Mechanistic studies of corrosion product flaking on copper and copper-based alloys in marine environments

AbstractThe mechanism of corrosion product flaking on bare copper sheet and three copper-based alloys in chloride rich environments has been explored through field and laboratory exposures. The tendency for flaking is much more pronounced on Cu and Cu–4wt%Sn than on Cu–15wt%Zn and Cu–5wt%Al–5wt%Zn. This difference is explained by the initial formation of zinc and zinc–aluminum hydroxycarbonates on Cu15Zn and Cu5Al5Zn, which delays the formation of CuCl, a precursor of Cu2(OH)3Cl. As a result, the observed volume expansion during transformation of CuCl to Cu2(OH)3Cl, and concomitant corrosion product flaking, is less severe on Cu15Zn and Cu5Al5Zn than on Cu and Cu4Sn

Bioaccessibility, bioavailability and toxicity of commercially relevant iron- and chromium-based particles: in vitro studies with an inhalation perspective

<p>Abstract</p> <p>Background</p> <p>Production of ferrochromium alloys (FeCr), master alloys for stainless steel manufacture, involves casting and crushing processes where particles inevitably become airborne and potentially inhaled. The aim of this study was to assess potential health hazards induced by inhalation of different well-characterized iron- and chromium-based particles, i.e. ferrochromium (FeCr), ferrosiliconchromium (FeSiCr), stainless steel (316L), iron (Fe), chromium (Cr), and chromium(III)oxide (Cr₂O₃), in different size fractions using in vitro methods. This was done by assessing the extent and speciation of released metals in synthetic biological medium and by analyzing particle reactivity and toxicity towards cultured human lung cells (A549).</p> <p>Results</p> <p>The amount of released metals normalized to the particle surface area increased with decreasing particle size for all alloy particles, whereas the opposite situation was valid for particles of the pure metals. These effects were evident in artificial lysosomal fluid (ALF) of pH 4.5 containing complexing agents, but not in neutral or weakly alkaline biological media. Chromium, iron and nickel were released to very low extent from all alloy particles, and from particles of Cr due to the presence of a Cr(III)-rich protective surface oxide. Released elements were neither proportional to the bulk nor to the surface composition after the investigated 168 hours of exposure. Due to a surface oxide with less protective properties, significantly more iron was released from pure iron particles compared with the alloys. Cr was predominantly released as Cr(III) from all particles investigated and was strongly complexed by organic species of ALF. Cr₂O₃particles showed hemolytic activity, but none of the alloy particles did. Fine-sized particles of stainless steel caused however DNA damage, measured with the comet assay after 4 h exposure. None of the particles revealed any significant cytotoxicity in terms of cell death after 24 h exposure.</p> <p>Conclusion</p> <p>It is evident that particle and alloy characteristics such as particle size and surface composition are important aspects to consider when assessing particle toxicity and metal release from alloy particles compared to pure metal particles. Generated results clearly elucidate that neither the low released concentrations of metals primarily as a result of protective and poorly soluble surface oxides, nor non-bioavailable chromium complexes, nor the particles themselves of occupational relevance induced significant acute toxic response, with exception of DNA damage from stainless steel.</p

Surface–rain interactions: Differences in copper runoff for copper sheet of different inclination, orientation, and atmospheric exposure conditions

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Influence of surface oxide characteristics and speciation on corrosion, electrochemical properties and metal release of atomized 316L stainless steel powders

Surface oxide characteristics of powder particles are important to consider for any toxicological risk assessment based on in-vitro or in-vivo tests. This study focuses on a multi-analytical approach (X-ray photoelectron spectroscopy, Auger electron spectroscopy, scanning- and transmission electron microscopy, and different electrochemical techniques) for in-depth characterization of surface oxides of inert-gas-atomized (GA) AISI 316L stainless steel powder, compared with massive sheet and a water-atomized (WA) 316L powder. Implications of differences in surface oxide phases and their surface distribution on corrosion, electrochemical properties and metal release are systematically discussed. Cr was enriched in an inner surface layer for both GA powders, with Mn and S enriched in the outermost surface oxide. The surface oxide was 2-5 nm thick for both GA powder size fractions, amorphous for the GA powder size

Metal bioaccessibility in synthetic bodyfluids–A way to considerpositive and negative alloying effects in hazard assessments

