Chemical Ionization Research Articles

Pressure-Driven Switching of Photoelectron Impact Ionization-Chemical Ionization/Penning Ionization in Vacuum Ultraviolet Photoionization Mass Spectrometry.

Vacuum ultraviolet photoionization (VUV-PI) is a soft ionization technique that operates under pressures ranging from vacuum to ambient pressure. VUV-PI has played an essential role in direct sampling mass spectrometry. In this study, new ionization processes initiated by photoelectrons have been studied through the inclusion of a radio frequency (RF) electric field at different pressures. After deducting the contribution of single photoionization (SPI), the signal intensity of 1 ppmv toluene (C7H8+) in Ar was approximately 5-fold higher than that in N2. Mixed gases with different ionization energies (IEs) and excitation energies (EEs) were further investigated to reveal that metastable species were involved in the enhancement process. Reactant ions were produced by photoelectron impact ionization (PEI), which further triggered ion-molecule reactions, i.e., chemical ionization (CI). Metastable species were produced by photoelectron impact excitation (PEE), which further triggered Penning ionization (PenI). Analytes with IEs above 10.6 eV, such as CO2 (IE = 13.78 eV) and CHCl3 (IE = 11.37 eV), could be sensitively ionized by PenI with a sensitivity comparable to SPI. Except for the contribution of SPI, the dominant ionization process was switched from PEI-CI to PenI when the pressure was elevated from 50 to 500 Pa, as the electron energy gradually decreased and was only able to produce metastable states based on the kinetic energy balance equation of electrons. The conversion processes and conditions from PEI-CI to PenI will provide novel insights to develop new selective and sensitive VUV-PI sources and understand the ionization mechanism in other discharge ionization sources.

Discriminating Superimposed Alteration Associated with Epigenetic Base and Precious Metal Vein Systems in the Rouyn-Noranda Mining District, Quebec; Implications for Exploration in Ancient Volcanic Districts

Abstract The Rouyn-Noranda mining district of Quebec contains 20 Cu-Zn (±Au ±Ag) volcanogenic massive sulfide (VMS) deposits, including the giant and gold-rich Quemont and Horne deposits. Mineralized epigenetic veins are also present, but their origin and relative timing remain enigmatic. The nature and extent of their alteration signatures and the effect of their superposition on district-scale alteration patterns is unknown. The VMS-related quartz-sulfide Cu-Zn-Ag veins have δ18Oquartz values of 8.5 ± 0.8‰, reflecting δ18Ofluid compositions of –0.4 to 3.1‰ (250°–350°C) that are typical of Archean seawater. They are associated with a proximal Fe-rich chlorite alteration and marginal spotted sericite-chlorite alteration with whole-rock δ18O values of 2.9 to 5.9‰ and are interpreted to have formed within the structurally controlled discordant upflow zones of a VMS hydrothermal system. Younger gold-bearing quartz-carbonate veins were emplaced along mechanical anisotropies created by mafic dikes during north-south compression and the formation of regional E-trending faults, folds, and cleavage. They are characterized by δ18Oquartz values of 11.3 ± 0.8‰, reflecting δ18Ofluid compositions of 2.4 to 5.9‰ (250°–350°C), typical of a metamorphic fluid, possibly mixed with a lower δ18O upper crustal fluid. They are associated with ankerite, calcite, muscovite, chlorite, albite, and quartz ± hematite alteration with whole-rock δ18O values of 5.8 to 10.3‰. Chemical abrasion-isotope dilution-thermal ionization mass spectrometry (CA-ID-TIMS) U-Pb zircon ages for two tonalite intrusions constrain the maximum age of the Cu-Zn-Ag veins to 2697.6 ± 0.7 Ma and the minimum age to 2695.3 ± 1.0 Ma, which is also the maximum age of the gold quartz-carbonate veins. Superposition of alteration related to the gold quartz-carbonate veins on previously chlorite- and sericite-altered rocks has resulted in mixed alteration signals with whole-rock δ18O values of ~6 to 8‰ that have perturbed and masked regional alteration patterns related to older VMS mineralization, such as those found in the Quemont and Horne deposits. These results indicate that defining alteration vectors in camps that have superimposed hydrothermal systems requires full consideration of the hydrothermal history of the camp, and if such constraints are lacking, whole-rock δ18O values should not be used as a stand-alone exploration method.

