High-resolution Absorption Research Articles

Rapid calculation of atmospheric molecular absorption characteristics in the terahertz band based on wideband K-distribution method

This paper focuses on rapidly calculating atmospheric molecular absorption properties in the 0.3–30 THz frequency range of terahertz waves. It conducts research related to spectral radiation models and fast computation model databases. Based on the latest version of the High-resolution transmission molecular absorption database-2020, in conjunction with the line-by-line (LBL) spectral radiative calculation method, the spectral absorption characteristics of nine atmospheric molecules (H2O, CO2, O3, NO, N2O, NO2, NH3, SO2, CH4) are analyzed. The relative contributions of the eight other gas molecules absorption abilities in the terahertz range are examined, with H2O molecule serving as the reference. Taking into account the non-gray absorption properties of atmospheric molecules and the need for fast computation, this study divides the frequency range of 0.3–30 THz into 24 calculation bands based on the spectral absorption distribution characteristics of atmospheric molecules. Utilizing LBL calculations with a resolution of 0.01 cm−1, a non-correlated wideband K-distribution model (WBK) is developed, which achieves nearly the same computational accuracy as LBL. Furthermore, the WBK radiation calculation model is validated under both uniform and non-uniform atmospheric conditions based on earth atmospheric environmental parameters. An exponential kernel fitting coefficient table for the rapid calculation of atmospheric molecular absorption coefficients is established based on the WBK radiation calculation model to improve computational efficiency further. This database enables fast calculation of 24 broadband absorption coefficients (corresponding to 7 Gaussian integration points) within 0–100 km altitude in earth atmosphere.

Improved Terahertz Time-Domain Spectroscopy via the Extended Kalman Filter

To implement terahertz time-domain spectroscopy (THz-TDS) systems that have short integration time and maintain performance, the extended Kalman filter (EKF) has been used. Performance of EKF with THz-TDS on vapor samples and solid samples is untested. Previous EKF methods were not adaptive for use on multiple THz-TDS systems. We provide an adaptive EKF method that can work on any THz setup, to improve maximum measurable absorption coefficient. Our adaptive EKF method responds to THz pulse properties. The adaptive EKF is exhaustively demonstrated for six different time-constant data sets spanning 1 ms to 300 ms for THz-TDS on vapor with electro-optic THz detection. The acquisition time saved is quantified and shown to significantly reduce acquisition time from 2.58 ms to 1 ms. This improvement of 2.58 times will have a significant effect to move spectral imaging from taking hours to taking minutes. Vapor absorption lines are maintained. We show the adaptive EKF maintain correct spectral information when compared to the high-resolution transmission molecular absorption (HITRAN) database. The adaptive EKF is also demonstrated for THz-TDS on vapor with photoconductive THz detection, thus demonstrating adaptability, and is applied for THz-TDS of a solid sample of polyethylene terephthalate glycol.

Measurements and calculations of CO2-broadening and shift coefficients of water vapor transitions in the 5150–5550 cm−1 spectral region

The high-resolution H2O absorption spectra induced by CO2 pressure have been recorded using a Bruker IFS 125 HR FTIR spectrometer at room temperature in the 5150–5550 cm–1 spectral region. A multispectrum fitting procedure has been applied to these spectra to recover the spectral line parameters using the speed-dependent Voigt profile. The water vapor line broadening and shift coefficients for lines of two vibrational bands ν2+ν3 and ν1+ν2 were obtained. An uncertainty of the broadening coefficients for the unblended H2O absorption lines was estimated to be 2–3%. The calculations of line-broadening and line-shifting parameters were performed using the semi-empirical method which is based on the impact theory and enables a realistic prediction modified by introducing additional parameters obtained by using empirical data. The root mean square deviations of measured and calculated line widths and shifts were 0.0086 and 0.0053 cm−1 atm−1, respectively.

