithms like vertex component analysis in order to get a simple deterministic false color image showing the chemical composition of the target. This is shown for an artificial polymer sample, measured at a distance of 15 m.

Thermal destruction of organic waste hydrophobicity for agricultural soils application.

Use of organic amendments is a good strategy for combating the growing problem of soil degradation due to deterioration of organic matter content, particularly severe in semi-arid European Mediterranean regions, while at the same time providing an opportunity for recycling organic wastes. Olive mill pomace (OMP), the main by-product of the olive oil industry, is being used increasingly in olive grove soils for this purpose. Although the positive effects of OMP amendments have been widely studied, they also have some negative effects on soil. One of the most critical is that they increase water repellency (WR) due to the presence of poorly evolved, strongly aliphatic compounds. This detrimental effect has received very little attention, although it may impair plant water availability and infiltration rates, increase erosion and lower long-term soil quality. This study proposed, for the first time, thermal treatment as an effective way of reducing WR in organic amendments (i.e. mixtures of OMP, olive tree pruning, chicken manure and spent coffee grounds) prior to their application to soil. Thermal treatment at 275 °C proved effective in removing WR, while lower temperatures (175 or 225 °C) can even increase it. Changes by thermal treatment in the characteristics of the organic amendments studied with FTIR and UV-Vis spectroscopy and thermogravimetric analysis showed that it strongly reduced the aliphatic compounds mainly responsible for their hydrophobicity, concentrated aromatic compounds and increased thermostability. Heating also reduced phytotoxicity, making all of the organic amendments usable in the field (germination index over 100%). Therefore, heating at 275 °C could be an acceptable option for removing WR from organic amendments, enhancing their quality with more stable evolved characteristics.

Authentication of canned fish packing oils by means of Fourier transform infrared spectroscopy.

The authentication of packing oil from commercial canned tuna and other tuna-like fish species was examined by means of attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and chemometrics. Using partial least squares discriminant analysis (PLS-DA), it was possible to differentiate olive oil from seed oils. Discrimination of olive oil from high-oleic sunflower oil was possible, despite the latter having a degree of unsaturation more similar to olive oil than to sunflower oil. However, in the samples analyzed, sunflower oil could not be differentiated clearly from those labeled with the generic term "vegetable oil". Furthermore, the authentication of extra virgin olive oil, although more difficult, could be achieved using ATR-FTIR spectroscopy. The method could be applied regardless of fish type, without interference from fish lipids.

In situ noninvasive Raman microspectroscopic investigation of polychrome plasterworks in the Alhambra.

A totally non-invasive in situ investigation in one of the main halls of the Palace of the Lions in the Alhambra (Granada, Spain) has been carried out. Analyses were made with a fiber-optic portable Raman microspectrometer placed on scaffolding platforms at a height of ca. 12 m above the ground level during the period of conservation works. The objects of this study are the decorated plasterworks in the seven vaults of the Hall of the Kings. Together with the results, the different practical problems related to the positioning of the instrumental setup and the influence of the local environment during the analysis are discussed. In general, high quality spectra were obtained despite difficulties for micro-probe head positioning and sometimes the vibrations of the corresponding scaffold. Different typical antiquity pigments have been identified: cinnabar, minium, carbon black and lapis lazuli. Furthermore, the luminescence pattern from lapis lazuli found in most blue decorations has allowed the establishment of the natural origin and provenance of the pigment. Apart from this natural lapis lazuli, synthetic ultramarine blue was also found in one of the vaults showing up a recent restoration. In addition, some degradation products of cinnabar and minium were identified, with the major advantage of providing real-time information to the conservators during their work.

Feasibility study on the use of infrared spectroscopy for the direct authentication of Iberian pig fattening diet.

The feasibility of using both middle- and near-infrared spectroscopy for discrimination between subcutaneous fat of Iberian pigs reared on different fattening diets has been evaluated. The sample set was formed by subcutaneous fat of pigs fattened outdoors (extensively) with natural resources (montanera) and pigs fattened on commercial feeds, either with standard feed or with especial formulations with higher content in oleic acid (HO-formulated feed). Linear discriminant analysis was used to classify the samples according to the fattening diet using the scores obtained from principal component analysis of near- and middle-infrared spectra as variables to construct the discriminant functions. The most influential variables were identified using a stepwise procedure. The discriminant potential of each spectral region was investigated. Best results were obtained with the combination of both regions with 91.7% of the standard feed and 100% of montanera and HO-formulated feed samples correctly classified. Chemical explanations are provided based on the correlation of these variables with fatty acid content in the samples.