Measurement report: Insights into the chemical composition and origin of molecular clusters and potential precursor molecules present in the free troposphere over the southern Indian Ocean: observations from the Maïdo Observatory (2150 m a.s.l., Réunion)

Abstract. New particle formation (NPF) in the free troposphere (FT) is thought to be a significant source of particles over the oceans. The entrainment of particles initially formed in the marine FT is further suspected to be a major contributor to cloud condensation nuclei (CCN) number concentrations in the marine boundary layer (BL). Yet, little is known about the process and, more broadly, about the composition of the marine FT, which remains poorly explored due to access difficulties. Here we report measurements performed in April 2018 at the Maïdo Observatory with a nitrate-based chemical ionization atmospheric pressure interface time-of-flight mass spectrometer, which have allowed the first molecular-level characterization of the remote marine FT composition. A number of molecules and clusters were identified and classified into nine groups according to their chemical composition; among the identified species, the groups containing methanesulfonic acid (MSA) and C2 amines show signals that are on average significantly higher when the site is under conditions representative of the marine FT (compared to the BL). The correlation analysis revealed apparent connections between the signals of the identified compounds and several variables concurrently measured at the site (under FT conditions) or related to air mass history, suggesting that oxalic acid, malonic acid, and observed C2 amines could be of terrestrial origin, with, in addition, a possible marine source for oxalic acid and amines, while iodic acid, sulfur species, and maleic acid have a dominant marine origin. Identification of FT conditions at the site was based on the analysis of the standard deviation of the wind direction; this parameter, which can easily be derived from continuous measurements at the site, is shown in the first part of the study to be a relevant tracer when compared to predictions from the Meso-NH atmospheric model. Similar to other high-altitude sites, FT conditions are mainly encountered at night at Maïdo; therefore, the link to NPF could not be established, and further research is needed to assess the composition of precursors to nanoparticle formation in the marine FT.

NO3− loss from nitrate adducts of explosives by thermal decomposition in tandem Ion mobility spectrometry and by collision induced dissociation in tandem mass spectrometry

Nitrate adducts of nitroglycerin (NG) and 1,3-dinitroglycerin (1,3-DNG) were produced from atmospheric pressure chemical ionization with chloride reagent ions and in-source decomposition of M·Cl−. The nitrate adducts subsequently dissociated in the drift region with enthalpies of 109 ± 9 kJ mol −1 at 142–150 °C for NG·NO3− and 101 ± 8 kJ mol−1 at 161–173 °C for 1,3-DNG·NO3−. Similar behavior was not observed generally for other explosives although nitrate adducts of each explosive could be formed using electrospray ionization with a nitrate salt solution. Ion abundances were measured over a range of ion energies with collision induced dissociation in tandem mass spectrometry and models from Density Functional Theory were used to correlate the experimental findings to structural motifs and other adduct properties. The computational modeling showed that adduct stability is dominated by the electrostatic interaction between the nitrate ion and the dipole moment of the neutral explosive. Specifically, explosives having the ability to adapt a conformer with a large dipole moment showed the most stable adducts. Other binding contributions are possible yet were found to be minor in the explosive adducts studied here.

Quantitative Analysis of NDMA in Drug Products: A Proposed High-Throughput Approach Using Headspace–SIFT-MS

Since the initial 2018 recall of angiotensin receptor blockers due to unacceptable levels of mutagenic N-nitrosodimethylamine (NDMA) impurity, numerous drug products delivering diverse active pharmaceutical ingredients (APIs) have been recalled. Regulators and the industry are working together to understand and address this widescale problem. Conventional analysis of NDMA utilizes liquid or gas chromatography-based procedures that can involve complicated sample preparation and slow sample analysis. Selected ion flow tube mass spectrometry (SIFT-MS) analyses NDMA directly in the gas phase using soft chemical ionization, with an LOQ of 2 ng g−1. Through the novel application of the multiple headspace extraction (MHE) technique, NDMA was quantified directly and rapidly from the drug product without dissolution, at levels well below the regulatory acceptable intake of 96 ng day−1. A comparative analysis of recalled metformin using MHE-SIFT-MS and a conventional liquid chromatography–mass spectrometry/mass spectrometry (LC-MS/MS) method showed good agreement. Use of the novel MHE-SIFT-MS approach may enable a wider screening of drug products to be conducted, since it provides around a three-fold increase in daily sample throughput.

