Speciation Information Research Articles

Free gallium (III) determination with AGNES (Absence of Gradients and Nernstian Equilibrium Stripping)

Gallium is being extensively used in technological applications. Increasing emissions to the environment classify it as an emerging contaminant. Speciation information, such as the free gallium concentration, [Ga3+], is fundamental for understanding/predicting its bioavailability and potential toxicity to biota. In this work, [Ga3+] in aqueous solutions at pH2 and 3 has been measured with AGNES (Absence of Gradients and Nernstian Equilibrium Stripping). The deposition times to reach equilibrium, for a fixed accumulation factor or gain, were longer than those required with other metals such as Zn, Pb, Cd and In. This is attributed to the electrodic irreversibility of the couple Ga0/Ga3+ on the mercury electrode together with low concentrations of relatively poorly labile and/or poorly reversible (for the electrodic transfer) hydroxy complexes. When the AGNES-SCP variant was applied in the Hanging Mercury Drop Electrode with radius 141 μm, and the transition time was ≤10 s, the correction of the deposited mass with a depletion factor was essential. The speciation capacity of AGNES for Ga was evaluated with the phthalate ligand at pH 3 and the experimental results obtained were very similar to the theoretical results predicted with the stability constants in the NIST and Brown-Ekberg databases.

In situ X-ray absorption spectroscopy using the FAME autoclave: a window into fluid-mineral-melt interactions in the Earth’s crust

ABSTRACT We discuss the X-ray absorption spectroscopy (XAS) methods elaborated using the high pressure and high-temperature autoclaves installed at FAME and FAME-UHD beamlines. These methods are based on the in situ acquisition of X-ray transmission and fluorescence spectra of hydrothermal fluids and silicate melts and enable the derivation of both solubility and speciation information about metal complexes. The technological assets of our autoclaves are described across a wide range of experimental conditions spanning from different types of hydrothermal fluids, from liquid-like to vapor-like densities having metal concentrations of <1–10,000 ppm, to magmatic fluid-melt systems at 1000°C. Scientific examples are presented to illustrate the use and the advantages of our spectroscopic ‘micro-batch’ reactors. Finally, the integration of our autoclave setups on the FAME-UHD crystal analyzer spectrometer and the benefits of this technique are demonstrated.

Gold Nanoparticle-Modified Carbon-Fiber Microelectrodes for the Electrochemical Detection of Cd2+ via Fast-Scan Cyclic Voltammetry.

Neurotoxic heavy metals, such as Cd2+, pose a significant global health concern due to their increased environmental contamination and subsequent detrimental health hazards they pose to human beings. These metal ions can breach the blood-brain barrierblood-brain barrier, leading to severe and often irreversible damage to the central nervous system and other vital organs. Therefore, developing a highly sensitive, robust, and rapid in vivo detection method for these hazardous heavy metal ions is of the utmost importance for early detection, thus initiating timely therapeutics. Detecting ultra-low levels of toxic metal ions in vivo and obtaining accurate speciation information remains a challenge with conventional analytical techniques. In this study, we fabricated a novel carbon carbon-fiber microelectrode (CFM)-based sensor that can detect Cd2+ ions using fast-scan cyclic voltammetry by electrodepositing gold nanoparticles (AuNP). We optimized electrochemical parameters that generate a unique cyclic voltammogram (CV) of Cd2+ at a temporal resolution of 100 ms with our novel sensor. All our experiments were performed in tris buffer that mimics the artificial cerebellum fluid. We established a calibration curve resulting in a limit of detection (LOD) of 0.01 µM with a corresponding sensitivity of 418.02 nA/ µM. The sensor's selectivity was evaluated in the presence of other metal ions, and it was noteworthy to observe that the sensor retained its ability to produce the distinctive Cd2+ CV, even when the concentration of other metal ions was 200 times higher than that of Cd2+. We also found that our sensor could detect free Cd2+ ions in the presence of complexing agents. Furthermore, we analyzed the solution chemistry of each of those Cd2+-ligand solutions using a geochemical model, PHREEQC. The concentrations of free Cd2+ ions determined through our electrochemical data align well with geochemical modeling data, thus validating the response of our novel sensor. Furthermore, we reassessed our sensor's LOD in tris buffer based on the concentration of free Cd2+ ions determined through PHREEQC analysis, revealing an LOD of 0.00132 µM. We also demonstrated the capability of our sensor to detect Cd2+ ions in artificial urine samples, showcasing its potential for application in actual biological samples. To the best of our knowledge, this is the first AuNP-modified, CFM-based Cd2+ sensor capable of detecting ultra-low concentrations of free Cd2+ ions in different complex matrices, including artificial urine at a temporal resolution of 100 ms, making it an excellent analytical tool for future real-time, in vivo detection, particularly in the brain.