Ion mobility spectrometry of volatile compounds from Iberian pig fat for fast feeding regime authentication.

Characteristic ion mobility spectra for volatile compounds present in fat were used to authenticate the feeding regime of Iberian pigs. Volatile compounds were obtained by heating the solid samples at 150 degrees C for 40 min. This produced a headspace that was introduced in the spectrometer ionization chamber by means of a highly purified nitrogen stream. The spectra thus, obtained for the fat samples were processed chemometrically in order to assess their usefulness for discriminating meat from free-range pigs fed on pasture and acorns and confined pigs fed with commercial feed including high-oleic acid products. Principal component analysis was used as both an exploratory tool and a variable reduction method, and linear discriminant analysis was employed to classify 65 subcutaneous fat samples according to pig feeding regime. Only 2.3% of the samples from pigs reared in confinement were misclassified. 95.5% of the free-range samples were correctly predicted.

Ultrasonic trapping of microparticles in suspension and reaction monitoring using Raman microspectroscopy.

An ultrasonic standing wave around 2 MHz has been used for trapping and concentration of suspended micrometer-size particles in a flow cell, whereas Raman microspectroscopy was used as a nondestructive technique to provide molecular information about the trapped particles. With this approach, detection and discrimination of different polymer microparticles based on their characteristic Raman spectra was performed. Dextran, poly(vinyl alcohol), and melamine resin-based beads, with and without functionalization, were used for this purpose. Furthermore, taking advantage of the flow-through characteristics of the cell and the versatility of the employed flow system, full control over the media surrounding the trapped particles was achieved. This allowed us to perform chemical reactions on the trapped particles and to monitor spectral changes in real time. Here retention of cation-exchanger beads loaded with silver ions and subsequent reduction of the silver ions was demonstrated. In this way, surface-enhanced Raman (SER) active beads were prepared and retained in the focus of the Raman microscope by means of the ultrasonic field. Injection of analytes in the flow system thus allowed recording of their SER spectra. Using 9-aminoacridine, a linear dependence of the found SER signal in the range from 1 to 10 microM has been achieved. The repeatability in the recorded SER intensities was on the order of 4-5%. This included bead retention, surface-enhanced Raman layer synthesis, and analyte detection.

Fourier-transform infrared (FTIR) spectroscopy for monitoring and determining the degree of crystallisation of polyhydroxyalkanoates (PHAs).

FTIR spectroscopy has been used to monitor and determine the degree of crystallisation in a sample of polyhydroxybutyrate-co-14%valerate (PHB-co-14%HV). Time series spectra of solution-cast films of the polymer revealed spectral changes attributed to the onset of crystallisation. Curve fitting was used to obtain an absolute measure of crystallinity. Mean centred principal-component analysis (PCA) revealed that 99.9% of the spectral variance could be attributed to factor 1. The loadings plot for factor 1 contained features attributable to crystalline and amorphous phases. These features were opposite in sign, indicating that changes in the spectra with the onset of crystallisation are simultaneous and opposite in direction, i.e. as the crystalline band increases the amorphous band decreases. Cross-peaks in asynchronous 2D correlation maps indicate there are likely to be very minor components that are changing out of phase. The presence of these minor components is supported by examination of the loadings of higher factors in the PCA model. PCA has been shown to be suitable for determining the number of dynamic spectral features and has enabled relative and objective monitoring of crystallisation kinetics.

Probing intermolecular interactions in water/ionic liquid mixtures by far-infrared spectroscopy.

Far-infrared spectra in the range from 600 to 20 cm-1 of two hydrophilic (1-ethyl-3-methylimidazolium tetrafluoroborate and 1-butyl-3-methylimidazolium tetrafluoroborate) and one hydrophobic (1-butyl-3-methylimidazolium hexafluorophosphate) ionic liquids and their mixtures with water at different concentrations are reported. Shifts of the librational water bands depending on the nature of the anion are found to be related to the strength of the interaction between the water molecules and the anions. For both hydrophilic ionic liquids, the librational band is centered around 460 cm-1, whereas for the hydrophobic ionic liquid, it is shifted to 388 cm-1, indicating less hindered rotation of single water molecules. Multivariate curve resolution, paying special attention to the spectral range from 50 to 350 cm-1, was used to investigate the presence of different species with increasing water concentration. For both hydrophilic ionic liquids, a band located at 153 cm-1 was resolved into two different contributions. A small contribution at 202 cm-1 can be attributed to intermolecular interactions between water molecules forming dimers. The major contribution (centered at 148 cm-1) corresponds to water molecules that do not bond to each other via H-bonding. It is therefore assigned to a hindered translation arising from the stretching of the hydrogen bond between BF4- anions and water molecules. Formation of water dimers in the hydrophobic ionic liquid does not occur. Furthermore, the spectral contribution of the stretching of H-bonds between water molecules and PF6- cannot be unambiguously detected, which indicates an extremely weak interaction between water molecules and this anion.