H[formula omitted]O-HF dimer rotational spectra: New measurements and re-analysis

New measurements of the H2O-HF dimer high resolution absorption spectrum are performed using a relatively warm (240–260 K) equilibrium gas mixture with two complementary spectrometers: a video spectrometer and spectrometer with radio-acoustic detection. Positions of over hundred H2O-HF lines in the 158–345 GHz range are refined (their uncertainty is reduced by about order of magnitude) and several tens of lines are newly measured. These data are re-fitted together with previous measurements giving a refined set of constants of effective Hamiltonian which characterizes the dimer intermolecular dynamics. The new data improves significantly (from 100 to about 10 kHz) the accuracy of rotational constants corresponding to separate series of lines with fixed Ka.

Strontium monofluoride – a new molecule to measure fluorine using high-resolution continuum source flame molecular absorption spectrometry and its application for gasoline analysis

In this work, for the first time, strontium monofluoride was generated in an air-acetylene flame of a high-resolution continuum source molecular absorption spectrometer with the aim of fluorine determination via molecular absorption. The particular task was the determination of organic fluorine in gasoline/its components dissolved in xylene. Sequential measurements in the area of the most intensive absorption of the molecule were executed to select the spectral range for analysis. The acquired spectra differed from the ones from the literature, especially the emission spectra. The best and comparable sensitivity has been registered near 651 nm and 663 nm in measurements of rotations from the range of the X2Σ+ → A2Π electronic transition of the SrF molecule. Unfortunately, SrOH molecules were also spontaneously formed and absorbed radiation in the selected area. No other spectral interferences were found, except absorption by the SrBr molecule, which could have been formed in the flame despite a relatively low energy bond of 330 kJ/mol. The dependence of generation of the SrF and the SrOH molecules on the flame conditions was studied for pure solvent (xylene) and solutions of investigated samples of gasoline type. The effect of the SrOH molecule was overcome by blank subtraction or the least square background correction. The last method had to be used to overcome the SrBr effect. Due to the various combustion properties of various hydrocarbons and their different behaviour in flame, applying the simplified standard addition method became indispensable. As a source of strontium, an oil Sr standards or Sr acetylacetonate (SrAA) were investigated. The crucial benefit of SrF molecule application was the relatively good solubility (and relatively low price) of SrAA. Under the selected conditions, the characteristic concentration of fluorine was 1.9 and 2.0 mg/L, while the instrumental detection limit was 0.5 and 0.8 mg/L for the 651 and 663 nm ranges, respectively. The analytical technique enables the analysis of samples diluted to a small degree, e.g. 1:3 v:v and the best method detection limit is 1.3 mg/L. The proposed method is fast and cheap.

Utilization of Extraction Procedures for Evaluating Environmental Risk from Waste Materials.

Several procedures for extracting content from different waste materials types were investigated, with the aim of evaluating their environmental impact. The waste materials consisted of wastes from bauxite ore processing by means of the Bayer process (red mud, Ajka, Hungary), bauxite ore using the sintering process followed by the Bayer process (brown-red mud, Žiar nad Hronom, Banská Bystrica region, Slovakia) and sulphide ores (metal-rich post-flotation tailing, Lintich, Slovakia). The extraction procedures were carried out with the aim of isolating "mobilizable" fractions using 0.05 M ethylenediaminetetraacetic acid (EDTA) and 0.43 M acetic acid (AA) (representing environmental risk during changes in normal environmental conditions) and "maximum potentially mobilizable" fractions using 2 M HNO3 (representing the total environmental risk). The content of chosen toxic heavy metals (THMs) (Cd, Cr, Cu, Pb, Ni, Zn) and Fe, Mn as metals creating Fe/Mn oxides in the extracts and solutions after microwave digestion was determined using high-resolution continuum source flame atomic absorption spectrometry (HR CS FAAS). On the basis of the results obtained in this study, it is possible to state that different origin of waste materials is reflected in different mobility of toxic heavy metals into the surrounding environment. From the point of view of toxic heavy metals mobility, disposal site of wastes after bauxite processing are much less of a threat to the environment than disposal site of flotation sludge after processing sulphide ores. The single extraction of 0.43 M AA is more effective than the extraction of 0.05 M EDTA for the purposes of determining the content of metals in the mobilizable fraction of tailing waste materials. The mobility of the studied toxic heavy metals in the Lintich tailing decreases in the direction from the lagoon to the dam, which may indicate the fact that the dam serves to a certain extent to inhibit the mobility of metals into the surrounding ecosystem.