Combined X-ray absorption and SEM–EDX spectroscopic analysis for the speciation of thorium in soil

Mobility and bioavailability of radionuclides in the environment strongly depend on their aqueous speciation, adsorption behavior and the solubility of relevant solid phases. In the present context, we focus on naturally occurring Th-232 at a location in central Sri Lanka presenting high background radiation levels. Four different soil samples were characterized using X-ray Absorption Spectroscopy (XAS) at the Th L3-edge (16.3 keV), Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray (EDX) spectroscopy. X-ray Absorption Near Edge Structure (XANES) spectra are applied as a fingerprint indication for Th existing in different chemical environments. Linear combination fitting (LCF) of the Extended X-ray Absorption Fine Structure (EXAFS) data involving reference Th-monazite (phosphate) and thorianite (oxide) compounds suggested that Th is mostly present as Th-phosphate (76 ± 2%) and Th-oxide (24 ± 2%), even though minor amounts of thorite (silicate) were also detected by SEM–EDX. Further studies on selected individual particles using micro-focus X-ray Fluorescence (μ-XRF) and micro-X-ray Absorption Spectroscopy (μ-XAS) along with SEM–EDX elemental mapping provided information about the nature of Th-bearing mineral particles regarding mixed phases. This is the first study providing quantitative and XAS based speciation information on Th-mineral phases in soil samples from Sri Lanka.

Vanadium Speciation in Ancient Shales Revealed through Synchrotron-Based X-ray Spectroscopy

Redox-sensitive trace elements, such as vanadium, are frequently used as paleoredox proxies to infer the redox status of ancient marine depositional environments. When applied to vanadium, this approach relies on an accurate understanding of vanadium geochemistry in marine sediments. This, in turn, requires the application of analytical techniques capable of providing reliable chemical information on vanadium host phases of vanadium and thus the ability to distinguish authigenic from detrital phases. The increasing availability of synchrotron-based X-ray spectroscopic techniques capable of providing chemical speciation information at both the bulk and micro-scale presents an opportunity to refine our understanding of vanadium geochemistry in ancient marine sediments. Here, we show the utility of synchrotron-based X-ray absorption near-edge structure (XANES) spectroscopy and scanning X-ray fluorescence microscopy (SXFM) for investigating vanadium host phases in ancient marine sediments. The studied samples from the 1400 Ma Xiamaling Formation came from strongly contrasting depositional settings (ranging from oxic to euxinic) with a wide range of vanadium enrichments (enrichment factors from 0.7 to 9.6), yet vanadium speciation determined by XANES was consistently found to be phyllosilicate-hosted vanadium (III). High-resolution elemental imaging by SXFM coupled with global statistical colocalization analyses revealed strong associations between vanadium and potassium, consistent with vanadium hosted by potassium-rich clay minerals. These findings, while demonstrating the power of synchrotron-based X-ray methods, imply that differentiating authigenic and detrital vanadium in ancient marine sediments is unlikely to be possible given that post-depositional processes result in similar chemical speciation for both fractions. This will also limit the reliability of vanadium isotope system studies that depend on differentiating authigenic and detrital fractions using selective extraction procedures.

Electrodeposition of dopamine onto carbon fiber microelectrodes to enhance the detection of Cu2+ via fast-scan cyclic voltammetry.

