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Hydrogen as an alternative fuel for engines is gaining interest to decarbonize the heavy-duty sector. Hydrogen combustion in engines conventionally relies on the Otto cycle and either port fuel or direct injection. This combustion concept usually results in poor power density and non-ideal efficiencies due to the lean premixed operation and low compression ratio required to avoid preignition and knocking. In this study, hydrogen is directly injected at high pressures into the combustion chamber and spark-ignited with two different ignition systems (inductive and nanosecond repetitively pulsed discharge) at the periphery of the jet, with fuel conversion taking place predominantly in jet-guided (diffusion) mode while injection remains active. A rapid compression expansion machine (RCEM) is used to investigate the jet-guided hydrogen combustion thermodynamically and optically by combining high-speed Schlieren and OH* chemiluminescence imaging, and spark-induced breakdown spectroscopy (SIBS). SIBS reveals low air to fuel ratios at ignition time and location, ranging from 2.8 up to pure air depending on the condition and significant variation among repetitions. Both OH* chemiluminescence and Schlieren images illustrate how air entrainment pushes the flame-plasma kernel from the ignition location at the periphery of the jet towards the fuel-richer core, resulting in fast combustion of the already premixed fuel. Subsequently, the combustion process becomes dominated by the mixing dynamics. Under conditions of low in-cylinder pressures, the Heat Release Rate (HRR) closely follows the injected mass flow rate multiplied by the lower heating value of hydrogen, i.e., the combustion is mixing controlled. However, as the cylinder pressure increases, the mixing and combustion rates fall below the injected mass flow until lower densities are reached again. The delay between the start of injection and ignition primarily impacts the premixed peak, but the in-cylinder pressure and ignition source also play significant roles. This distinctive combustion process shows essential similarities to compression ignition Diesel combustion. The process holds the potential to achieve high efficiency, as hydrogen can be burned using process parameters typical of Diesel combustion without facing the constraints of knock or preignition and a complete absence of soot. [Display omitted] • Thermodynamic and optical analysis of Jet-guided spark-ignited hydrogen combustion in a Rapid Compression Expansion Machine. • Premixed phase of the combustion affected by the delay between the start of injection and ignition. • Influence of the pressure ratio between injection and in-cylinder pressure during diffusion combustion. • Hydrogen jet-guided combustion shows similarities to compression ignition. Diesel combustion. [ABSTRACT FROM AUTHOR]

Hydrogen is a volatile element, both as a molecular gas and as atomic hydrogen in materials. A method is described for the detection of the corresponding dynamic hydrogen in matter, as opposed to the relatively stable bond hydrogen ("static hydrogen"). The method is based on laser-stimulated hydrogen desorption using nanosecond laser pulses in the UV optical range. The principle, already established for surface hydrogen on nonabsorbent metals has been extended to hydrogen affine bulk systems. The feasibility of the idea is demonstrated by quantifying hydrogen in hydrogen-permeable metal membranes. Model experiments, such as HD exchange, provide input to the model to extract the surface hydrogen concentration of dynamic hydrogen from laser-stimulated hydrogen desorption while eliminating the influence of the laser-matter interaction on the quantification. An estimate of the limit of detection is given.

Chlorinated paraffins (CP) are complex molecular mixtures occurring in a wide range of isomers and homologs of environmental hazards, whose analytical complexity demand advanced mass spectrometry (MS) methods for their characterization. The reported formation of chlorinated olefins (COs) and other transformation products during CP biotransformation and degradation can alter the MS analysis, increasing the high resolution required to distinguish CPs from their degradation products. An advanced setup hyphenating a plasma ionization source and an external high-performance data acquisition and processing system to the legacy hybrid LTQ Orbitrap XL mass spectrometer is reported. First, the study demonstrated the versatility of a liquid sampling atmospheric pressure glow discharge, as a soft ionization technique, for CP analysis. Second, enhanced resolution and sensitivity provided by the absorption mode Fourier transform spectral representation on this legacy mass spectrometer are shown. The developed Orbitrap-based platform allowed the detection of new isotopic clusters and CPs and COs to be distinguished at medium resolution (setting 30,000 at m/z 400, ~ 400 ms transients), and even chlorinated di-olefins (CdiOs) at higher resolution (setting 100,000 at m/z 400, ~ 1500 ms transients). Overall, such proof-of-principle instrumental improvements are promising for environmental and analytical research in the field of CP analysis., (© 2024. The Author(s).)

