Off-line Techniques Research Articles

Protocols for bulk off-line fluid inclusion extraction for the analysis of δ13C-CH4 and δ13C-CO2 using a cavity ring-down spectroscopy (CRDS) analyser

Fluid inclusions are a window into deep geological fluids, providing unique access to their nature and composition. The isotopic composition of CO2 and CH4 hosted in fluid inclusions is a powerful proxy to assess the origin and transformation of deep geological fluids, giving insights into carbon sources, fluxes, and degassing in a wide variety of geodynamic settings. Over the last 5 decades, techniques have been developed to extract fluid inclusions from their host minerals and measure their bulk composition. These techniques are often challenged by analytical artifacts including high blank levels of CO2 and CH4, fluid re-speciation, gas adsorption, and diffusion. Since these processes may alter the pristine composition of gases liberated from fluid inclusions, rigorous protocols are needed in order to evaluate the isotopic integrity of the extracted volatile species. In this study, we introduce new protocols for bulk off-line fluid inclusion extraction for the analysis of δ13C-CH4 and δ13C-CO2 using a Cavity Ring-Down Spectroscopy (CRDS) analyser (Picarro G2201-i). Two mechanical fluid extraction techniques are compared: ball milling in ZrO2 jars and sample crushing in a stainless steel sealed tube under a hydraulic press. Blanks and isotopically labelled tests with the ball milling technique suggest that rotation speed, grinding stock filling degree and filling type alter the CH4 and CO2 concentrations and isotopic compositions measured by the CRDS analyser. In contrast, the crushing technique does not generate measurable quantities of blank CH4 and CO2. The protocols presented in this study allow to extract, detect, and analyse δ13C of CH4 and CO2 for concentrations above 10 and 1,000 ppm respectively. Interlaboratory experiments allowed to replicate previously measured δ13C-CH4 values in natural fluid inclusions within 1‰ with both extraction techniques. This study highlights the potential of combining simple bulk off-line fluid inclusion extraction techniques with a CRDS analyser for δ13C analysis of CO2 and CH4 without gas separation being required.

Photonuclear reactions on 59Co at bremsstrahlung end-point energies of 40–130 MeV* *Supported in part by the Ministry of Science and Higher Education of the Russian Federation (075-15-2021-1360), and by the project of the National Center for Physics and Mathematics (NCPM) No. 6 ''Nuclear and Radiation Physics,'' direction 6.5.1

Relative yields were measured in the 40−130 MeV bremsstrahlung induced reactions of 59Co. The experiments were performed with the beam from the electron linear accelerator LINAC-200 using the activation and off-line γ-ray spectrometric techniques. The bremsstrahlung photon flux was calculated with the Geant4 program. The cross sections were calculated by using the computer code TALYS-1.96 with different models and were found to be in good agreement with the experimental data.

Monitoring Aggregation Processes in Multiphase Systems: A Review

Particle aggregation is essential in many industrial processes, spanning the pharmaceutical and food industries, polymer production, and the environment, among others. However, aggregation can also occur, in some processes, as a non-desired side effect. Thus, to be able to monitor aggregation in industrial processes is of high importance to guarantee that the final, required product characteristics are obtained. In this paper, we present an extensive review of the different techniques available for monitoring particle characteristics in industrial processes involving particulate materials, with special emphasis on aggregation processes. These methods include both off-line and on-line techniques, based either on image acquisition techniques or different radiation scattering techniques (light-scattering and ultrasound spectroscopy). The principles behind each technique are addressed, together with their relevant applications, advantages, and disadvantages.

Real-Time Monitoring of Air Pollution Health Impacts Using Breath-Borne Gaseous Biomarkers from Rats.

