X-ray emission spectroscopy of bulk liquid water in "no-man's land".

The structure of bulk liquid water was recently probed by x-ray scattering below the temperature limit of homogeneous nucleation (TH) of ∼232 K [J. A. Sellberg et al., Nature 510, 381-384 (2014)]. Here, we utilize a similar approach to study the structure of bulk liquid water below TH using oxygen K-edge x-ray emission spectroscopy (XES). Based on previous XES experiments [T. Tokushima et al., Chem. Phys. Lett. 460, 387-400 (2008)] at higher temperatures, we expected the ratio of the 1b1' and 1b1″ peaks associated with the lone-pair orbital in water to change strongly upon deep supercooling as the coordination of the hydrogen (H-) bonds becomes tetrahedral. In contrast, we observed only minor changes in the lone-pair spectral region, challenging an interpretation in terms of two interconverting species. A number of alternative hypotheses to explain the results are put forward and discussed. Although the spectra can be explained by various contributions from these hypotheses, we here emphasize the interpretation that the line shape of each component changes dramatically when approaching lower temperatures, where, in particular, the peak assigned to the proposed disordered component would become more symmetrical as vibrational interference becomes more important.

Reabsorption of soft x-ray emission at high x-ray free-electron laser fluences.

We report on oxygen K-edge soft x-ray emission spectroscopy from a liquid water jet at the Linac Coherent Light Source. We observe significant changes in the spectral content when tuning over a wide range of incident x-ray fluences. In addition the total emission yield decreases at high fluences. These modifications result from reabsorption of x-ray emission by valence-excited molecules generated by the Auger cascade. Our observations have major implications for future x-ray emission studies at intense x-ray sources. We highlight the importance of the x-ray pulse length with respect to the core-hole lifetime.

Comparison of x-ray absorption spectra between water and ice: new ice data with low pre-edge absorption cross-section.

The effect of crystal growth conditions on the O K-edge x-ray absorption spectra of ice is investigated through detailed analysis of the spectral features. The amount of ice defects is found to be minimized on hydrophobic surfaces, such as BaF2(111), with low concentration of nucleation centers. This is manifested through a reduction of the absorption cross-section at 535 eV, which is associated with distorted hydrogen bonds. Furthermore, a connection is made between the observed increase in spectral intensity between 544 and 548 eV and high-symmetry points in the electronic band structure, suggesting a more extended hydrogen-bond network as compared to ices prepared differently. The spectral differences for various ice preparations are compared to the temperature dependence of spectra of liquid water upon supercooling. A double-peak feature in the absorption cross-section between 540 and 543 eV is identified as a characteristic of the crystalline phase. The connection to the interpretation of the liquid phase O K-edge x-ray absorption spectrum is extensively discussed.

Noncontact salt and fat distributional analysis in salted and smoked salmon fillets using X-ray computed tomography and NIR interactance imaging.

To be able to monitor the salting process of cold smoked salmon, a nondestructive imaging technique for salt analysis is required. This experiment showed that X-ray computed tomography (CT) can be used for nondestructive distributional analysis of NaCl in salmon fillets during salting, salt equilibration, and smoking. The combination of three X-ray voltages (80, 110, and 130 kV) gave the best CT calibrations for NaCl, with a prediction error (root mean square error of cross-validation, RMSECV) of 0.40% NaCl and a correlation (R) of 0.92 between predicted values and reference values. Adding fat predictions based on NIR interactance imaging further improved the NaCl prediction performance, giving RMSECV = 0.34% NaCl and R = 0.95. It was also found that NIR interactance imaging alone was able to predict NaCl contents locally in salted salmon fillets with RMSECV = 0.56% and R = 0.86.

Screening of acrylamide contents in potato crisps using process variable settings and near-infrared spectroscopy.

In order to study the formation of acrylamide in potato crisps during processing, an experimental design was set up. The design variables were drying time (6 levels), frying temperature (2 levels) and frying time (8 levels). The design contained 36 samples, which were analysed for acrylamide contents using LC high-resolution mass spectroscopy (LC-HRMS), and fat contents using the Soxhlet apparatus. Prior to analysis, all potato crisp samples were ground and analysed on an NIRSystems 6500 near-infrared (NIR) spectrometer. The acrylamide contents were modelled by: (i) design variables using multiple linear regression, (ii) NIR spectra using partial least squares regression (PLSR) and (iii) design variables and NIR spectra in combination using a novel technique combining least squares regression on the former, and PLSR on the latter. The results showed that the NIR spectra alone or in combination with the design variables gave better prediction models for acrylamide than the design variables alone. This implies that the spectra contain chemical information that is not purely a result of the processing variables that were investigated in this experiment. NIR spectroscopy is proposed as a possible tool for screening and identification of potato crisps with a high acrylamide content.

Low-cost approaches to robust temperature compensation in near-infrared calibration and prediction situations.

The traditional way of handling temperature shifts and other perturbations in calibration situations is to incorporate the non-relevant spectral variation in the calibration set by measuring the samples at various conditions. The present paper proposes two low-cost approaches based on simulation and prior knowledge about the perturbations, and these are compared to traditional methods. The first approach is based on augmentation of the calibration matrix through adding simulated noise on the spectra. The second approach is a correction method that removes the non-relevant variation from new spectra. Neither method demands exact knowledge of the perturbation levels. Using the augmentation method it was found that a few, in this case four, selected samples run under different conditions gave approximately the same robustness as running all the calibration samples under different conditions. For the carbohydrate data set, all robustification methods investigated worked well, including the use of pure water spectra for temperature compensation. For the more complex meat data set, only the augmentation method gave comparable results to the full global model.