Vibrationally Resolved Absorption and Fluorescence Cross Sections of Adamantane in the Far-ultraviolet Spectral Range on an Absolute Scale

High-resolution absorption, dispersed fluorescence emission, and photoionization cross sections are presented for gas-phase adamantane excited by synchrotron radiation in the exciting-photon energy range of 6–30 eV. Relative and absolute absorption cross sections of so-far unmatched resolution of down to 0.27 cm−1 line width in the region from 6.4–28 eV are shown along with newly discovered vibronic substructures around the HOMO–LUMO transition. Absorption line positions are provided with very high accuracy and listed in tabular form to be used as spectral fingerprints for the detection of adamantane in interstellar media, where its column density may be determined via the absolute cross sections. The fluorescence emission lies in the ultraviolet range from 190–250 nm and is excited starting at the HOMO–LUMO transition at 6.49 eV, which corresponds to the highest fluorescence emission energy. Hitherto unreported fluorescence in the same spectral range and relative photoionization cross sections in the exciting-photon energy range up to 30 eV are also presented along with lifetime measurements for differentiation of the involved electronic states.

Determination of thallium in water samples via solid sampling HR-CS GF AAS after preconcentration on chromatographic paper

A method for determining thallium in water samples via solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry (SS HR-CS GF AAS) after preconcentration using chromatographic filter paper as a solid support was proposed. The effects of pH, stirring time, and sample volume in the analyte preconcentration step were studied. The presence of potential interferences in the sample and the type of masking agent were also examined. In the proposed procedure, the sample was placed in contact with the solid phase in a polypropylene tube, and after stirring for 3 min, thallium determination was performed via HR-CS GF AAS directly on chromatographic filter paper. A preconcentration factor of 55, a precision of 9.4% (n = 10; 10 μg L−1), a limit of detection of 0.018 μg L−1, and a limit of quantification of 0.059 μg L−1 were achieved. Analyte addition and recovery tests were performed, and the results ranged from 91% to 110%. The accuracy of the method was evaluated by analyzing a water reference material. The procedure was used to determine thallium in water samples collected in Barreiras, Bahia, Brazil. The results were compared with those obtained using inductively coupled plasma‒mass spectrometry (ICP‒MS). Thallium concentrations in the analyzed samples ranged from <0.059 to 0.80 μg L−1.

Diode laser absorption spectroscopy for real-time detection of breath oxygen

In this paper, a high-resolution laser absorption spectrometer is developed using a distributed feedback (DFB) diode laser in the spectral region near 760 nm, which is designed for the highly sensitive detection of oxygen (O2) in breathing gas. To investigate the spectrometer performance, O2 absorption line at 13146.580 cm−1 was selected, and detailed experiments on air-broadening coefficient, self-broadening coefficient and spectral line intensity were conducted. Compared to the corresponding data listed in the HITRAN2020 database, the results show that the errors for air-broadening coefficient, self-broadening coefficient and line intensity, were −6.832%, 4.082% and 4.667%, respectively. Finally, the developed laser absorption spectrometer was primarily evaluated for real-time analysis of O2 content in human breath analysis. The results indicate that the measured O2 concentrations in several volunteers range from 16% to 16.5%, which is in agreement with the levels reported in the literature for healthy humans.

High-resolution absorption spectroscopy of room-temperature and jet-cooled ammonia between 59,000 and 93,000 cm−1

We present new high-resolution photoabsorption spectra of ammonia spanning the region between 59,000 cm−1 and 93,000 cm−1 that were recorded by using the Fourier Transform Spectrometer at the Synchrotron SOLEIL. This region extends from just above the Franck-Condon envelope for the Ã1A2″ ← X̃1A1′ transition to well above the NH3+X̃+2A2″ ionization threshold. The spectra were recorded at a measured resolution of 0.23 cm−1 in both a room-temperature cell (293 K) and in a slit-jet supersonic expansion (∼70 K). The absolute photoabsorption cross section with an uncertainty of ± 5% is also reported for the room-temperature spectrum. The present resolution is a factor of 10 – 100 times higher than in other recently reported broad band spectra of ammonia, and many of the observed bands show partially resolved rotational structure. We have attempted to assign this structure for a number of these bands. The oscillator strengths extracted from the data are in good agreement with previous measurements but, in the case of structured bands, the present higher resolution measurements return higher peak absorption cross sections, that increase further when the sample is cooled. The present higher resolution spectra suggest that a number of previous vibronic band assignments that were based on quantum defect considerations may require some revision. Finally, we discuss the substantial differences between the photoabsorption and photoionization data just above the first ionization threshold.