Offline techniques are adopted for studying air pollution health impacts, thus failing to provide in situ observations. Here, we have demonstrated their real-time monitoring by online analyzing an array of gaseous biomarkers from rats' exhaled breath using an integrated exhaled breath array sensor (IEBAS) developed. The biomarkers include total volatile organic compounds (TVOC), CO2, CO, NO, H2S, H2O2, O2, and NH3. Specific breath-borne VOCs were also analyzed by a gas chromatography-ion mobility spectrometer (GC-IMS). After real-life ambient air pollution exposures (2 h), the pollution levels of PM2.5 and O3 were both found to significantly affect the relative levels of multiple gaseous biomarkers in rats' breath. Eleven biomarkers, especially NO, H2S, and 1-propanol, were detected as significantly correlated with PM2.5 concentration, while heptanal was shown to be significantly correlated with O3. Likewise, significant changes were also detected in multiple breath-borne biomarkers from rats under lab-controlled O3 exposures with levels of 150, 300, and 1000 μg/m3 (2 h), compared to synthetic air exposure. Importantly, heptanal was experimentally confirmed as a reliable biomarker for O3 exposure, with a notable dose-response relationship. In contrast, conventional biomarkers of inflammation and oxidative stress in rat sera exhibited insignificant differences after the 2 h exposures. The results imply that breath-borne gaseous biomarkers can serve as an early and sensitive indicator for ambient pollutant exposure. This work pioneered a new research paradigm for online monitoring of air pollution health impacts while obtaining important candidate biomarker information for PM2.5 and O3 exposures.

Online and Offline Prioritization of Chemicals of Interest in Suspect Screening and Non-targeted Screening with High-Resolution Mass Spectrometry.

Recent advances in high-resolution mass spectrometry (HRMS) have enabled the detection of thousands of chemicals from a single sample, while computational methods have improved the identification and quantification of these chemicals in the absence of reference standards typically required in targeted analysis. However, to determine the presence of chemicals of interest that may pose an overall impact on ecological and human health, prioritization strategies must be used to effectively and efficiently highlight chemicals for further investigation. Prioritization can be based on a chemical's physicochemical properties, structure, exposure, and toxicity, in addition to its regulatory status. This Perspective aims to provide a framework for the strategies used for chemical prioritization that can be implemented to facilitate high-quality research and communication of results. These strategies are categorized as either "online" or "offline" prioritization techniques. Online prioritization techniques trigger the isolation and fragmentation of ions from the low-energy mass spectra in real time, with user-defined parameters. Offline prioritization techniques, in contrast, highlight chemicals of interest after the data has been acquired; detected features can be filtered and ranked based on the relative abundance or the predicted structure, toxicity, and concentration imputed from the tandem mass spectrum (MS2). Here we provide an overview of these prioritization techniques and how they have been successfully implemented and reported in the literature to find chemicals of elevated risk to human and ecological environments. A complete list of software and tools is available from https://nontargetedanalysis.org/.

Fission cross-section measurements for the 238U(n,f)97m+gNb, 238U(n,f)133gTe and 238U(n,f)130gSb reactions induced by D-T neutrons

In this study, we conducted measurements of the independent fission cross-sections of 238U(n, f)97m+gNb, 238U(n, f)133gTe reactions and the cumulative cross section of 238U(n, f)130gSb reactions induced by neutron at energies around 14 MeV, i.e., 14.1 ± 0.3, 14.5 ± 0.3 and 14.7 ± 0.3 MeV. The measurement results were obtained by the neutron activation method in combination with off-line γ-ray spectrometry techniques. The neutron flux was monitored on line by the accompanying α-particle from T(d, n)4He reaction, and the neutron energies were determined by the cross-section ratio of 90Zr(n, 2n)8+gZr to 93Nb(n, 2n)92mNb reactions. The independent fission cross-sections of the fission reactions were obtained by subtracting the influence of precursor nuclei or excited states. The obtained results are as follows: for 238U(n, f)97m+gNb, the independent cross sections are 1.0 ± 0.89, 0.98 ± 0.85 and 0.78 ± 0.70 mb at the specified neutron energy points. For 238U(n, f)133gTe, the independent fission cross-sections are 26.8 ± 2.8, 27.7 ± 2.9 and 20.5 ± 2.3 mb, respectively, at the same neutron energy points. As for 238U(n, f)130gSb, the obtained cumulative fission cross-sections are 5.35 ± 0.58, 5.05 ± 0.53 and 4.03 ± 0.44 mb, respectively, at the specified neutron energy points.

Comprehensive study of nanostructured Bi2Te3 thermoelectric materials - insights from synchrotron radiation XRD, XAFS, and XRF techniques.