Chlorinated paraffins (CPs) are complex mixtures of polychlorinated n -alkanes with multiple carbon- (C-, n C = 9-30) and chlorine homologues (Cl-, n Cl = 3-18). The mass spectrometric analysis of CPs is time-consuming and challenging, especially when interferences between CPs, their transformation products, or from the matrix are numerous. These analytical challenges and the lack of appropriate and accessible data evaluation tools are obstacles to their analysis. CP-Hunter is a web-based, open-access data processing platform for the automatic analysis of mass spectra of CPs and their transformation products. Extracts of two consumer plastic materials and sewage sludge were evaluated with CP-Hunter. C- and Cl-homologue distributions were obtained in quasi-real-time and the posterior calculated fingerprints were in agreement with the ones obtained by traditional methods. However, the data extraction and evaluation time were now reduced from several minutes to seconds. The implemented signal deconvolution method, i.e., to resolve mass spectrometric interferences, provides robust results, even when severe matrix effects are present. CP-Hunter facilitates the untargeted analysis of unknown products and the detection and elimination of false positive signals. Finally, data evaluation with CP-Hunter is performed locally without the transfer of data to external servers. The tool is safe, public, and accessible at https://cphunter.cheminfo.org/.

Experimental characterization of the structural, electronic and dynamic properties of dilute systems in aqueous solvents, such as nanoparticles, molecules and proteins, are nowadays an open challenge. X-ray absorption spectroscopy (XAS) is probably one of the most established approaches to this aim as it is element-specific. However, typical dilute systems of interest are often composed of light elements that require extreme-ultraviolet to soft X-ray photons. In this spectral regime, water and other solvents are rather opaque, thus demanding radical reduction of the solvent volume and removal of the liquid to minimize background absorption. Here, we present an experimental endstation designed to operate a liquid flat jet of sub-micrometre thickness in a vacuum environment compatible with extreme ultraviolet/soft XAS measurements in transmission geometry. The apparatus developed can be easily connected to synchrotron and free-electron-laser user-facility beamlines dedicated to XAS experiments. The conditions for stable generation and control of the liquid flat jet are analyzed and discussed. Preliminary soft XAS measurements on some test solutions are shown., (open access.)