Toward Part-per-Million Precision in the Determination of an Ion's Collision Cross Section Using Multipass Cyclic Ion Mobility.

In cyclic ion mobility (cIMS), ions are permitted to travel multiple passes around the drift cell, increasing the distance traveled and the relative separation between ions. This study tests the hypothesis that multiple passes around the cell can also result in improved precision when measuring an ion's mobility and the collision cross section (TWCCS) derived therefrom. Experiments were performed with a diverse set of compounds, including 16 polycyclic aromatic hydrocarbons using gas chromatographic atmospheric pressure chemical ionization and a set of drug molecules by direct infusion electrospray ionization. The average periodic drift time, viz., the average time required for the ion to travel around the cIMS cell once, shifts dramatically, approaching part-per-million (ppm) precision as the number of passes increases to ∼100. Extrapolation of the precision of the CCS values with respect to the number of passes led to the prediction that the precision will reach 1000 ppm after 50 passes, 100 ppm after 100 passes, and <10 ppm after 150 passes. Experiments wherein the number of passes exceeded 100 produced TWCCS values having within-run precisions ranging between 15 and 117 ppm. The improved precision with an increasing number of passes may be a consequence of mitigating space-charge effects by allowing the ions to occupy a larger region of the cIMS cell. A method is proposed to enable practical measurements of TWCCS with ppm precision and is demonstrated to characterize an unknown drug mixture.

Analysis of vitamin D and its metabolites in biological samples – Part I: Optimization and comparison of UHPSFC-MS/MS and UHPLC-MS/MS methods

Fat-soluble vitamin D is an essential bioactive compound important for human health. Insufficient vitamin D levels can result not only in bone disease but also in other disorders, such as cancer, metabolic disorders, and diseases related to poor immune function. The current methods commonly used for vitamin D analysis are often applied to determine the levels of the most abundant metabolite in plasma, i.e., 25-OH-D2/D3. These methods do not consider the presence of other hydroxylated and esterified metabolites, including isomers and epimers, which are typically found in low concentrations.In this study, we developed a fast and selective ultra-high performance supercritical fluid chromatography (UHPSFC) method using a 150 mm long 1-amino anthracene (1-AA) column and a mobile phase consisting of carbon dioxide and methanol/isopropanol (1/1, v/v) mixed with 8 % water. After thorough optimization of column temperature and back pressure, the separation of four vitamin D3 esters, vitamin D3 and D2, and eight mono- and di-hydroxylated metabolites, including three groups of isomers, was achieved in 10 min. Two ion sources, atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization optimized within this study, were compared in tandem mass spectrometry (MS/MS) detection. No significant sensitivity differences were observed. Subsequently, the same 1-AA column chemistry was examined in ultra-high performance liquid chromatography (UHPLC) as the stationary phase that could hypothetically bring different selectivity in the separation of vitamin D and its metabolites. However, this hypothesis was rejected, and C18 was used as a stationary phase in the final optimized UHPLC-MS/MS method. Despite detailed optimization, the final 15 min UHPLC method was not able to separate di-hydroxylated isomers of vitamin D3, while it enabled better resolution of esterified forms compared to UHPSFC.Optimized methods provided similar repeatability of retention times and peak areas, with RSD < 2 % and 10 %, respectively. The lowest limits of quantification were in the range of 1.2 – 4.9 ng/mL for UHPSFC-APCI-MS/MS, while for UHPLC-APCI-MS/MS, they were typically in the range of 2.6 – 9.6 ng/mL. Based on the obtained results, the UHPSFC-APCI-MS/MS method was the most promising approach for fast, selective, and sensitive analysis that could be applied in the analysis of biological samples with emphasis on the separation of both hydroxylated and esterified metabolites, including isomeric forms.