The etiology of neurodegenerative diseases is poorly understood; however, studies have shown that heavy metals, such as copper, play a critical role in neurotoxicity, thus, adversely affecting the development of these diseases. Because of the limitations associated with classical metal detection tools to obtain accurate speciation information of ultra-low concentrations of heavy metals in the brain, analysis is primarily performed in blood, urine, or postmortem tissues, limiting the translatability of acquired knowledge to living systems. Inadequate and less accurate data obtained with such techniques provide little or no information for developing efficient therapeutics that aid in slowing down the deterioration of brain cells. In this study, we developed a biocompatible, ultra-fast, low-cost, and robust surface-modified electrode with carbon fibers by electrodepositing dopamine via fast-scan cyclic voltammetry (FSCV) to detect Cu2+ in modified tris buffer. We studied the surface morphology of our newly introduced sensors using high-resolution images by atomic force microscopy under different deposition conditions. The limit of detection (LOD) of our surface-modified sensor was 0.01µM (0.64ppb), and the sensitivity was 11.28 nA/µM. The LOD and sensitivity are fifty and two times greater, respectively, compared to those of a bare electrode. The sensor's response is not affected by the presence of dopamine in the matrix. It also exhibited excellent stability to multiple subsequent injections and repeated measurements of Cu2+ over a month, thus showing its strength to be developed into an accurate, fast, robust electrochemical tool to monitor ultra-low concentrations of heavy metals in the brain in real time.

Exploring low-temperature oxidation chemistry of 2- and 3-pentanone

The low-temperature oxidation chemistry of 2- and 3-pentanone was investigated over a wide range of conditions using a jet-stirred reactor (JSR) and a rapid compression machine (RCM). The JSR oxidation experiment was performed at the pressure of 93.3 kPa over a temperature range of 600-1000 K. Detailed speciation information was obtained using synchrotron vacuum ultraviolet photoionization mass spectrometry. Ignition delay times (IDTs) of 2- and 3-pentanone were measured in an RCM from 640 to 820 K at pressures of 15 and 25 bar and an equivalence ratio of 1.0. The two C5 ketones showed NTC behavior and two-stage ignition phenomena. Mole fraction time histories of intermediate species during the two-stage ignition process of both ketones were obtained using a fast-sampling system coupled with gas chromatography. There are distinct differences between 2- and 3-pentanone in species concentration profiles and IDTs. A kinetic mechanism for the low-temperature oxidation of 2- and 3-pentanone was developed, which can satisfactorily predict all available measurements. The reaction path analyses indicate that the intramolecular hydrogen migration reaction of ROO radicals tends to produce resonance-stabilized QOOH radical structures. The secondary oxygen addition reaction of resonance-stabilized QOOH radicals thus is the most important source of OH radicals in the low-temperature oxidation of ketone fuels. The intramolecular hydrogen migration reactions are slowed down in the presence of the carbonyl functional group, which makes the low-temperature reactivity of the two C5 ketones lower than that of n-pentane. The position of the carbonyl functional group affects the species pools during the oxidation of the two ketones to a great extent. Larger production of CH4, C3H6, CH3COCH3, and C2H5CHO were observed in 2-pentanone oxidation, while the production of CH3CHO was favored during 3-pentanone oxidation both in the JSR and RCM experiments. The different lengths of the carbon chain on both sides of the carbonyl group in 2- and 3-pentanone resulted in the difference in the species distribution.

Speciation Analysis Method of Heavy Metals in Organic Fertilizers: A Review

Heavy metals in organic fertilizers pose a risk to the agricultural ecosystem. The environmental risk of heavy metals depends not only on the total amount but also on the speciation. Hence, more information on heavy metals speciation in organic fertilizers is needed to avoid adverse effect. At present, the speciation information of heavy metals is usually obtained by the single-extraction method and sequential extraction method. Common heavy metals that have received attention include Cu, Zn, Pb, Cd, Cr, Hg and As. There is a lack of reviews on speciation analysis methods for heavy metals, specifically in organic fertilizers. This work aims to comprehensively review the methods, explore the problems of the sequence extraction procedure and summarize the factors affecting the distribution of heavy metals speciation. Each sequence extraction procedure of heavy metals in organic fertilizers is described in detail, and the affecting factors are proposed. The review could contribute proposing the directions of optimizing the sequence extraction procedure of heavy metals in organic fertilizers in the future.