Exposure of humans to chlorinated paraffins (CPs) and chlorinated olefins (COs) can occur via contact with CP-containing plastic materials. Such plastic materials can contain short-chain CPs (SCCPs), which are regulated as persistent organic pollutants (POPs) under the Stockholm Convention since 2017. Municipal wastewater treatment plants (WWTP) collect effluents of thousands of households and their sludge is a marker for CP exposure. We investigated digested sewage sludge collected in the years 1993, 2002, 2007, 2012, and 2020 from a Swiss WWTP serving between 20000 and 23000 inhabitants. A liquid chromatography mass spectrometry (R > 100000) method, in combination with an atmospheric pressure chemical ionization source (LC-APCI-MS), was used to detect mass spectra of CPs and olefinic side products. A R-based automated spectra evaluation routine (RASER) was applied to search for ∼23000 ions whereof ∼6000 ions could be assigned to CPs, chlorinated mono- (COs), di- (CdiOs) and tri-olefins (CtriOs). Up to 230 CP-, 120 CO-, 50 CdiO- and 20 CtriO-homologues could be identified in sludge. Characteristic fingerprints were deduced describing C- and Cl-homologue distributions, chlorine- (n Cl ) and carbon- (n C ) numbers of CPs and COs. In addition, proportions of saturated and unsaturated material were determined together with proportions of different chain length classes including short- (SC), medium- (MC), long- (LC) and very long-chain (vLC) material. A substantial reduction of SCCPs of 84% was observed from 1993 to 2020. Respective levels of MCCPs, LCCPs and vLCCPs decreased by 61, 69 and 58%. These trends confirm that banned SCCPs and non-regulated CPs are present in WWTP sludge and higher-chlorinated SCCPs were replaced by lower chlorinated MCCPs. Combining high-resolution mass spectrometry with a selective and fast data evaluation method can produce characteristic fingerprints of sewage sludge describing the long-term trends in a WWTP catchment area., Competing Interests: Declaration of competing interest All authors declare that there are no conflicts of interest., (Copyright © 2023 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Chlorinated paraffins (CPs) are complex mixtures consisting of various C homologues ( n C ≈ 10-30) and Cl homologues ( n Cl ≈ 2-20). Technical CP mixtures are produced on a large scale (>10 6 t/y) and are widely used such as plasticizers in plastic and coolants in metalwork. Since 2017, short-chain CPs (C 10 -C 13 ) are classified as persistent organic pollutants (POPs) by the Stockholm Convention but longer-chain CPs are not regulated. Analysis of technical CP mixtures is challenging because they consist of hundreds of homologues and millions of constitutional isomers and stereoisomers. Furthermore, such mixtures can also contain byproducts and transformation products such as chlorinated olefins (COs). We applied a liquid-chromatography method coupled to an atmospheric pressure chemical ionization technique with a high-resolution mass detector (LC-APCI-Orbitrap-MS) to study CP and CO homologues in two plastic materials. Respective mass spectra can contain up to 23,000 signals from 1320 different C-Cl homologue classes. The R-based automated spectra evaluation routine (RASER) was developed to efficiently search for characteristic ions in these complex mass spectra. With it, the time needed to evaluate such spectra was reduced from weeks to hours, compared to manual data evaluation. Unique sets of homologue distributions could be obtained from the two plastic materials. CPs were found together with their transformation products, the chlorinated mono-olefins (COs), di-olefins (CdiOs), and tri-olefins (CtriOs) in both plastic materials. Based on these examples, it can be shown that RASER is an efficient and selective tool for evaluating high-resolution mass spectra of CP mixtures containing hundreds of homologues.

The kinetics of most of chemical energy storage and conversion processes is rate-limited by the mass transport through matter. There is an uncertainty on the corresponding kinetic models, especially if based solely on kinetic theory. Henceforth analytical strategies coupled to setups, in order to capture data for overcoming this limitation are essential. Operando chemical imaging of the kinetics process supports the identification of rate-limiting barriers and definition of actionable kinetic insights. After an overview of the chemical and physical processes in various energy storage/conversion systems, and examples of chemical imaging applied on them, analytical challenges are discussed with particular focus on novel methods and fundamental limitations. Despite convincing success technologies, various scientific challenges of operando chemical kinetics await solution. Apart from technical improvements of the analysis instrumentation, promising developments are seen in advanced digital science., (Copyright 2022 Andreas Borgschulte, Emanuel Billeter, Alessia Cesarini, Yousuf Hemani, Marco Knobloch, Kevin Kraft, Filippo Longo, Claudia Masucci, Marin Nikolic, Di Qu, Davide Bleiner. License: This work is licensed under a Creative Commons Attribution 4.0 International License.)