Assessment of some element content and potential health risks in infant formulas available in Turkish markets

Accurately determining the composition of essential and toxic elements in commercial infant formulas is critical to ensuring safe nutrition for infants. In this study, the concentrations of essential and toxic elements (Pb, Ni, Cd, Al, Cr, Cu, Fe, Mn, Zn, Co) in infant formulas were determined using high-resolution continuum-source flame atomic absorption spectrometry (HR-CS FAAS) and have been evaluated for health risk. The measured values for concentrations from lowest to highest were (in mg/kg): 36.38–77.45 (Zn), 6.28–12.88 (Al), 2.37–4.91 (Cu), 22.01–51.64 (Fe), and 0.55–2.06 (Mn). The highest concentrations of Ni and Cd were 0.18 and 0.09 mg/kg, respectively, while the lowest concentrations for these metals were below the detection limit. The Cr, Co and Pb levels were below the detection limits in all samples. According to the risk assessment conducted for infants aged 0–24 months, which involved calculating the estimated daily intake (EDI), the estimated weekly intake (EWI), the target hazard quotient (THQ), and the hazard index (HI), it was found that the THQ values range from 0.00 to 0.06 for Ni, from 0.00 to 0.69 for Cd, and from 0.17 to 0.22 for Al. However, since the HI for all age groups is less than 1, it can be concluded that there is no health concern for the elements Ni, Cr, Cd, Pb, Al, and Co.

Temperature Dependence of the Electronic Absorption Spectrum of NO2.

The nitrogen dioxide (NO2) radical is composed of the two most abundant elements in the atmosphere, where it can be formed in a variety of ways including combustion, detonation of energetic materials, and lightning. Relevant also to smog and ozone cycles, together these processes span a wide range of temperatures. Remarkably, high-resolution NO2 electronic absorption spectra have only been reported in a narrow range below about 300 K. Previously, we reported [ J. Phys. Chem. A 2021, 125, 5519-5533] the construction of quasi-diabatic potential energy surfaces (PESs) for the lowest four electronic states (X̃, Ã, B̃, and C̃) of NO2. In addition to three-dimensional PESs based on explicitly correlated MRCI(Q)-F12/VTZ-F12 ab initio data, the geometry dependence of each component of the dipoles and transition dipoles was also mapped into fitted surfaces. The multiconfigurational time-dependent Hartree (MCTDH) method was then used to compute the 0 K electronic absorption spectrum (from the ground rovibrational initial state) employing those energy and transition dipole surfaces. Here, in an extension of that work, we report an investigation into the effects of elevated temperature on the spectrum, considering the effects of the population of rotationally and vibrationally excited initial states. The calculations are complemented by new experimental measurements. Spectral contributions from hundreds of rotational states up to N = 20 and from 200 individually-characterized vibrational states were computed. A spectral simulation tool was developed that enables modeling the spectrum at various temperatures─by weighting individual spectral contributions via the partition function, or for pure excited initial states, which can be probed via transient absorption spectroscopy. We validate these results against experimental absorption spectroscopy data at high temperatures, as well as via a new measurement from the (1,0,1) initial vibrational state.

In-Situ Analysis of Corrosion Products in Molten Salt: X-ray Absorption Reveals Both Ionic and Metallic Species.