In this contribution, a comprehensive study of nanostructured Bi2Te3 (BT) thermoelectric material was performed using a combination of synchrotron radiation-based techniques such as XAFS, and XRF, along with some other laboratory techniques such as XRD, XPS, FESEM, and HRTEM. This study aims to track the change in morphological, compositional, average and local/electronic structures of Bi2Te3 of two different phases; nanostructure (thin film) and nanopowders (NPs). Bi2Te3 nanomaterial was fabricated as pellets using zone melting process in a one step process, while Bi2Te3 thin film was deposited on sodalime glass substrate using a vacuum thermal evaporation technique. Synchrotron radiation-based Bi LIII-edge fluorescence-mode X-ray absorption fine structure (XAFS) technique was performed to probe locally the electronic and fine structures of BT thin film around the Bi atom, while transmission-mode XAFS was used for BT NPs distributed in the PVP matrix. The structural features of the collected Bi LIII XANES spectra of thin film and powder samples of BT are compared with the simulated XANES spectrum of BT calculated using FDMNES code at 5 Å cluster size. Combining different off-line structural characterization techniques (XRD, FESEM, XPS, and HRTEM), along with those of synchrotron radiation-based techniques (XAFS and XRF) is necessary for complementary and supported average crystal, chemical, morphological and local electronic structural analyses for unveiling the variation between Bi2Te3 in the nanostructure/thin film and nanopowder morphology, and then connecting between the structural features and functions of BT in two different morphologies. After that, we measured the Seebeck coefficient and the power factor values for both the BT nanopowder and thin film.

Pros and Cons of Separation, Fractionation and Cleanup for Enhancement of the Quantitative Analysis of Bitumen-Derived Organics in Process-Affected Waters—A Review

Oil sands process-affected water (OSPW) contains a diverse mixture of inorganic and organic compounds. Naphthenic acids (NAs) are a subset of the organic naphthenic acid fraction compounds (NAFCs) and are a major contributor of toxicity to aquatic species. Thousands of unique chemical formulae are measured in OSPW by accurate mass spectrometry and high-resolution mass spectrometry (MS) analysis of NAFCs. As no commercial reference standard is available to cover the range of compounds present in NAFCs, quantitation may best be referred to as “semi-quantitative” and is based on the responses of one or more model compounds. Negative mode electrospray ionization (ESI-) is often used for NAFC measurement but is prone to ion suppression in complex matrices. This review discusses aspects of off-line sample preparation techniques and liquid chromatography (LC) separations to help reduce ion suppression effects and improve the comparability of both inter-laboratory and intra-laboratory results. Alternative approaches to the analytical parameters discussed include extraction solvents, salt content of samples, extraction pH, off-line sample cleanup, on-line LC chromatography, calibration standards, MS ionization modes, NAFC compound classes, MS mass resolution, and the use of internal standards.

On the transition to gasoline-to-olefins chemistry in the cracking reactions of 1-octene over H-ZSM-5 catalysts

The cracking reactions of 1-octene over H-ZSM-5 zeolite are studied via micro-reactor and off-line spectroscopic techniques for up to 72 h on stream and a temperature range of 473–673 K. 1-Octene is found to react via a two-cycle hydrocarbon pool mechanism, with strong similarities to that reported for methanol-to-hydrocarbons chemistry. This dual-cycle mechanism requires temperatures of 673 K or higher to function with full efficiency, with lower temperatures deactivating portions of the cyclic mechanism, leading to premature deactivation of the catalyst through over-production of coke species. Inelastic neutron scattering is used to study the coke composition, identifying two distinct deactivation mechanisms depending on reaction temperature. The catalyst is also found to slowly progress from an aromatic-heavy to an olefin-heavy product regime even at full efficiency due to progressive blockage of active sites by amorphous carbon-rich coke. Artificial aging of the zeolite, through steam treatment, is found to shift the catalyst lifetime so that it commences at a later stage in this process, resulting in increased light olefin production. The reduced aromatic production also means that deactivation of the catalyst occurs more slowly in steamed catalysts than in fresh ones, after an equivalent time-on-stream. Collectively, these observations connect with the application of ZSM-5 catalysts to facilitate gasoline-to-olefins chemistry in fluidised catalytic cracking unit operations.

Detection of synthetic analogues of insulin-like growth factor 1 in different biological fluids by liquid chromatography quadrupole time-of-flight mass spectrometry: comparison of different immunoaffinity protocols.