Characterization of the Vaporization Inlet for Aerosols (VIA) for online measurements of particulate highly oxygenated organic molecules (HOMs)

Abstract. Particulate matter has major climate and health impacts, and it is therefore of utmost importance to be able to measure the composition of these particles to gain insights into their sources and characteristics. Many methods, both offline and online, have been employed over the years to achieve this goal. One of the most recent developments is the Vaporization Inlet for Aerosols (VIA) coupled to a nitrate Chemical Ionization Mass Spectrometer (NO3-CIMS), but a thorough understanding of the VIA–NO3-CIMS system remains incomplete. In this work, we ran a series of tests to assess the impacts from different systems and sampling parameters on the detection efficiency of highly oxygenated organic molecules (HOMs) in the VIA–NO3-CIMS system. Firstly, we found that the current VIA system (which includes an activated carbon denuder and a vaporization tube) efficiently transmits particles (&gt; 90 % for particles larger than 50 nm) while also removing gaseous compounds (&gt; 97% for tested volatile organic compounds – VOCs). One of the main differences between the VIA and traditional thermal desorption (TD) techniques is the very short residence time in the heating region, on the order of 0.1 s. We found that this short residence time, and the corresponding short contact with heated surfaces, is likely one of the main reasons why relatively reactive or weakly bound peroxides, for example, were observable using the VIA. However, the VIA also requires much higher temperatures in order to fully evaporate the aerosol components. For example, the evaporation temperature of ammonium sulfate particles using the VIA was found to be about 100–150 °C higher than in typical TD systems. We also observed that the evaporation of particles with larger sizes occurred at slightly higher temperatures compared to smaller particles. Another major aspect that we investigated was the gas-phase wall losses of evaporated molecules. With a more optimized interface between the VIA and the NO3-CIMS, we were able to greatly decrease wall losses and thus improve the sensitivity compared to our earlier VIA work. This interface included a dedicated sheath flow unit to cool the heated sample and provide the NO3-CIMS with the needed high flow (10 L min−1). Our results indicate that most organic molecules observable by the NO3-CIMS can evaporate and be transported efficiently in the VIA system, but upon contact with the hot walls of the VIA, the molecules are instantaneously lost. This loss potentially leads to fragmentation products that are not observable by the NO3-CIMS. Thermograms, obtained by scanning the VIA temperature, were found to be very valuable for both quantification purposes and for estimating the volatility of the evaporating compounds. We developed a simple one-dimensional model to account for the evaporation of particles and the temperature-dependent wall losses of the evaporated molecules, and we thereby estimate the concentration of HOMs in secondary organic aerosol (SOA) particles. Overall, our results provide much-needed insights into the key processes underlying the VIA–NO3-CIMS method. Although there are still some limitations that could be addressed through hardware improvements, the VIA–NO3-CIMS system is a very promising and useful system for fast online measurements of HOMs in the particle phase.

Comprehensive Analysis of Lutein and Loroxanthin in Scenedesmus obliquus: From Quantification to Isolation.

Carotenoids are hydrophobic pigments produced exclusively by plants, fungi, and specific microbes. Microalgae are well suited for the production of valuable carotenoids due to their rapid growth, efficient isoprenoid production pathway, and ability to store these compounds within their cells. The possible markets for bio-products range from feed additives in aquaculture and agriculture to pharmaceutical uses. The production of carotenoids in microalgae is affected by several environmental conditions, which can be utilized to enhance productivity. The current study focused on optimizing the extraction parameters (time, temperature, and extraction number) to maximize the yield of carotenoids. Additionally, the impact of various nitrogen sources (ammonia, nitrate, nitrite, and urea) on the production of lutein and loroxanthin in Scenedesmus obliquus was examined. To isolate the carotenoids, 0.20 g of biomass was added to 0.20 g of CaCO3 and 10.0 mL of ethanol solution containing 0.01% (w/v) pyrogallol. Subsequently, the extraction was performed using an ultrasonic bath for a duration of 10 min at a temperature of 30 °C. This was followed by a four-hour saponification process using a 10% methanolic KOH solution. The concentration of lutein and loroxanthin was measured using HPLC-DAD at 446 nm, with a flow rate of 1.0 mL/min using a Waters YMC C30 Carotenoid column (4.6 × 250 mm, 5 μm). The confirmation of carotenoids after their isolation using preparative chromatography was achieved using liquid chromatography-tandem mass spectrometry (LC-MS/MS) with an atmospheric pressure chemical ionization (APCI) probe and UV-vis spectroscopy. In summary, S. obliquus shows significant promise for the large-scale extraction of lutein and loroxanthin. The findings of this study provide strong support for the application of this technology to other species.