Understanding and controlling the chemical processes between molten salts and alloys is vital for the safe operation of molten-salt nuclear reactors. Corrosion processes in molten salts are highly dependent on the redox potential of the solution that changes with the presence of fission and corrosion processes, and as such, reactor designers develop electrochemical methods to monitor the salt. However, electrochemical techniques rely on the deconvolution of broad peaks, a process that may be imprecise in the presence of multiple species that emerge during reactor operation. Here, we describe in situ measurements of the concentration and chemical state of corrosion products in molten FLiNaK (eutectic mixture of LiF-NaK-KF) by high-resolution X-ray absorption spectroscopy. We placed a NiCr foil in molten FLiNaK and found the presence of both Ni2+ ions and metallic Ni in the melt, which we attribute to the foil disintegration due to Cr dealloying.

Synthesis, Characterization, and Stability of Two Americium Vanadates, AmVO3 and AmVO4.

In search for chemically stable americium compounds with high power densities for radioisotope sources for space applications, AmVO3 and AmVO4 were prepared by a solid-state reaction. We present here their crystal structure at room temperature solved by powder X-ray diffraction combined with Rietveld refinement. Their thermal and self-irradiation stabilities have been studied. The oxidation states of americium were confirmed by the Am M5 edge high-resolution X-ray absorption near-edge structure (HR-XANES) technique. Such ceramics are investigated as potential power sources for space applications like radioisotope thermoelectric generators, and they have to endure extreme conditions including vacuum, high or low temperatures, and internal irradiation. Thus, their stability under self-irradiation and heat treatment in inert and oxidizing atmospheres was tested and discussed relative to other compounds with a high content of americium.

Closed-Vessel Conductively Heated Digestion of Dry Dog Food for Spectrometric Determination of Essential Nutrients

The closed-vessel conductively heated digestion system (CHDS) was evaluated to digest dry dog foods for further determination of K, Na, Cu, Fe, Mn, and Zn by high-resolution continuum source flame atomic absorption spectrometry (HR-CS FAAS). The CHDS method was optimized using a fractional factorial design with five variables (HNO3 concentration, H2O2 volume, temperature, holding time, and pre-digestion time) at two levels. The accuracy of the CHDS procedure was checked by the analysis of reference materials from the National Institute of Standards and Technology (NIST SRM 1577b Bovine Liver and 2976 Mussel Tissue) and Brazilian Agricultural Research Corporation (Embrapa MR-E1002A Fish Food). Also, the digestion efficiencies were calculated from residual carbon contents (RCCs). The RCC and blank values in the CHDS digested samples were consistently low, which is suitable for determinations using ICP OES and ICP-MS techniques. For comparison, all samples were also digested by microwave-assisted digestion in closed vessels (MW-AD). Results for Na, K, Cu, Fe, Mn, and Zn determined in sample digests obtained by CHDS were not statistically different at a 95% confidence level from those observed for MW-AD. Limits of quantification (LOQ) calculated from digests in CHDS and MW-AD were comparable, and the values provided adequate limits for elemental determinations in dog foods. Data from mineral composition and moisture were employed in a clustering analysis (HCA) and the discrimination of the samples among different manufacturers and food for dogs at different life stages was possible.

Numerical Investigation of on-Chip Multi-Gas Sensing Using a Low-Repetition-Frequency Microcavity Kerr Comb With Backward Interference Structure

By integrating a microcavity Kerr frequency comb with an interferometric arm structure for backward coupling with a slot sensing waveguide, we present a new on-chip multi-gas sensing device. The microcavity used for frequency comb generation has a novel symmetric double-ring structure with a large roundtrip length, which makes it possible to obtain high-resolution frequency-resolved absorption spectra. In the meanwhile, a flat octave-spanning broadband spectrum is obtained by dispersion engineering of the Si <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> N <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4</sub> -based micro-rings with a horizontal single slot structure. Without the use of an additional gas cell, the large-length sensing waveguide allows for improved integration. A multiple soliton comb with high pump-to-frequency comb conversion efficiency under the optimization of the microcavity structure to improve pump depletion was obtained. The simulation shows its high stability and application feasibility, and the sensing performance of several gas species in different wavelength regions is verified and analyzed.

FlexPES: a versatile soft X-ray beamline at MAX IV Laboratory.