Technical chlorinated paraffins (CPs) are produced via radical chlorination of n-alkane feedstocks with different carbon chain-lengths (∼C 10 -C 30 ). Short-chain CPs (SCCPs, C 10 -C 13 ) are classified as persistent organic pollutants (POPs) under the Stockholm Convention. This regulation has induced a shift to use longer-chain CPs as substitutes. Consequently, medium-chain (MCCPs, C 14 -C 17 ) and long-chain (LCCPs, C > 17 ) CPs have become dominant homologues in recent environmental samples. However, no suitable LCCP-standard materials are available. Herein, we report on the chemical synthesis of single-chain C 18 -CP-materials, starting with a pure n-alkane and sulfuryl chloride (SO 2 Cl 2 ). Fractionation of the crude product by normal-phase liquid-chromatography and pooling of suitable fractions yielded in four C 18 -CP-materials with different chlorination degrees (m Cl,EA  = 39-52%). In addition, polar side-products, tentatively identified as sulfite-, sulfate- and bis-sulfate-diesters, were separated from CPs. The new single-chain materials were characterized by LC-MS, 1 H-NMR and EA. LC-MS provided Relative retention times for different C 18 -CP homologues and side-products. Mathematical deconvolution of full-scan mass spectra revealed the presence of chloroparaffins (57-93%) and chloroolefins (COs, 7-26%) in the four single-chain C 18 -CP-materials. Homologue distributions and chlorination degrees were deduced for CPs and COs. 1 H-NMR revealed chemical shift ranges of mono-chlorinated (δ = 3.2-5.3 ppm) and non-chlorinated (δ = 1.0-3.2 ppm) hydrocarbon moieties. The synthesized C 18 -single-chain standard materials and respective spectroscopic data are useful to identify and quantify LCCPs in various materials and environmental samples. CP- and CO-distributions resemble the ones of existing SCCP and MCCP reference materials and technical mixtures. Furthermore, these materials now allow specific studies on the environmental fate and the transformation of long-chain chloroparaffins and chloroolefins., (Copyright © 2021 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Transformation studies of chlorinated paraffins (CPs) and the effects of CP transformation products on humans, biota and environment are rare. The focus here is on hydroxylation reactions. As for polyhalogenated persistent organic pollutants (POPs) in general, hydroxylation reactions convert lipophilic material to more polar compounds with increased mobility. We investigated the in-vitro transformation of single-chain CP-mixtures to hydroxylated products with the dehalogenase LinB from Sphingobium indicum. C 11 -, C 12 - and C 13 -single-chain CP-homologues were exposed to LinB and mono-hydroxylated (CP-ols) and di-hydroxylated (CP-diols) transformation products were formed. Liquid-chromatography coupled to mass-spectrometry (LC-MS) was used to detect hydroxylated products and to separate them from the starting material. The presented data can be used to identify these CP-ol and CP-diol homologues in other samples. Hydroxylated products had lower chlorination degrees (n Cl ) than respective CP-starting-materials. Reactive and persistent CP-material was found in each homologue group. Reactive material is converted within hours by LinB, while more persistent CPs are transformed within days. Homologue-specific kinetic models were established to simulate the stepwise hydroxylation of persistent CPs to mono- and di-hydroxylated products. First-order rate constants for the formation of CP-ols (k 1 ) and CP-diols (k 2 ) were deduced for different homologues. Lower-chlorinated CP-ols did not accumulate to large extent and were transformed quickly to CP-diols, while higher-chlorinated CP-ols and -diols both accumulated. By enzymatic transformation of single-chain CPs with LinB, we synthesized unique sets of mono- and di-hydroxylated materials, which can be used as analytical standards and as starting materials for metabolic, toxicity and environmental fate studies., (Copyright © 2021 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Structure, reactivity and physico-chemical properties of polyhalogenated compounds determine their up-take, transport, bio-accumulation, transformation and toxicity and their environmental fate. In technical mixtures of chlorinated paraffins (CPs), these properties are distributed due to the presence of thousands of homologues. We hypothesized that roles of CP dehalogenation reactions, catalyzed by the haloalkane dehalogenase LinB, depend on structural properties of the substrates, e.g. chlorination degree and carbon-chain length. We exposed mixtures of chlorinated undecanes, dodecanes and tridecanes in-vitro to LinB from Sphingobium Indicum bacteria. These single-chain CP-materials also contain small amounts of chlorinated olefins (COs), which can be distinct by mathematical deconvolution of respective mass-spectra. With this procedure, we obtained homologue-specific transformation kinetics of substrates differing in saturation degree, chlorination degree and carbon chain-length. For all homologues, two-stage first-order kinetic models were established, which described the faster conversion of reactive material and the slower transformation of more persistent material. Half-lifes of 0.5-3.2 h and 56-162 h were determined for more reactive and more persistent CP-material. Proportions of persistent material increased steadily from 18 to 67% for lower (Cl 6 ) to higher (Cl 11 ) chlorinated paraffins and olefins. Conversion efficiencies decreased with increasing chlorination degree from 97 to 70%. Carbon-chain length had only minor effects on transformation rates. Hence, the conversion was faster and more efficient for lower-chlorinated material, and slower for higher-chlorinated and longer-chained CPs and COs. Current legislation has banned short-chain chlorinated paraffins (SCCPs) and forced a transition to longer-chain CPs. This may be counterproductive with regard to enzymatic transformation with LinB., (Copyright © 2021 The Authors. Published by Elsevier Ltd.. All rights reserved.)