Soot particles produced by incomplete combustion processes are one of the major components of urban air pollution. Chemistry at their surfaces lead to the heterogeneous conversion of several key trace gases; for example NO ₂ interacts with soot and is converted into HONO, which rapidly photodissociates to form OH in the troposphere. In the dark, soot surfaces are rapidly deactivated under atmospheric conditions, leading to the current understanding that soot chemistry affects tropospheric chemical composition only in a minor way. We demonstrate here that the conversion of NO ₂ to HONO on soot particles is drastically enhanced in the presence of artificial solar radiation, and leads to persistent reactivity over long periods. Soot photochemistry may therefore be a key player in urban air pollution.

Untargeted metabolomics is an analytical approach with numerous applications serving as an effective metabolic phenotyping platform to characterize small molecules within a biological system. Data quality can be challenging to evaluate and demonstrate in metabolomics experiments. This has driven the use of pooled quality control (QC) samples for monitoring and, if necessary, correcting for analytical variance introduced during sample preparation and data acquisition stages. Described herein is a scoping literature review detailing the use of pooled QC samples in published untargeted liquid chromatography-mass spectrometry (LC-MS) based metabolomics studies. A literature query was performed, the list of papers was filtered, and suitable articles were randomly sampled. In total, 109 papers were each reviewed by at least five reviewers, answering predefined questions surrounding the use of pooled quality control samples. The results of the review indicate that use of pooled QC samples has been relatively widely adopted by the metabolomics community and that it is used at a similar frequency across biological taxa and sample types in both small- and large-scale studies. However, while many studies generated and analyzed pooled QC samples, relatively few reported the use of pooled QC samples to improve data quality. This demonstrates a clear opportunity for the field to more frequently utilize pooled QC samples for quality reporting, feature filtering, analytical drift correction, and metabolite annotation. Additionally, our survey approach enabled us to assess the ambiguity in the reporting of the methods used to describe the generation and use of pooled QC samples. This analysis indicates that many details of the QC framework are missing or unclear, limiting the reader's ability to determine which QC steps have been taken. Collectively, these results capture the current state of pooled QC sample usage and highlight existing strengths and deficiencies as they are applied in untargeted LC-MS metabolomics.

Formaldehyde (FA) is a ubiquitous endogenous and environmental metabolite that is thought to exert cytotoxicity through DNA and DNA-protein crosslinking, likely contributing to the onset of the human DNA repair condition Fanconi Anaemia. Mutations in the genes coding for FA detoxifying enzymes underlie a human inherited bone marrow failure syndrome (IBMFS), even in the presence of functional DNA repair, raising the question of whether FA causes relevant cellular damage beyond genotoxicity. Here, we report that FA triggers cellular redox imbalance in human cells and inCaenorhabditis elegans. Mechanistically, FA reacts with the redox-active thiol group of glutathione (GSH), altering the GSH:GSSG ratio and causing oxidative stress. FA cytotoxicity is prevented by the enzyme alcohol dehydrogenase 5 (ADH5/GSNOR), which metabolizes FA-GSH products, lastly yielding reduced GSH. Furthermore, we show that GSH synthesis protects human cells from FA, indicating an active role of GSH in preventing FA toxicity. These findings might be relevant for patients carrying mutations in FA-detoxification systems and could suggest therapeutic benefits from thiol-rich antioxidants like N-acetyl-L-cysteine.

The reactivity of NO₂ on irradiated TiO₂/SiO₂ films was studied, with different TiO₂ contents, as proxies for NO_x de-polluting materials. The influence of the photocatalyst concentration, the role of molecular oxygen and the effect of nitrate on the reactivity of TiO₂ films were investigated. NO, HONO and nitrate anions are produced as a consequence of the NO₂ loss on UV-illuminated TiO₂ films. The photoinduced nitrate conversion into NO_x and HONO at the TiO₂ surface is discussed as being a renoxification process, which involves the NO₃ radical. The presence of O₂ in the carrier gas modifies the NO and HONO production yields in the heterogeneous reaction between NO₂ and TiO₂ as well as the products of the renoxification process. Depending on the nature of the surface, the interaction between NO₂ and nitrate with TiO₂ may generate HONO that may have a negative impact on air quality.