The effect of blue light on atmospheric corrosion of Cu and on the antimicrobial properties was explored upon exposure mimicking the condition of hygienic surface disinfection. The results show that blue light illumination enhanced the formation of Cu2O, resulting in a slightly increased corrosion resistance of Cu without pre-deposited NaCl, whereas the enhanced formation of Cu2O, CuCl and/or Cu(OH)3Cl on copper with pre-deposited NaCl caused concomitant corrosion product flaking and a reduced corrosion resistance. The blue light induced enhancement of Cu corrosion led to increased surface roughness and more pronounced integration of bacteria within the corrosion products.

Expanding applications and production of engineered nanoparticles lead to an increased risk for their environmental dispersion. Systematic knowledge of surface transformation and dissolution of nanoparticles is essential for risk assessment and regulation establishment. Such aspects of Co- and Ni-based nanoparticles including metals, oxides, and solution combustion synthesized metal nanoparticles (metal cores with carbon shells) were investigated upon environmental interaction with organic matter, simulated by natural organic matter (NOM) and degradation products from zooplankton and algae (eco-corona biomolecules, EC) in freshwater (FW). The presence of NOM and EC in FW results in negative surface charges of the nanoparticles reduces the extent of nanoparticles agglomeration, and increases concentration, mainly due to the surface adsorption of carboxylate groups of the organic matter. The dissolution of the Co-based nanoparticles was for all conditions (FW, FW with NOM or EC) higher than the Ni-based, except for Co3O4 being nearly non-soluble. The surface transformation and dissolution of nanoparticles are highly exposure and time-dependent, and surface- and environment specific. Therefore, no general correlation was observed between dissolution and, particle types, surface conditions, or EC/NOM adsorption. This underlines the importance of thorough investigations of nanoparticles adsorption/desorption, degradation, and exposure scenarios for developing regulatory relevant protocols and guidelines.

The attention to rare earth oxide nanoparticles (NPs), including yttrium oxide (Y2O3), has increased in many fields due to their unique structural characteristics and functional properties. The aim of our study was to investigate the mechanisms by which bio-corona formation on Y2O3 NPs affects their environmental fate and toxicity. The Y2O3 NPs induced toxicity to freshwater filter feeder Daphnia magna at particle concentrations of 1 and 10 mg/L, regardless of particle size. Interactions between naturally excreted biomolecules (e.g. protein, lipids, and polysaccharides) derived from D. magna, and the Y2O3 NPs (30–45 nm) resulted in the formation of an eco-corona, which reduced their toxic effects toward D. magna at a particle concentration of 10 mg/L. No effects were observed at lower concentrations or for the other particle sizes investigated. Copper-zinc (Cu-Zn) superoxide dismutase, apolipophorins, and vitellogenin-1 proteins proved to be the most prominent proteins of the adsorbed corona, and possibly a reason for the reduced toxicity of the 30–45 nm Y2O3 NPs toward D. magna.

Increased use and production of engineered nanoparticles (NPs) lead to an elevated risk of their diffuse dispersion into the aquatic environment and increased concern on unknown effects induced by their release into the aquatic ecosystem. An improved understanding of the environmental transformation processes of NPs of various surface characteristics is hence imperative for risk assessment and management. This study presents results on effects of natural organic matter (NOM) on the environmental transformation and dissolution of metal and metal oxide NPs of different surface and solubility properties in synthetic freshwater (FW) with and without NOM. Adsorption of NOM was evident on most of the studied NPs, except Sb and Sb2O3, which resulted in the formation of negatively charged colloids of higher stability and smaller size distribution compared with the same NPs in FW only. The dissolution rate of the NPs in the presence of NOM correlated with the strength of interactions between the carboxylate group of NOM and the particle surface, and resulted in either no (Mn, Sb, ZnO NPs), increased (Co, Sn NPs) and decreased (Ni, NiO, Sb2O3, Y2O3 NPs) levels of dissolution. One type of metal NP from each group (Mn, Ni, Sn) were investigated to assess whether observed differences in adsorption of NOM and dissolution would influence their ecotoxic potency. The results showed Mn, Ni, and Sn NPs to generate intracellular reactive oxygen species (ROS) in a time and dose-dependent manner. The extent of ROS generation in FW was similar for both Mn and Ni NPs but higher for Sn NPs. These findings are possibly related to interactions and infiltration of the NPs with the cells, which lead to redox imbalances which could induce oxidative stress and cell damage. At the same time, the presence of NOM generally reduced the intracellular ROS generation by 20-40% for the investigated NPs and also reduced cytotoxicity of Sn NPs, which can be attributed to the stronger interaction of carboxylate groups of NOM with the surface of the NPs.

Corrosion effects on copper exposed in a humid atmosphere with formic acid (mimicking indoor corrosion) have been explored through successive increase in surface lateral resolution from macroscale (IRRAS, GIXRD) over microscale (LOM, SEM, IR microscopy) to nanoscale (Nano-FTIR, FIB/SEM/EDS). Initial more uniform growth of Cu2O is followed by more varying topography and thickness until local removal of Cu2O enables the aqueous adlayer to react with the copper substrate. Local formation of Cu(OH)(HCOO) and adjacent Cu2O provide microscopic and spectroscopic evidence of corrosion cells. Nano-FTIR shows that the density of Cu(OH)(HCOO) nuclei, but not their size, increases with exposure time.