Insulin-like growth factor 1 analogues are prohibited in sport for their ability to enhance athletic performance in several sport disciplines. Their detection presents several analytical challenges, mainly due to the minimum required performance limits fixed by the World Anti-Doping Agency. Here, we are presenting analytical workflows to detect IGF-1 and its analogues in different biological matrices. Several off-line immunocapture techniques and protocols were comparatively evaluated. Separation and detection were performed by using standard flow reverse-phase liquid chromatography coupled toa time-of-flight mass spectrometer. The best recoveries were obtained using magnetic beads or pipette tips functionalized with protein A. The analytical workflows were fully validated for qualitative determinations: all the target analytes were clearly distinguishable from the interference of the matrices, with limits of detection and identification in the range of 0.05-0.30ng/mL in urine and 0.5-2.0ng/mL in serum/plasma. The extraction efficiency proved to be repeatable (CV% < 10) with recoveries higher than 50%. Intra- and inter-day precision were found to be smaller than 10 and 15%, respectively. The method was successfully applied to the analysis of authentic matrix samples containing the target peptides at the minimum required performance limits, proving that the method developed can be successfully applied to detect and identify IGF-1 analogues for doping control purposes in all the matrices selected. The analytical workflow developed hereto detect the target peptides in different matrices can be readily implemented in anti-doping laboratories and has the potential to be adapted for the simultaneous analysis of different similarly sized peptide hormones of doping relevance.

Portable Nanoparticle-Enhanced Sensor for Tigecycline Determination in Biological Fluids and in the Presence of Its Degradation Products

Tigecycline (TGC) is a novel potent antibiotic with recently proven anticancer activity against leukemia, glioma, and lung cancer. In-line TGC potentiometric sensors are fabricated for monitoring TGC in its pure form, pharmaceutical formulation, presence of its degradation products, and spiked human plasma. In-line sensors act as greener, portable, and economical alternatives to the classical off-line separation-based techniques. Classical and advanced liquid-contact (LC) and solid-contact (SC) sensors were fabricated, where the best performance was observed with the modified SC sensor (sensor VI) with potassium tetrakis (4-chlorophenyl) borate as ionic exchanger, β-cyclodextrin ionophore and cobalt oxide nanoparticles, showing a Nernstian response of 30 mV decade−1 in the linear range of 10−2–10−6 M. Statistical comparison was carried out for the results obtained from proposed SC sensors and the official method on TGC pure form. Additionally, method greenness was evaluated using a semi-quantitative analytical eco-scale, scoring approximately 95 points, which was the highest greenness achievement score when compared to the proposed LC sensors or British Pharmacopeial chromatographic method.

Real-time environmental surveillance of SARS-CoV-2 aerosols

Real-time surveillance of airborne SARS-CoV-2 virus is a technological gap that has eluded the scientific community since the beginning of the COVID-19 pandemic. Offline air sampling techniques for SARS-CoV-2 detection suffer from longer turnaround times and require skilled labor. Here, we present a proof-of-concept pathogen Air Quality (pAQ) monitor for real-time (5 min time resolution) direct detection of SARS-CoV-2 aerosols. The system synergistically integrates a high flow (~1000 lpm) wet cyclone air sampler and a nanobody-based ultrasensitive micro-immunoelectrode biosensor. The wet cyclone showed comparable or better virus sampling performance than commercially available samplers. Laboratory experiments demonstrate a device sensitivity of 77–83% and a limit of detection of 7-35 viral RNA copies/m3 of air. Our pAQ monitor is suited for point-of-need surveillance of SARS-CoV-2 variants in indoor environments and can be adapted for multiplexed detection of other respiratory pathogens of interest. Widespread adoption of such technology could assist public health officials with implementing rapid disease control measures.

Production of Volatile Organic Compounds by Ozone Oxidation Chemistry at the South China Sea Surface Microlayer

Ozone (O3) oxidation chemistry on proxy compounds of the sea surface microlayer (SML) generates volatile organic compounds (VOCs) in the atmosphere. To shed light on the proposed significance of this chemistry, we investigated the formation of VOCs through heterogeneous chemistry of O3 (100 ppb) with authentic SML collected from 10 sites in the South China Sea using a reactor coupled to proton transfer reaction–time of flight–mass spectrometry (PTR–TOF–MS) and subsequently identified by off-line techniques. On the basis of the semi-quantitative data of the identified compounds, we estimated the production rates of acetone, acetaldehyde, propanal, hexanal, heptanal, octanal, and nonanal, which correspond to the experimental conditions applied in this study. These results provide a significant update to our understanding of abiotic formation of VOCs in the marine atmosphere, which should be considered in future model studies to properly evaluate the VOC contribution of ozone heterogeneous chemistry with the SML.