Speciation and isotopic analysis of zinc in size-fractionated aerosol samples related to its source and chemical processes

Zinc (Zn) in aerosols plays important roles for biological activity and attracts public attention from the perspective of environmental measures. Because of its high volatility and water solubility, Zn is readily released into the atmosphere by human activities and supplied to natural water. To explore the origin and formation process of Zn in atmospheric aerosols, it is important to investigate isotopic (= δ66Zn) and speciation information of Zn in size-fractioned aerosols. We measured light δ66Zn (e.g., δ66ZnIRMM = −1.32‰ as the lowest value; IRMM-3702 is used for the normalization in this study) mainly for the particles ranging from 0.65 to 4.7 μm for the samples collected at Tsukuba, Chiba, and a motorway tunnel (Yasumiyama Tunnel in Hiroshima) in particular for the samples collected in 2002, but δ66ZnIRMM in the particle sizes increased above −0.8‰ for the samples collected in 2011 and 2016. Zn species in aerosols were estimated based on X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy, suggesting that (i) Zn oxalate and sulfate and (ii) Zn oxide, sulfide, and carbonate are main Zn species in fine and coarse particles, respectively. In particular, Zn chloride was found mainly in the middle particle size range (2.1–4.7 μm), which corresponds to the range with light δ66Zn, suggesting that the light δ66Zn was caused by emission of Zn chloride during artificial combustion processes in accordance with other studies. The origins of Zn in aerosols are assumed to have three endmembers; (A) tire and brake wears and road dust, (B) industrial emissions, and (C) vehicular exhaust. Their formation mechanisms are related to vaporization and mixing processes based on the results of combined analysis of atmospheric concentration, speciation, and isotopic composition of Zn with different particle sizes. These trends could be successfully interpreted by species-specific δ66Zn values: component (A) consisting mainly of Zn oxide and sulfide with relatively heavier δ66Zn, component (B) Zn chloride and sulfate secondarily formed in the droplet mode having lightest δ66Zn among all the species, and (C) Zn oxalate with δ66Zn closer to 0‰ due to its emission by the complete combustion in vehicle engines. Species-specific Zn isotope data obtained by the simultaneous application of speciation and isotopic analyses of Zn in size-fractionated aerosols complementary provide novel information on the initial generation and secondary processes for the formation of Zn species in the aerosols.

Biological elemental analysis: A cute‐meet of microfluidic device to inductively coupled plasma mass spectrometry

AbstractThe elemental analysis in disease diagnosis and biomedicine screening generally aims at alleviating the difficulties of sample pretreatment techniques, elucidating the distribution and speciation information of elements in bio‐samples as well as elevating resolution of multidimensional elemental profiling. The integration of microfluidic techniques with inductively coupled plasma mass spectrometry (ICP‐MS) has been demonstrated to possess great potential in these aspects due to the versatile microstructure design, rapid sample pretreatment, extremely low sample consumption, and high‐sensitivity/high‐throughput elemental detection capability. Herein, an overview of the advancements in microfluidic‐based ICP‐MS for precise biological elemental determination is provided. A few microfluidic approaches for multiplex and effective manipulation of clinical samples followed by detection with ICP‐MS are highlighted, that is, high spatiotemporal resolution sampling, high‐purity elemental microextraction device, and high signal‐to‐noise ratio elemental analysis. In addition, other front‐end techniques are discussed for converting various types of samples into a suitable form for detection, for example, laser ablation and time of flight MS. The opportunities and outstanding challenges of microfluidic‐based ICP‐MS elemental investigations in clinical diagnosis and biomedical studies are also depicted.

Molecular beam mass spectrometry study on plasma-assisted low-temperature oxidation of ethylene