FlexPES is a soft X-ray beamline on the 1.5 GeV storage ring at MAX IV Laboratory, Sweden, providing horizontally polarized radiation in the 40-1500 eV photon energy range and specializing in high-resolution photoelectron spectroscopy, fast X-ray absorption spectroscopy and electron-ion/ion-ion coincidence techniques. The beamline is split into two branches currently serving three endstations, with a possibility of adding a fourth station at a free port. The refocusing optics provides two focal points on each branch, and enables either focused or defocused beam on the sample. The endstation EA01 at branch A (Surface and Materials Science) is dedicated to surface- and materials-science experiments on solid samples at ultra-high vacuum. It is well suited not only to all flavours of photoelectron spectroscopy but also to fast (down to sub-minute) high-resolution X-ray absorption measurements with various detectors. Branch B (Low-Density Matter Science) has the possibility to study gas-phase/liquid samples at elevated pressures. The first endstation of this branch, EB01, is a mobile setup for various ion-ion and electron-ion coincidence techniques. It houses a versatile reaction microscope, which can be used for experiments during single-bunch or multi-bunch delivery. The second endstation, EB02, is based on a rotatable chamber with an electron spectrometer for photoelectron spectroscopy studies on primarily volatile targets, and a number of peripheral setups for sample delivery, such as molecular/cluster beams, metal/semiconductor nanoparticle beams and liquid jets. This station can also be used for non-UHV photoemission studies on solid samples. In this paper, the optical layout and the present performance of the beamline and all its endstations are reported.

Magnetic Adsorbent Decorated with Poly(N-Isopropylacrylamide) (PNIPAM) Brushes for the Vortex-Assisted Solid Phase Extraction (VASPE) of Lead in Water, Cigarettes and Soil with High-Resolution Continuum Source Flame Atomic Absorption Spectrometry (HR-CS FAAS) Detection

Here is reported the synthesis of a magnetic phosphorus-containing adsorbent decorated with poly(N-isopropylacrylamide) (PNIPAM) brushes via surface-initiated atom transfer radical polymerization (SI-ATRP) and its application for vortex assisted solid phase extraction of lead in water, cigarettes and soil. The adsorbent was characterized using Fourier-transform infrared spectroscopy (FT-IR) and energy dispersive x-ray (EDX) spectroscopy. A high-resolution continuum source flame atomic absorption spectrometer (HR-CS FAAS) was used for the quantification of lead. All factors affecting the extraction efficiency including the solution pH, adsorbent dose, sample volume, vortex time, and elution protocols were optimized. The limits of detection (LOD) and quantification (LOQ) were determined to be 0.05 µg L−1 and 0.18 µg L−1, respectively. The preconcentration and enhancement factors were 20 and 18. Validation was performed using TMDA 64.3 fortified water and INCT-OBTL-5 tobacco leaves certified reference materials with satisfactory recoveries. The method was shown to be sensitive, efficient and reproducible.

Measurement of Doppler effects in a cryogenic buffer-gas cell

Buffer-gas cooling is a universal cooling technique for molecules and used for various purposes. One of its applications is using molecules inside a buffer-gas cell for low-temperature spectroscopy. Although a high-intensity signal is expected in the cell, complex molecular dynamics is a drawback for precise spectroscopy. In this study, we performed high-resolution absorption spectroscopy of low-J transitions in the $\tilde{A}^2\Pi (0,0,0)-\tilde{X}^2\Sigma ^+(0,0,0)$ band of calcium monohydroxide (CaOH). CaOH molecules were produced by laser ablation in a copper cell and cooled to $\sim$5\,K using helium buffer gas. We probed the Doppler effects in a buffer-gas cell by injecting counter-propagating lasers inside the cell. The time evolutions of the Doppler width and shift were simulated using a dedicated Monte Carlo simulation and compared with data.

Comparison of excitation and kinetic temperatures in a laser-produced plasma using absorption spectroscopy.

High-resolution tunable laser absorption spectroscopy is used to measure time-resolved absorption spectra for six neutral uranium transitions in a laser-produced plasma. Analysis of the spectra shows that kinetic temperatures are similar for all six transitions, but excitation temperatures are higher than kinetic temperatures from 10-100 μs, indicating departures from local thermodynamic equilibrium.