90 Graphene – Exposure and Emissions at Two Pilot Plants

Abstract Graphene is a nanomaterial suitable for a wide variety of applications. The industrial production and use of graphene is, hence, increasing rapidly. The main challenge in assessing graphene exposure is that graphene is a carbon structure, making it comparable to look for a needle in a haystack. We have explored the possibility to analyze elemental carbon and black carbon as a measure of personal graphene exposure. Exposure and emission measurements for graphene were conducted at two pilot plants using on- and off-line techniques. One plant produces graphene, up to 10 tons per year, using liquid exfoliation technique. The other plant uses graphene to coat paper in a conventional roll-to-roll process. The measurements were conducted both stationary (in the emission zone and in the background) and as personal measurements (in the breathing zone of the workers). We have analyzed elemental carbon and black carbon as a measure of the personal exposure. In the emission and background zone we have measured number of particles and lung deposited surface area concentration of particles &amp;lt;300nm, mass concentration, and we have collected samples for electron microscopy analysis. The exposure was in general low, but we identified tasks with an increase emissions. Measurements of elemental carbon is a promising technique for occupational hygienists to find possible exposure to graphene.

On-site Insulation Tests for MV cable using Very Low Frequency and Damped AC Techniques

MV cables are vital components in urban power networks. Several insulation test techniques are proposed for guaranteeing the operation of MV cables. In this paper, two kinds of off-line testing techniques are introduced, namely Tanδ measurement using VLF and PD detection using DAC. Firstly, the operation principle of each technique is introduced. Then, a simulation model was built in Simulink platform to demonstrate the operation processes of detecting the defects in the cable. At last, an on-site case using both VLF and DAC techniques is introduced for presenting the functions of different techniques.

Characterization of PFAS Air Emissions from Thermal Application of Fluoropolymer Dispersions on Fabrics

ABSTRACT During thermal processes utilized in affixing fluoropolymer coatings to fibers and fabrics, coating components are vaporized. It is suspected that per- and polyfluoroalkyl substances (PFAS) from the dispersions may undergo chemical transformations at the temperatures used, leading to emitted PFAS thermal byproducts. It is important to characterize these emissions to support evaluation of resulting environmental and health impacts. In this study, a bench-scale system was built to simulate this industrial process via thermal application of dispersions to fiberglass utilizing relevant temperatures and residence times in sequential drying, baking, and sintering steps. Experiments were performed with two commercially available dispersions and a simple model mixture containing a single PFAS species (6:2 fluorotelomer alcohol [6:2 FTOH]). Vapor-phase emissions were sampled and characterized by several off-line and real-time mass spectrometry techniques for targeted and non-targeted PFAS. Results indicate multiple PFAS thermal transformation products and multiple non-halogenated organic species were emitted from the exit of the high temperature third (sintering) furnace when 6:2 FTOH was the only PFAS present in the aqueous mixture. This finding supports the hypothesis that temperatures typical of these industrial furnaces may also induce chemical transformations within the fluorinated air emissions. Experiments using the two commercial fluoropolymer dispersions indicate air emissions of part-per-million by volume (ppmv) concentrations of heptafluoropropyl-1,2,2,2-tetrafluoroethyl ether (Fluoroether E1), as well as other PFAS at operationally relevant temperatures. We suspect that E1 is a direct thermal decomposition product (via decarboxylation) of 2,3,3,3-tetrafluoro-2-(heptafluoropropoxy)propanoic acid (commonly referred to as HFPO-DA) present in the dispersions. Other thermal decomposition products, including the monomer, tetrafluoroethene, may originate from the PFAS used to stabilize the dispersion or from the polymer particles in suspension. This study represents the first researcher-built coating application simulator to report nontargeted PFAS emission characterization, real-time analyses, and the quantification of 30 volatile target PFAS.