Exploration of Choline Chloride Based Type II and Type III Deep Eutectic Solvents: A Computational and Experimental Approach

AbstractDeep eutectic solvents (DESs) of choline chloride with citric acid (CACC), Maleic acid (MACC) and Magnesium chloride hexahydrate (MAGCC) were synthesized in 1 : 1 molar ratio and investigated experimentally and computationally. For the computational study, density functional theory (DFT) calculation with B3LYP/6‐31 (+, +) G (d,p) level of theory for MACC and CACC and at B3LYP/SDD basis set for MAGCC was employed and the FT‐IR spectroscopy was used for experimental evaluation. For understanding the orientation of bonds and hydrogen bonding present in DESs geometrically optimized structures were used. Through frontier molecular orbital (FMO) theory and HOMO−LUMO values and various quantum chemical parameters, viz., ionization potential (IP), electron affinities (EA), electro negativity (χ), chemical potential (μ), global softness (σ) and hardness (η), electrophilicity index (ω) were calculated for all DESs. These computational values made it clear that MAGCC is the most stable among the three DESs due to the high value of global hardness (η) (3.291 eV) and HOMO−LUMO energy gap (Egap) (6.582 eV) and lowest value of softness (σ) (0.152 eV), CACC shows the moderate values (η=2.452, Egap=4.905 and σ=0.204 eV). While MACC is found to be the least stable and most reactive among three DESs with values of η, Egap and σ, 1.970, 3.940 and 0.254 eV, respectively. Furthermore, MESP analysis gives an idea about the electrophilic and nucleophilic surface region of DESs. This study will give valuable information for a better understanding of DESs and the applicability of computational calculations in the future.

Application of Chemical Ionization in the Analysis of Ethylphosphonic Acid Derivatives.

The microsynthesis of 32 dialkyl derivatives of ethylphosphonic acid and the same number of monoalkyl derivatives was carried out to perform comparative studies using gas chromatography combined with mass spectrometry in chemical ionization mode which is one of the analytical techniques recommended by the Organisation for the Prohibition of Chemical Weapons (OPCW). The huge number of possible representatives makes it difficult to have complete spectral libraries of all substances in this class. Therefore, we decided to synthesize and instrumentally analyze only representatives of the selected series of homologues in this work. The analysis of the obtained results allowed us to find the rules for predicting mass spectra and the factors determining the retention parameters. Symmetrical diesters and monoesters of ethylphosphonic acid were selected for this study. During the conducted experiments using chemical ionization with methane as the reaction gas, protonated analyte molecules with high relative intensities were obtained; in many cases, these are base peaks in the spectrum. The obtained results allow grouping of the synthesized compounds depending on the introduced alkyl substituent. Retention data of the tested analytes were collected during the research by using electron ionization. The retention parameters of the tested compounds from each homologous series were also summarized and compared. Chemical Warfare Agents (CWA) analysis continues to be an important issue, especially in the context of the regular Proficiency Tests organized by the OPCW for identifying chemical compounds that are of interest to the Chemical Weapons Convention. Five compounds were synthesized whose spectra were not available in EI mass spectral libraries, and their retention indices were unknown. The identification of these substances was supported by the CI mass spectra and retention data, using previously developed relationships. Therefore, it is reasonable to conclude that the research method used is useful and effective.

Integrating density functional theory and chemical ionization mass spectrometry techniques to assess benzophenone derivatives in food packaging: implications for enhancing food quality and safety.

Benzophenone and related derivatives are widely used as photoinitiators for food packaging to cure inks or lacquers with ultraviolet (UV) light on cardboard and paper. However, there are concerns about the potential health risks of their migration into food. Knowing the physical and chemical properties of benzophenone and its derivatives could play a significant role in their quantification and analysis using chemical ionization mass spectrometry (CI-MS) methods. These parameters are evaluated using B3LYP/6-311++** density functional theory (DFT) implemented on Gaussian code. Ion-molecule chemistry through the selection of reagent ions, reaction energetics and kinetics, thermodynamic stability, and reactivity of molecules deemed to foster VOC identification and quantification via CI-MS techniques. The VOCs under study are expected to undergo exothermic reactions from H3 O+ , NH4 + , NO+ , and O2 + ions, except endothermic proton transfer from NH4 + to 2-hydroxy-4-methoxybenzophenone and 2,3,4-trihydroxy benzophenone. These compounds possess less proton affinities than NH3 and are least stable in their protonated forms. The DFT computed properties provide the basis for developing reliable and accurate methods to detect and measure the presence of benzophenone and its derivatives in packaging materials and food products.