The chemical kinetics of plasma-assisted low-temperature oxidation of ethylene (C2H4) is explored by molecular beam mass spectrometry and kinetic modeling. In the experiments, a dielectric barrier discharge (DBD) flow reactor coupled with photoionization and electron ionization molecular beam mass spectrometry (PI-MBMS/EI-MBMS) is employed to provide detailed speciation information, including ions, radicals, and molecules in C2H4/O2/Ar systems (∼340 K, 30 Torr). A series of hydrocarbons and oxygenated intermediates including ethenol, methyl hydroperoxide, ethyl hydroperoxide, diacetylene, vinylacetylene, and hydroxyacetaldehyde is detected for the first time in this system. A kinetic mechanism that contains both combustion and plasma reaction networks is developed. The path fluxes of fuel consumption and oxygenates formation are obtained based on the rate of production analysis. Based on our experimental observations and modeling analysis, new insights into the kinetics of C2H4/O2/Ar plasmas are provided. The fuel is mainly consumed through OH addition, dissociation after e/Ar* collision, reactions with O/O(1D), and dissociative ionization. H abstraction reactions that are favored in alkane plasmas contribute little to the fuel consumption of ethylene. Formation pathways of C1 oxygenates are mainly initiated by CH3 produced by O/O(1D) reactions with fuel, and the subsequent pathways of OH/H addition to the fuel are responsible for the formation of most C2 oxygenates. Oxygen addition-elimination reactions of C2H4OH isomers are the sources of ethenol formation. The concentration profiles for some of the species under different oxygen mole fractions are measured. The two distinct patterns of species mole fraction profiles with increasing oxygen concentrations indicate the different dominating formation pathways, namely oxidation pathways and non-oxidation pathways. And the competition between oxidation effects and plasma effects is displayed by the non-monotonic mole fractions profiles of oxidation products.

Metal contaminants of emerging concern in aquatic systems

Environmental context There is potential for a range of metals being used in emerging industries to pose a risk if they reach aquatic environments. This is assessed by evaluating known environmental concentrations against available toxicity data. In most instances risks are low with current usage. Areas are identified where additional data are needed. Abstract The environmental concentrations and aquatic toxicity of a range of technology-critical metals comprising platinum group and rare earth group elements, together with gallium, germanium, indium, lithium, niobium, rhenium, tantalum, tellurium and thallium, have been reviewed to determine whether they pose a risk to aquatic ecosystem health. There is a reasonable body of toxicity data for most, but the quality is quite variable, and more data are required. Chronic toxicity EC10 or NOEC values are generally in the low mg L–1 range, far higher than the current environmental concentrations in the ng L–1 range, meaning that the existing risks to ecosystem health are extremely low. Missing are reliable toxicity data for niobium and tantalum, while confounding results for lanthanum toxicity need to be resolved. There is a likelihood that the currently low concentrations of most of these elements will increase in future years. Whether these concentrations are in bioavailable forms remains to be reliably determined. For most of the elements, measured speciation information is scarce, and unfortunately the thermodynamic data required to calculate their speciation are incomplete. In addition to this problem of uncertain speciation for some of these metals, notably those present in oxidation states of III or higher, there is also a need to explore the links between speciation and bioavailability for these higher valence metals. For circumneutral solutions, the calculated concentrations of the free metal ion tend to be very low for these metals and under such conditions the link between metal speciation and bioavailability is unclear.

Decrease of radionuclide sorption in hydrated cement systems by organic ligands: Comparative evaluation using experimental data and thermodynamic calculations for ISA/EDTA-actinide-cement systems

The sufficient retardation of radionuclide release by sorption is a central issue in assessing the safety of radioactive waste disposal systems and risks posed by contaminated sites. Various types of radioactive wastes and natural environments contain organic substances that can stabilize aqueous radionuclide complexes and therefore lead to a decrease of sorption. This effect can be quantified by sorption reduction factors (SRFs). The present study focuses on testing a methodology to quantify SRFs in the presence of organic ligands for cement systems. Three approaches for the estimation of SRFs were compared for a wide range of systems including representative organic ligands (iso-saccharinic acid: ISA and ethylenediaminetetraacetic acid: EDTA) and selected key radionuclides (trivalent-, tetravalent- and hexavalent-actinides): 1) analogy with solubility enhancement factors (SEFs) derived from published solubility data, 2) calculation based on radionuclide speciation as predicted by thermodynamic calculations, and 3) direct quantification from published experimental sorption data in ternary systems. Our approach allows to critically evaluate the dependence of SRFs in various systems on the chosen method of quantification, in accordance with the data availability for a given system. Our comparisons suggest that reliable SRFs can only be derived from sorption measurements in ternary systems, i.e, where the effect can be directly measured in the presence of solid surface, radionuclide and organic ligand. On the other hand, SRFs often need to be derived in the absence of such direct evidence, and approximations based on analogies and speciation information can be applied to estimate SRFs in such cases. However, such estimates may be subject to substantial uncertainties. This should not be seen as a fundamental hindrance to the use of approximations, but uncertainties need to be clearly acknowledged and an SRF should reflect this e.g. by providing (additional) conservative estimates.