Event-Triggered Hybrid Energy-aware Scheduling in Manufacturing Systems

Incorporating renewable energy sources (RESs) into manufacturing systems has been an active research area in order to address many challenges originating from the unpredictable nature of RESs such as photovoltaics. In the energy-aware scheduling for manufacturing systems, the traditional off-line scheduling techniques cannot always work well due to their lack of robustness with respect to uncertainties coming from imprecise models or unexpected situations. On the other hand, on-line scheduling or rescheduling, which can improve the robustness by using the model and the latest measurements simultaneously, suffer from a high computational cost. This work proposes a hybrid scheduling framework, which combines the advantages of both off-line scheduling and on-line scheduling, to provide a balanced solution between robustness and computational cost. A novel concept of partially-dispatchable state is introduced. It can be treated as a constant in scheduling when the model works well. When the model does not work well, it is triggered as the variable to tune to improve the performance. Such an event-triggered structure can reduce the number of rescheduling and computational costs while achieving a reasonable performance and enhancing system robustness. Moreover, the choice of partially-dispatchable state also provides an extra design freedom in achieving green manufacturing. Simulation examples on a manufacturing system, which consists of a 100-kW solar photovoltaic system, a 10-machine flow shop production line, a 50-kWh energy storage system, a 100-kW gas turbine, and the grid for power supply, demonstrate the validity and applicability of this event-triggered hybrid scheduling (ETHS) framework.

ADASSM: Adversarial Data Augmentation in Statistical Shape Models From Images.

Statistical shape models (SSM) have been well-established as an excellent tool for identifying variations in the morphology of anatomy across the underlying population. Shape models use consistent shape representation across all the samples in a given cohort, which helps to compare shapes and identify the variations that can detect pathologies and help in formulating treatment plans. In medical imaging, computing these shape representations from CT/MRI scans requires time-intensive preprocessing operations, including but not limited to anatomy segmentation annotations, registration, and texture denoising. Deep learning models have demonstrated exceptional capabilities in learning shape representations directly from volumetric images, giving rise to highly effective and efficient Image-to-SSM networks. Nevertheless, these models are data-hungry and due to the limited availability of medical data, deep learning models tend to overfit. Offline data augmentation techniques, that use kernel density estimation based (KDE) methods for generating shape-augmented samples, have successfully aided Image-to-SSM networks in achieving comparable accuracy to traditional SSM methods. However, these augmentation methods focus on shape augmentation, whereas deep learning models exhibit image-based texture bias resulting in sub-optimal models. This paper introduces a novel strategy for on-the-fly data augmentation for the Image-to-SSM framework by leveraging data-dependent noise generation or texture augmentation. The proposed framework is trained as an adversary to the Image-to-SSM network, augmenting diverse and challenging noisy samples. Our approach achieves improved accuracy by encouraging the model to focus on the underlying geometry rather than relying solely on pixel values.

(Invited) Analytical Solutions for Quality Assurance across the Battery Manufacturing Process

Battery performance degradation and potentially dangerous incidents such as thermal runaway and fire can originate from defects in lithium battery components or during cell assembly. Therefore, quality assurance is extremely important aspect of the manufacturing process to identify and eliminate defects that may give rise to cell failure and dangerous incidents. From validating raw material purity and monitoring electrode thickness, to inspection of component alignment and integrity during assembly, different analytical capabilities are used to ensure quality is maintained through battery manufacturing workflow. In this presentation examples of using in-line and off-line analytical characterization techniques, such as in-line basis weight and thickness measurement systems and electron microscopes, to monitor the quality during battery manufacturing process will be discussed. Advances in in-line and off-line metrology and quality control tools are an important enabler for solving the current challenges and facilitating future growth in electric propulsion and energy storage technologies.

Cross-sections of photonuclear reactions 65Cu(γ, n)64Cu and 63Cu(γ, xn)63−xCu in the energy range E γmax = 35–94 MeV

The flux-averaged cross-sections for the reactions , , , and have been measured within the bremsstrahlung end-point energy range of 35–94 MeV. The experiments were performed with the electron beam from the NSC KIPT linear accelerator LUE-40 with the use of the activation and off-line γ-ray spectrometric techniques. Theoretical calculation of the flux-average cross-sections was conducted using the cross-section values from the TALYS1.95 code, run with default options. It is shown that the experimental average cross-sections for the reactions , , and are systematically higher than the theoretical estimates based on the TALYS1.95 code. The obtained values supplement the data of different laboratories for the and reactions of and . For the reaction , the values of were measured for the first time.