Due to their enhanced reactivity, metal and metal-oxide nanoscale zero-valent iron (nZVI) nanomaterials have been introduced into remediation practice. To ensure that environmental applications of nanomaterials are safe, their possible toxic effects should be described. However, there is still a lack of suitable toxicity tests that address the specific mode of action of nanoparticles, especially for nZVI. This contribution presents a novel approach for monitoring one of the most discussed adverse effects of nanoparticles, i.e., oxidative stress (OS). We optimized and developed an assay based on headspace-SPME-GC-MS analysis that enables the direct determination of volatile oxidative damage products (aldehydes) of lipids and proteins in microbial cultures after exposure to commercial types of nZVI. The method employs PDMS/DVB SPME fibers and pentafluorobenzyl derivatization, and the protocol was successfully tested using representatives of bacteria, fungi, and algae. Six aldehydes, namely, formaldehyde, acrolein, methional, benzaldehyde, glyoxal, and methylglyoxal, were detected in the cultures, and all of them exhibited dose-dependent sigmoidal responses. The presence of methional, which was detected in all cultures except those including an algal strain, documents that nZVI also caused oxidative damage to proteins in addition to lipids. The most sensitive toward nZVI exposure in terms of aldehyde production was the yeast strain Saccharomyces cerevisiae, which had an EC50 value of 0.08 g/L nZVI. To the best of our knowledge, this paper is the first to document the production of aldehydes resulting from lipids and proteins as a result of OS in microorganisms from different kingdoms after exposure to iron nanoparticles.

Department of Analytical Chemistry Helmholtz Center for Environmental Research UFZ Permoserstr 15 04318 Leipzig Germany

Institute of Hydrodynamics of the Czech Academy of Sciences Pod Patankou 30 5 CZ 166 12 Prague 6 Czech Republic

Institute of Microbiology of the Czech Academy of Sciences Vídeňská 1083 CZ 142 20 Prague 4 Czech Republic Institute for Environmental Studies Faculty of Science Charles University Benátská 2 CZ 128 01 Prague 2 Czech Republic

Regional Centre of Advanced Technologies and Materials Palacký University Šlechtitelů 27 CZ 783 71 Olomouc Czech Republic

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