Complexation of Np(V) with the Dicarboxylates, Malonate, and Succinate: Complex Stoichiometry, Thermodynamic Data, and Structural Information

The complexation of Np(V) with malonate and succinate is studied by different spectroscopic techniques, namely, attenuated total reflection Fourier transform infrared (ATR FT-IR) and extended X-ray absorption fine-structure (EXAFS) spectroscopy, as well as by quantum chemistry to determine the speciation, thermodynamic data, and structural information of the formed complexes. For complex stoichiometries and the thermodynamic functions (log βn°(Θ), ΔrHn°, ΔrSn°), near infrared absorption spectroscopy (vis/NIR) is applied. The complexation reactions are investigated as a function of the total concentration of malonate ([Mal2-]total) and succinate ([Succ2-]total), ionic strength [Im = 0.5-4.0 mol kg-1 Na+(Cl-/ClO4-)], and temperature (Θ = 20-85 °C). Besides the solvated NpO2+ ion, the formation of two Np(V) species with the stoichiometry NpO2(L)n1-2n (n = 1, 2, L = Mal2-, Succ2-) is observed. With increasing temperature, the molar fractions of both complex species increase and the temperature-dependent conditional stability constants log βn'(Θ) at given ionic strengths are determined by the law of mass action. The log βn'(Θ) are extrapolated to IUPAC reference-state conditions (Im = 0) according to the specific ion interaction theory (SIT), revealing thermodynamic log βn°(Θ) values. For all formed complexes, [NpO2(Mal)-: log β1°(25 °C) = 3.36 ± 0.11, NpO2(Mal)23-: log β2°(25 °C) = 3.95 ± 0.19, NpO2(Succ)-: log β1°(25 °C) = 2.05 ± 0.45, NpO2(Succ)23-: log β2°(25 °C) = 0.75 ± 1.22], an increase of the stability constants with increasing temperature was observed. This confirmed an endothermic complexation reaction. The temperature dependence of the log βn°(T) values is described by the integrated Van't Hoff equation, and the standard reaction enthalpies and entropies for the complexation reactions are determined. Furthermore, the sum of the specific binary ion-ion interaction coefficients Δεn°(Θ) for the complexation reactions are obtained as a function of the t from the respective SIT modeling as a function of the temperature. In addition to the thermodynamic data, the structures of the complexes and the coordination modes of malonate and succinate are investigated using EXAFS spectroscopy, ATR-FT-IR spectroscopy, and quantum chemical calculations. The results show that in the case of malonate, six-membered chelate complexes are formed, whereas for succinate, seven-membered rings form. The latter ones are energetically unfavorable due to the limited space in the equatorial plane of the Np(V) ion (as NpO2+ cation).

A Study of the Corrosion of Polymethyl Methacrylate Coated Rebar Using Glancing Angle X-Ray Absorption Near Edge Spectroscopy

Polymer coatings can be used to mitigate the corrosion of steel in high-chloride environments. Obtaining speciation information from thin corrosion layers can be important for understanding corrosion mechanisms, including polymer coating failure. This study outlines the effectiveness of collecting glancing angle x-ray absorption near edge spectroscopy (GA-XANES) spectra at the Fe K-edge to obtain chemical speciation information at the polymer/steel interface without removal of the polymer film. The depth of penetration of the incident x rays can be altered by changing the incidence angle, allowing for more fluorescence signal from corrosion products to be detected relative to the Fe metal fluorescence signal in GA-XANES spectra. This study demonstrates the use of GA-XANES to study thin layers of steel corrosion and obtain depth profile information of steel corrosion products beneath a polymethyl methacrylate polymer coating.