Metal-based high-touch surfaces used for indoor applications such as doorknobs, light switches, handles and desks need to remain their antimicrobial properties even when tarnished or degraded. A novel laboratory methodology of relevance for indoor atmospheric conditions and fingerprint contact has therefore been elaborated for combined studies of both tarnishing/corrosion and antimicrobial properties of such high-touch surfaces. Cu metal was used as a benchmark material. The protocol includes pre-tarnishing/corrosion of the high touch surface for different time periods in a climatic chamber at repeated dry/wet conditions and artificial sweat deposition followed by the introduction of bacteria onto the surfaces via artificial sweat droplets. This methodology provides a more realistic and reproducible approach compared with other reported procedures to determine the antimicrobial efficiency of high-touch surfaces. It provides further a possibility to link the antimicrobial characteristics to physical and chemical properties such as surface composition, chemical reactivity, tarnishing/corrosion, surface roughness and surface wettability. The results elucidate that bacteria interactions as well as differences in extent of tarnishing can alter the physical properties (e.g. surface wettability, surface roughness) as well as the extent of metal release. The results clearly elucidate the importance to consider changes in chemical and physical properties of indoor hygiene surfaces when assessing their antimicrobial properties.

The corrosion inhibition of self-assembled octadecylphosphonic acid (ODPA) layers on non-oxidized and pre-oxidized copper and Langmuir-Blodgett deposited ODPA layers on pre-oxidized copper was investigated under a simulated indoor atmospheric corrosion environment containing 80% RH and 100 ppb formic acid. The corrosion process was monitored in-situ with infrared absorption/reflection spectroscopy, and the corrosion products were further characterised by grazing incidence X-ray diffraction. Nano-FTIR microscopy was used to reveal the nature, size, and distribution of the corrosion products on the nanoscale. The combination of pre-formed cuprite and ODPA layers, both with only some nanometres thickness, provided an excellent protection under this environment.

The mechanisms of bacterial contact killing induced by Cu surfaces were explored through high-resolution studies based on combinations of the focused ion beam (FIB), scanning transmission electron microscopy (STEM), high-resolution TEM, and nanoscale Fourier transform infrared spectroscopy (nano-FTIR) microscopy of individual bacterial cells of Gram-positive Bacillus subtilis in direct contact with Cu metal and Cu5Zn5Al1Sn surfaces after high-touch corrosion conditions. This approach permitted subcellular information to be extracted from the bioinorganic interface between a single bacterium and Cu/Cu5Zn5Al1Sn surfaces after complete contact killing. Early stages of interaction between individual bacteria and the metal/alloy surfaces include cell leakage of extracellular polymeric substances (EPSs) from the bacterium and changes in the metal/alloy surface composition upon adherence of bacteria. Three key observations responsible for Cu-induced contact killing include cell membrane damage, formation of nanosized copper-containing particles within the bacteria cell, and intracellular copper redox reactions. Direct evidence of cell membrane damage was observed upon contact with both Cu metal and Cu5Zn5Al1Sn surfaces. Cell membrane damage permits copper to enter into the cell interior through two possible routes, as small fragmentized Cu2O particles from the corrosion product layer and/or as released copper ions. This results in the presence of intracellular copper oxide nanoparticles inside the cell. The nanosized particles consist primarily of CuO with smaller amounts of Cu2O. The existence of two oxidation states of copper suggests that intracellular redox reactions play an important role. The nanoparticle formation can be regarded as a detoxification process of copper, which immobilizes copper ions via transformation processes within the bacteria into poorly soluble or even insoluble nanosized Cu structures. Similarly, the formation of primarily Cu(II) oxide nanoparticles could be a possible way for the bacteria to deactivate the toxic effects induced by copper ions via conversion of Cu(I) to Cu(II).

The interplay between atmospheric corrosion and antimicrobial efficiency of bare Cu and Cu5Zn5Al1Sn was studied upon exposures simulating high-touch surface conditions. The survival of the bacteria Bacillus subtilis during surface contact with Cu and Cu5Zn5Al1Sn was examined under different degrees of surface oxidation, tarnishing, wettability and copper ion release. Depending on surface conditions complete bacteria inhibition was obtained within 4 min on Cu and within 6-10 min on Cu5Zn5Al1Sn. The antibacterial efficiency increases slightly with copper release rate and is governed by complex interactions between the corroded metal surface, bacteria and extracellular polymeric substances produced by the bacteria.

The complex stratified patina formed on Sn-bronze in chloride-rich atmospheres has been explored through long-term field exposures and short-term laboratory investigations using a multi-analytical approach. The stratified patina is composed of Cu2O- and Cu-2(OH)(3)Cl-rich sublayers intercalated by Sn-oxides, mainly SnO2. The stratification is triggered by events of high chloride deposition, resulting in repeated dissolution and solidification of sublayers, whereby redox reactions between the intermediate products of Sn- and Cu-chlorides play a crucial role. Sn-induced patina stratification is a major reason for enhanced patina flaking on Sn-bronze and its accelerated corrosion rate compared to Cu metal in marine environments.