Impact of molecular composition on viscosity of heavy oil: Machine learning based on semi-quantitative analysis results from high-resolution mass spectrometry

The primary impediment to the recovery of heavy oil lies in its high viscosity, which necessitates a deeper understanding of the molecular mechanisms governing its dynamic behavior for enhanced oil recovery. However, there remains a dearth of understanding regarding the complex molecular composition inherent to heavy oil. In this study, we employed high-resolution mass spectrometry in conjunction with various chemical derivatization and ionization methods to obtain semi-quantitative results of molecular group compositions of 35 heavy oils. The gradient boosting (GB) model has been further used to acquire the feature importance rank (FIR). A feature is an independently observable property of the observed object. Feature importance can measure the contribution of each input feature to the model prediction result, indicate the degree of correlation between the feature and the target, unveil which features are indicative of certain predictions. We have developed a framework for utilizing physical insights into the impact of molecular group compositions on viscosity. The results of machine learning (ML) conducted by GB show that the viscosity of heavy oils is primarily influenced by light components, specifically small molecular hydrocarbons with low condensation degrees, as well as petroleum acids composed of acidic oxygen groups and neutral nitrogen groups. Additionally, large molecular aromatic hydrocarbons and sulfoxides also play significant roles in determine the viscosity.

Molecular analysis of secondary organic aerosol and brown carbon from the oxidation of indole

Abstract. Indole (ind) is a nitrogen-containing heterocyclic volatile organic compound commonly emitted from animal husbandry and from different plants like maize with global emissions of 0.1 Tg yr−1. The chemical composition and optical properties of indole secondary organic aerosol (SOA) and brown carbon (BrC) are still not well understood. To address this, environmental chamber experiments were conducted to investigate the oxidation of indole at atmospherically relevant concentrations of selected oxidants (OH radicals and O3) with or without NO2. In the presence of NO2, the SOA yields decreased by more than a factor of 2, but the mass absorption coefficient at 365 nm (MAC365) of ind-SOA was 4.3 ± 0.4 m2 g−1, which was 5 times higher than that in experiments without NO2. In the presence of NO2, C8H6N2O2 (identified as 3-nitroindole) contributed 76 % to all organic compounds detected by a chemical ionization mass spectrometer, contributing ∼ 50 % of the light absorption at 365 nm (Abs365). In the absence of NO2, the dominating chromophore was C8H7O3N, contributing to 20 %–30 % of Abs365. Indole contributes substantially to the formation of secondary BrC and its potential impact on the atmospheric radiative transfer is further enhanced in the presence of NO2, as it significantly increases the specific light absorption of ind-SOA by facilitating the formation of 3-nitroindole. This work provides new insights into an important process of brown carbon formation by interaction of two pollutants, NO2 and indole, mainly emitted by anthropogenic activities.

Variation in chemical composition and volatility of oxygenated organic aerosol in different rural, urban, and mountain environments