Environmental water samples analysis of pesticides by means of chemometrics combined with fluorimetric multioptosensing.

A single flow-through optosensor spectrofluorimetric system is proposed for the resolution of mixtures of three pesticides, alpha-naphthol, o-phenylphenol and thiabendazole, at microg l(-1) levels using a partial least-squares (PLS) calibration approach. The sensor was developed in conjunction with a monochannel flow-injection analysis system with fluorimetric detection using C18 silicagel as an active sorbent substrate in the flow cell. By using 20% methanol-water (v:v) solution as carrier solution, the multisensor responds linearly in the measuring range without requiring additional reagents or derivatization. First derivative emission spectra of the corresponding analytes recorded during the process of retention-elution were used to provide multivariate data. The different kinetic on the retention process of the analytes on the sensing zone allows the selection of a time matrix for each analyte providing best results in the PLS approach. Accurate prediction results were obtained for the three analytes with RMSEP values of 1.86%, 3.34% and 0.50% were obtained for alpha-naphthol, o-phenylphenol and thiabendazole respectively. In the analysis of environmental waters samples, a mean recovery of 103% was obtained.

Containerless reaction monitoring in ionic liquids by means of Raman microspectroscopy.

Reaction monitoring by Raman microspectroscopy in levitated room temperature ionic liquid (RTIL) droplets is reported. Due to their non-volatility, RTIL droplets are well-suited to act as wall-less microreactors. The droplets were produced by a piezoelectric flow-through microdispenser connected to an automated flow injection system and were levitated by an acoustic trap. Taking advantage of the flow system versatility, the sequence of reagents was easily changed to study a model organic reaction: the Knoevenagel condensation. The reaction was followed by Raman microspectrometry and the obtained spectra were analysed using multivariate curve resolution to retrieve the concentration profiles and pure spectra of reactants, intermediates and products involved in the reaction. In addition, information about solvation interactions was obtained by monitoring the desolvation process taking place when a volatile co-solvent evaporated from the droplet.

On-line reaction monitoring in the liquid phase using two mid-infrared quantum cascade lasers simultaneously.

On-line monitoring of a model reaction was performed by employing two pulsed mid-infrared Fabry-Pérot quantum cascade lasers (QCL). The emission maxima of the QCLs were located at 1393 and 1080 cm(-1). An optical system of parabolic mirrors and a ZnSe beam splitter combined the two laser beams and allowed a transmission cell to be probed with both QCLs simultaneously. The reaction mixture was pumped continuously through a cell that had an optical path of 48 microm. This dual QCL system allowed fast absorption measurements of the reaction mixture at two distinct wavenumbers. The reaction under study was the oxidation of sulfite to sulfate with hydrogen peroxide acting as oxidant. On-line measurements of the chemical reaction allowed direct, real-time monitoring of sulfate formation and hydrogen peroxide depletion.

Detection of albumin unfolding preceding proteolysis using Fourier transform infrared spectroscopy and chemometric data analysis.

The hydrolysis of bovine serum albumin with protease K at 60 degrees C has been studied by means of infrared spectroscopy. Two-dimensional correlation spectroscopy (2DCoS) has been used to study spectral changes in the reaction. The use of the multivariate curve resolution-alternating least-squares method applied to infrared measurements allowed the recovery of pure infrared spectra and concentration profiles of the different species involved in the reaction. Special attention was paid to the careful inspection of residuals again using 2DCoS. In this way, a heat-induced unfolding step previous to protein hydrolysis was identified. The infrared spectra of the intermediate species showed a more disordered structure than native albumin, the decrease in alpha-helix conformation being especially noticeable. The formation of beta-sheet aggregates due to heating was detected too.