Experimental and kinetic modeling investigation on 2,5-hexanedione oxidation in a jet-stirred reactor

Unique resonance stabilization features of R and QOOH radicals of 2,5-hexanedione [CH3C(=O)CH2CH2C(=O)CH3] facilitated the investigation on the roles of carbonyl group in the oxidation of ketones. This work presents the first study on the speciation from the oxidation of 2,5-hexanedione. A fuel-lean (ϕ=0.5) 2,5-hexanedione/O2/Ar mixture was investigated in a jet-stirred reactor (JSR) operated at atmospheric pressure, over a temperature range of 600–900 K. Synchrotron vacuum ultraviolet photoionization mass spectrometry was employed to acquire detailed speciation information. A detailed kinetic mechanism was proposed based on the “reaction classes” strategy and validated against the current measurements. No obvious low-temperature reactivity was observed under the investigated conditions, and the reason was attributed to the unfavored ROO = QOOH isomerization reactions of both two RO2 radicals, while the energetically favored HO2-elimination reactions produce inert HO2 radicals in the low-temperature regime. β-scission reactions dominate the consumption of fuel radicals. The prediction of fuel reactivity strongly depends on the reactions involving the small hydrocarbon species and H-atom abstraction reactions. The competition between the reaction pair of CH3+HO2 = CH3O+OH and CH3+HO2 = CH4+O2 is the most influential factor for the fuel reactivity in the studied temperature regimes. Based on the experimental observations and kinetic modeling analyses, fuel consumption and major intermediates formation pathways in 2,5-hexanedione were illustrated.

A rapid compression machine coupled with time-resolved molecular beam mass spectrometry for gas-phase kinetics studies.

Rapid compression machines (RCMs) are used to simulate a single stroke of an internal combustion engine. After a high-speed compression process, a high-pressure and low-to-intermediate temperature condition can be obtained, under which ignition processes are usually studied. With the help of different diagnostic methods, the detailed speciation information of the ignition process can be quantified. In this study, the molecular beam mass spectrometry (MBMS) diagnostic method was applied on an RCM to realize time-resolved concentration profile measurements. To realize the combination between RCM and MBMS, particle dampers were adopted to suppress the vibrations of the RCM, and a novel flexible interface was designed to maintain a high vacuum, which ensured the safe and effective operation of a high-repetition-rate time-of-flight mass spectrometer (HRR-TOF-MS). The detailed configuration of this diagnostic method is presented, and the data acquisition system and data analysis method are described. The arrangement was validated through the investigation of the well-studied decomposition of 1,3,5-trioxane at temperatures between 697 and 777K at 10 bars. The measured concentration profiles of 1,3,5-trioxane and formaldehyde were in good agreement with previous experimental and theoretical calculation results. The experimental results showed that the newly developed RCM coupled with the HRR-TOF-MS has advantages in time-resolved speciation measurements at low-to-intermediate temperatures and high pressures, and it can be applied in low-temperature combustion chemical kinetics studies.

Deciphering the Chemistry of Cultural Heritage: Targeting Material Properties by Coupling Spectral Imaging with Image Analysis.

The chemical study of materials from natural history and cultural heritage, which provide information for art history, archeology, or paleontology, presents a series of specific challenges. The complexity of these ancient and historical materials, which are chemically heterogeneous, the product of alteration processes, and inherently not reproducible, is a major obstacle to a thorough understanding of their making and long-term behavior (e.g., fossilization). These challenges required the development of methodologies and instruments coupling imaging and data processing approaches that are optimized for the specific properties of the materials. This Account discusses how these characteristics not only constrain their study but also open up specific innovative avenues for providing key historical information. Synchrotron methods have extensively been used since the late 1990s to study heritage objects, in particular for their potential to provide speciation information from excitation spectroscopies and to image complex heritage objects and samples in two and three dimensions at high resolution. We examine in practice how the identification of key intrinsic chemical specificities has offered fertile ground for the development of novel synchrotron approaches allowing a better stochastic description of the properties of ancient and historical materials. These developments encompass three main aspects: (1) The multiscale heterogeneity of these materials can provide an essential source of information in the development of probes targeting their multiple scales of homogeneity. (2) Chemical alteration can be described in many ways, e.g., by segmenting datasets in a semiquantitative way to jointly inform morphological and chemical transformation pathways. (3) The intrinsic individuality of chemical signatures in artifacts triggers the development of specific strategies, such as those focusing on weak signal detection. We propose a rereading of the advent of these new methodologies for analysis and characterization and examine how they have led to innovative strategies combining materials science, instrument development, history, and data science. In particular, we show that spectral imaging and the search for correlations in image datasets have provided a powerful way to address what archeologists have called the uncertainty and ambiguity of the material record. This approach has implications beyond synchrotron techniques and extends in particular to a series of rapidly developing approaches that couple spectral and spatial information, as in hyperspectral imaging and spatially resolved mass spectrometry. The preeminence of correlations holds promise for the future development of machine learning methods for processing data on historical objects. Beyond heritage, these developments are an original source of inspiration for the study of materials in many related fields, such as environmental, geochemical, or life sciences, which deal with systems whose alteration and heterogeneity cannot be neglected.