Abstract. The apparent volatility of atmospheric organic aerosol (OA) particles is determined by their chemical composition and environmental conditions (e.g., ambient temperature). A quantitative, experimental assessment of volatility and the respective importance of these two factors remains challenging, especially in ambient measurements. We present molecular composition and volatility of oxygenated OA (OOA) particles in different rural, urban, and mountain environments (including Chacaltaya, Bolivia; Alabama, US; Hyytiälä, Finland; Stuttgart and Karlsruhe, Germany; and Delhi, India) based on deployments of a filter inlet for gases and aerosols coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (FIGAERO-CIMS). We find on average larger carbon numbers (nC​​​​​​​) and lower oxygen-to-carbon (O : C) ratios at the urban sites (nC: 9.8 ± 0.7; O : C: 0.76 ± 0.03; average ±1 standard deviation) compared to the rural (nC: 8.8 ± 0.6; O : C: 0.80 ± 0.05) and mountain stations (nC: 8.1 ± 0.8; O : C: 0.91 ± 0.07), indicative of different emission sources and chemistry. Compounds containing only carbon, hydrogen, and oxygen atoms (CHO) contribute the most to the total OOA mass at the rural sites (79.9 ± 5.2 %), in accordance with their proximity to forested areas (66.2 ± 5.5 % at the mountain sites and 72.6 ± 4.3 % at the urban sites). The largest contribution of nitrogen-containing compounds (CHON) is found at the urban stations (27.1 ± 4.3 %), consistent with their higher NOx levels. Moreover, we parametrize OOA volatility (saturation mass concentrations, Csat) using molecular composition information and compare it with the bulk apparent volatility derived from thermal desorption of the OOA particles within the FIGAERO. We find differences in Csat values of up to ∼ 3 orders of magnitude and variation in thermal desorption profiles (thermograms) across different locations and systems. From our study, we draw the general conclusion that environmental conditions (e.g., ambient temperature) do not directly affect OOA apparent volatility but rather indirectly by influencing the sources and chemistry of the environment and thus the chemical composition. The comprehensive dataset provides results that show the complex thermodynamics and chemistry of OOA and their changes during its lifetime in the atmosphere. We conclude that generally the chemical description of OOA suffices to predict its apparent volatility, at least qualitatively. Our study thus provides new insights that will help guide choices of, e.g., descriptions of OOA volatility in different model frameworks such as air quality models and cloud parcel models.

Role of Hydroperoxyl Radicals in Heterogeneous Oxidation of Oxygenated Organic Aerosols.

Heterogeneous oxidative aging of organic aerosols (OA) occurs ubiquitously in the atmosphere, initiated by oxidants, such as the hydroxyl radicals (•OH). Hydroperoxyl radicals (HO2•) are also an important oxidant in the troposphere, and its gas-phase chemistry has been well studied. However, the role of HO2• in heterogeneous OA oxidation remains elusive. Here, we carry out •OH-initiated heterogeneous oxidation of several OA model systems under different HO2• conditions in a flow tube reactor and characterize the molecular oxidation products using a suite of mass spectrometry instrumentation. By using hydrogen-deuterium exchange (HDX) with thermal desorption iodide-adduct chemical ionization mass spectrometry, we provide direct observation of organic hydroperoxide (ROOH) formation from heterogeneous HO2• and peroxy radicals (RO2•) reactions for the first time. The ROOH may contribute substantially to the oxidation products, varied with the parent OA chemical structure. Furthermore, by regulating RO2• reaction pathways, HO2• also greatly influence the overall composition of the oxidized OA. Last, we suggest that the RO2• + HO2• reactions readily occur at the OA particle interface rather than in the particle bulk. These findings provide new mechanistic insights into the heterogeneous OA oxidation chemistry and help fill the critical knowledge gap in understanding atmospheric OA oxidative aging.

Improving the Sensitivity and Linear Range of Photoionization Ion Mobility Spectrometry via Confining the Ion Recombination and Space Charge Effects Assisted by Theoretical Modeling.

Photoionization (PI) is an efficient ionization source for ion mobility spectrometry (IMS) and mass spectrometry. Its hyphenation with IMS (PI-IMS) has been employed in various on-site analysis scenarios targeting a wide range of compounds. However, the signal intensity and linear dynamic range of PI-IMS at ambient pressure usually do not follow the Beer-Lambert law predictions, and the factors causing that negative deviation remain unclear. In this work, a variable pressure PI-IMS system was developed to examine the ion loss effects from factors like ion recombination and space charge by varying its working pressure from 1 to 0.1 bar. Assisted by theoretical modeling, it was found that ion recombination could contribute up to 90% of signal intensity loss for ambient pressure PI-IMS setups. Lowering the pressure and increasing the electric field in PI-IMS helped suppress the ion recombination process and thus an optimal pressure Poptimal appeared for best signal intensity, despite the decreased net ion number density and the increased space charge effect. A simplified theoretical equation taking ion recombination as the primary ion loss factor was derived to link Poptimal with analyte concentration and electric field in PI-IMS, enabling a swift optimization of the PI-IMS performance. For example, compared to ambient pressure, PI-IMS at a Poptimal of 0.4 bar provided a signal intensity increment of more than 400% for 0.716 ppmv toluene and also expanded the linear dynamic range by more than two times. Revealing factors influencing the PI-IMS response would also benefit the applications of other chemical ionization sources in IMS or mass spectrometry (MS).

