Chemical characterisation of benzene oxidation products under high- and low-NO_<i>x</i> conditions using chemical ionisation mass spectrometry

Aromatic hydrocarbons are a class of volatile organic compounds associated with anthropogenic activity and make up a significant fraction of urban volatile organic compound (VOC) emissions that contribute to the formation of secondary organic aerosol (SOA). Benzene is one of the most abundant species emitted from vehicles, biomass burning and industry. An iodide time-of-flight chemical ionisation mass spectrometer (ToF-CIMS) and nitrate ToF-CIMS were deployed at the Jülich Plant Atmosphere Chamber as part of a series of experiments examining benzene oxidation by OH under high- and low-NOx conditions, where a range of organic oxidation products were detected. The nitrate scheme detects many oxidation products with high masses, ranging from intermediate volatile organic compounds (IVOCs) to extremely low volatile organic compounds (ELVOCs), including C12 dimers. In comparison, very few species with C≥6 and O≥8 were detected with the iodide scheme, which detected many more IVOCs and semi-volatile organic compounds (SVOCs) but very few ELVOCs and low volatile organic compounds (LVOCs). A total of 132 and 195 CHO and CHON oxidation products are detected by the iodide ToF-CIMS in the low- and high-NOx experiments respectively. Ring-breaking products make up the dominant fraction of detected signal and 21 and 26 of the products listed in the Master Chemical Mechanism (MCM) were detected. The time series of highly oxidised (O≥6) and ring-retaining oxidation products (C6 and double-bond equivalent = 4) equilibrate quickly, characterised by a square form profile, compared to MCM and ring-breaking products which increase throughout oxidation, exhibiting sawtooth profiles. Under low-NOx conditions, all CHO formulae attributed to radical termination reactions of first-generation benzene products, and first-generation auto-oxidation products are observed. Several N-containing species that are either first-generation benzene products or first-generation auto-oxidation products are also observed under high-NOx conditions. Hierarchical cluster analysis finds four clusters, of which two describe photo-oxidation. Cluster 2 shows a negative dependency on the NO2/NOx ratio, indicating it is sensitive to NO concentration and thus likely to contain NO addition products and alkoxy-derived termination products. This cluster has the highest average carbon oxidation state (OSC‾) and the lowest average carbon number. Where nitrogen is present in a cluster member of cluster 2, the oxygen number is even, as expected for alkoxy-derived products. In contrast, cluster 1 shows no dependency on the NO2/NOx ratio and so is likely to contain more NO2 addition and peroxy-derived termination products. This cluster contains fewer fragmented species, as the average carbon number is higher and OSC‾ lower than cluster 2, and more species with an odd number of oxygen atoms. This suggests that clustering of time series which have features pertaining to distinct chemical regimes, for example, NO2/NOx perturbations, coupled with a priori knowledge, can provide insight into identification of potential functionality.

Silver-109/Silver/Gold Nanoparticle-Enhanced Target Surface-Assisted Laser Desorption/Ionisation Mass Spectrometry—The New Methods for an Assessment of Mycotoxin Concentration on Building Materials

This study aimed to detect and quantify mycotoxins on building materials using innovative laser mass spectroscopy methods—silver-109/silver/gold nanoparticle-enhanced target surface-assisted laser desorption/ionisation mass spectrometry (109AgNPs, AgNPs and AuNPs SALDI). Results from SALDI-type methods were also compared with commonly used matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. Standards of seven moulds mycotoxin in a final concentration of 100 µg/mL for patulin, citrinin, 3-nitropropionic acid, alternariol and 20 µg/mL for sterigmatocystin, cyclopiazonic acid, roquefortine C in the mixture were tested in pure solutions and after extraction from the plasterboards. Among the studied SALDI-type method, the lowest detection limits and the highest signal intensity of the mycotoxins tested were obtained with the use of 109AgNPs SALDI MS. The 109AgNPs method may be considered as an alternative to the currently most frequently used method MALDI MS and also liquid chromatography tandem mass spectrometry LC-MS/MS for mycotoxin determination. Future studies should attempt to use these methods for mass spectrometry imaging (MSI) to evaluate spatial distribution and depth of mycotoxin penetration into building materials.

Liquid chromatography – high resolution mass spectrometry screening of Astragalus hamosus and Astragalus corniculatus

Astragalus hamosus and Astragalus corniculatus were examined for the presence of flavoalkaloids, acylated and highly glycosylated flavonoids. Non-purified extracts of the overground parts of the species were subjected to ultra-high performance liquid chromatography – high resolution electrospray ionisation mass spectrometry (UHPLC-HRESIMS) analysis and the results were compared to authentic reference substances. A flavoalkaloid of kaempferol was newly identified in an extract of A. hamosus. In addition, three compounds – quercetin and kaempferol flavonoids, acylated with hydroxymethylglutaric acid and alcesefoliside, were found in extracts of A. hamosus and A. corniculatus for the first time.

In situ characterisation of phytohormones from wounded Arabidopsis leaves using desorption electrospray ionisation mass spectrometry imaging

Phytohormones (plant hormones) are a group of small signalling molecules that act as important endogenous regulators in the plant development and stress responses. Previous research has identified phytohormone species, jasmonates,...