Computational Infrared Spectroscopy of 958 Phosphorus-Bearing Molecules

Phosphine is now well-established as a biosignature, which has risen to prominence with its recent tentative detection on Venus. To follow up this discovery and related future exoplanet biosignature detections, it is important to spectroscopically detect the presence of phosphorus-bearing atmospheric molecules that could be involved in the chemical networks producing, destroying or reacting with phosphine. We start by enumerating phosphorus-bearing molecules (P-molecules) that could potentially be detected spectroscopically in planetary atmospheres and collecting all available spectral data. Gaseous P-molecules are rare, with speciation information scarce. Very few molecules have high accuracy spectral data from experiment or theory; instead, the best current spectral data was obtained using a high-throughput computational algorithm, RASCALL, relying on functional group theory to efficiently produce approximate spectral data for arbitrary molecules based on their component functional groups. Here, we present a high-throughput approach utilizing established computational quantum chemistry methods (CQC) to produce a database of approximate infrared spectra for 958 P-molecules. These data are of interest for astronomy and astrochemistry (importantly identifying potential ambiguities in molecular assignments), improving RASCALL's underlying data, big data spectral analysis and future machine learning applications. However, this data will probably not be sufficiently accurate for secure experimental detections of specific molecules within complex gaseous mixtures in laboratory or astronomy settings. We chose the strongly performing harmonic ωB97X-D/def2-SVPD model chemistry for all molecules and test the more sophisticated and time-consuming GVPT2 anharmonic model chemistry for 250 smaller molecules. Limitations to our automated approach, particularly for the less robust GVPT2 method, are considered along with pathways to future improvements. Our CQC calculations significantly improve on existing RASCALL data by providing quantitative intensities, new data in the fingerprint region (crucial for molecular identification) and higher frequency regions (overtones, combination bands), and improved data for fundamental transitions based on the specific chemical environment. As the spectroscopy of most P-molecules have never been studied outside RASCALL and this approach, the new data in this paper is the most accurate spectral data available for most P-molecules and represent a significant advance in the understanding of the spectroscopic behavior of these molecules.

Phytosampling-a supplementary tool for particulate matter (PM) speciation characterization.

Ambient air particulate matter (PM) and PM-associated environmentally persistent free radicals (EPFRs) have been documented to contribute to pollution-related health effects. Studies of ambient air PM potentially bear artifacts stemming from the collection methods. We have investigated the applicability of PM phytosampling (PHS) as a supplementary tool to a classic PM sampler in respect of achieving better PM chemical composition assessment (primarily organic fraction). Phytosampling is a static PM collection method relying on the particle entrapment by the plant's leaf through electrostatic forces and surface trichomes. We have investigated the differences in the EPFR and polycyclic aromatic hydrocarbon (PAH) speciation and concentration on ambient air PM for PHS and high-volume PM sampler (HVS). The advantages of PHS are easy particle recovery from the matrix, collection under natural environmental conditions, and the ability to apply a dense collection network to accurately represent spatial pollutant distribution. The experimental results show that the PHS can provide valuable speciation information, sometimes different from that observed for HVS. For PM collected by PHS, we detected the larger contribution of oxygen-centered EPFRs, different decay behavior, and more consistent PAH distribution between different PM sizes compared to the PM from HVS. These results indicate that the isolation of samples from the ambient during HVS sampling and exposure to high-volume airflow may alter the chemical composition of the samples, while the PHS method could provide details on the original speciation and concentration and be more representative of the PM surface. However, PHS cannot evaluate an absolute air concentration of PM, so it serves as an excellent supplementary tool to work in conjunction with the standard PM collection method.