Molecular characteristics of eight lignites based on the big data obtained from Orbitrap mass spectrometry

Eight lignites from different regions were selected for thermal dissolution (TD) sequentially using cyclohexane, methanol and ethanol. The TD extracts of the eight coal samples were characterized using atmospheric pressure chemical ionization source (APCI)-Orbitrap mass spectrometry (MS). Chemometric methods were employed to deeply explore the molecular structural and composition information of the organic compounds detected by Orbitrap MS. The longest distance method in systematic clustering of chemometrics was employed to ascertain the optimal number of groups, which was found to be 7 by clustering 24 soluble portions (SPs) using Euclidean distance. Taking one group as an example, the similarities and differences of SPs within the group were derived based on the compositional class of O1N1, N1, O2N1 and O2, and heteroatom distribution patterns of the SPs were proposed and compared. The integration of high-resolution MS data and chemometric methods not only exposes the existence of heteroatomic compounds in lignite but also furnishes evidence for the origin and evolution of lignite, as well as a methodology for the high-value utilization of lignites from different sources.

Oxygenated organic molecules produced by low-NOx photooxidation of aromatic compounds: contributions to secondary organic aerosol and steric hindrance

Abstract. Oxygenated organic molecules (OOMs) produced by the oxidation of aromatic compounds are key components of secondary organic aerosol (SOA) in urban environments. The steric effects of substitutions and rings and the role of key reaction pathways in altering the OOM distributions remain unclear because of the lack of systematic multi-precursor study over a wide range of OH exposure. In this study, we conducted flow-tube experiments and used the nitrate adduct time-of-flight chemical ionization mass spectrometer (NO3--TOF-CIMS) to measure the OOMs produced by the photooxidation of six key aromatic precursors under low-NOx conditions. For single aromatic precursors, the detected OOM peak clusters show an oxygen atom difference of one or two, indicating the involvement of multi-step auto-oxidation and alkoxy radical pathways. Multi-generation OH oxidation is needed to explain the diverse hydrogen numbers in the observed formulae. In particular, for double-ring precursors at higher OH exposure, multi-generation OH oxidation may have significantly enriched the dimer formulae. The results suggest that methyl substitutions in precursor lead to less fragmented OOM products, while the double-ring structure corresponds to less efficient formation of closed-shell monomeric and dimeric products, both highlighting significant steric effects of precursor molecular structure on the OOM formation. Naphthalene-derived OOMs however have lower volatilities and greater SOA contributions than the other-type of OOMs, which may be more important in initial particle growth. Overall, the OOMs identified by the NO3--TOF-CIMS may have contributed up to 30.0 % of the measured SOA mass, suggesting significant mass contributions of less oxygenated, undetected semi-volatile products. Our results highlight the key roles of progressive OH oxidation, methyl substitution and ring structure in the OOM formation from aromatic precursors, which need to be considered in future model developments to improve the model performance for organic aerosol.

If speed is of the essence: rapid analysis of ambergris by APCI compact mass spectrometry

The use of atmospheric pressure chemical ionisation (APCI) compact mass spectrometry (CMS) was investigated for the analysis of jetsam and museum-archived ambergris and of ambergris components in perfumes. The data were compared with those from existing methods. Authentic samples of some individual ambergris constituents (ambrein, coprostanol, epicoprostanol and coprostanone), were also examined. Rapid APCI CMS was achieved using either a solids probe or a probe with solutions held in capillary melting point tubes. Interpretation is made of the spectra of the principal natural product components, the relative ion responses were measured and the elemental composition of key ions in the spectra confirmed using high resolution accurate mass APCI MS. Rapid analysis of ambergris by APCI CMS may prove to be a further convenient method of identifying ambrein, of measuring the relative ratios of ambrein and steroids in ambergris and even of quantifying the latter, with minimal sample preparation.