Hazard classification of metal alloys is today generally based on their bulk content, an approach that seldom reflects the extent of metal release for a given environment. Such information can instead be achieved via bioelution testing under simulated physiological conditions. The use of bioelution data instead of bulk contents would hence refine the current hazard classification of alloys and enable grouping. Bioelution data have been generated for nickel (Ni) and cobalt (Co) released from several stainless steel grades, one low-alloyed steel, and Ni and Co metals in synthetic sweat, saliva and gastric fluid, for exposure periods from 2 to 168 h. All stainless steel grades with bulk contents of 0.11–10 wt% Ni and 0.019–0.24 wt% Co released lower amounts of Ni (up to 400-fold) and Co (up to 300-fold) than did the low-alloyed steel (bulk content: 0.034% Ni, 0.015% Co). They further showed a relative bioaccessibility of Ni and Co considerably less than 1, while the opposite was the case for the low-alloyed steel. Surface oxide- and electrochemical corrosion investigations explained these findings in terms of the high passivity of the stainless steels related to the Cr(III)-rich surface oxide that readily adapted to the fluid acidity and chemistry

Influence of surface oxide characteristics and speciation on corrosion, electrochemical properties and metal release of atomized 316L stainless steel powders

Surface oxide characteristics of powder particles are important to consider for any toxicological risk assessment based on in-vitro or in-vivo tests. This study focuses on a multi-analytical approach (X-ray photoelectron spectroscopy, Auger electron spectroscopy, scanning- and transmission electron microscopy, and different electrochemical techniques) for in-depth characterization of surface oxides of inert-gas-atomized (GA) AISI 316L stainless steel powder, compared with massive sheet and a water-atomized (WA) 316L powder. Implications of differences in surface oxide phases and their surface distribution on corrosion, electrochemical properties and metal release are systematically discussed. Cr was enriched in an inner surface layer for both GA powders, with Mn and S enriched in the outermost surface oxide. The surface oxide was 2-5 nm thick for both GA powder size fractions, amorphous for the GA powder size

Surface-protein interactions on different stainless steel grades: effects of protein adsorption, surface changes and metal release

Implantation using stainless steels (SS) is an example where an understanding of protein-induced metal release from SS is important when assessing potential toxicological risks. Here, the protein-induced metal release was investigated for austenitic (AISI 304, 310, and 316L), ferritic (AISI 430), and duplex (AISI 2205) grades in a phosphate buffered saline (PBS, pH 7.4) solution containing either bovine serum albumin (BSA) or lysozyme (LSZ). The results show that both BSA and LSZ induce a significant enrichment of chromium in the surface oxide of all stainless steel grades. Both proteins induced an enhanced extent of released iron, chromium, nickel and manganese, very significant in the case of BSA (up to 40-fold increase), whereas both proteins reduced the corrosion resistance of SS, with the reverse situation for iron metal (reduced corrosion rates and reduced metal release in the presence of proteins). A full monolayer coverage is necessary to induce the effects observed. ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (doi:10.1007/s10856-013-4859-8) contains supplementary material, which is available to authorized users

Cobalt nanoparticles trigger ferroptosis-like cell death (oxytosis) in neuronal cells : Potential implications for neurodegenerative disease

Abstract The neurotoxicity of hard metal-based nanoparticles (NPs) remains poorly understood. Here, we deployed the human neuroblastoma cell line SH-SY5Y differentiated or not into dopaminergic- and cholinergic-like neurons to study the impact of tungsten carbide (WC) NPs, WC NPs sintered with cobalt (Co), or Co NPs versus soluble CoCl2. Co NPs and Co salt triggered a dose-dependent cytotoxicity with an increase in cytosolic calcium, lipid peroxidation, and depletion of glutathione (GSH). Co NPs and Co salt also suppressed glutathione peroxidase 4 (GPX4) mRNA and protein expression. Co-exposed cells were rescued by N-acetylcysteine (NAC), a precursor of GSH, and partially by liproxstatin-1, an inhibitor of lipid peroxidation. Furthermore, in silico analyses predicted a significant correlation, based on similarities in gene expression profiles, between Co-containing NPs and Parkinson's disease, and changes in the expression of selected genes were validated by RT-PCR. Finally, experiments using primary human dopaminergic neurons demonstrated cytotoxicity and GSH depletion in response to Co NPs and CoCl2 with loss of axonal integrity. Overall, these data point to a marked neurotoxic potential of Co-based but not WC NPs and show that neuronal cell death may occur through a ferroptosis-like mechanism.Peer reviewe

Adsorption of bio-organic eco-corona molecules reduces the toxic response to metallic nanoparticles in <i>Daphnia magna</i>

As the use of engineered nanomaterials increases, so does the risk of them spreading to natural ecosystems. Hitherto, knowledge regarding the toxic properties of nanoparticles (NP’s) and their potential interactions with natural bio-organic molecules adsorbed to them, and thereby forming surface coronas, is limited. However, we show here that the toxic effect of NPs of tungsten carbide cobalt (WC–Co) and cobalt (Co) on the crustacean Daphnia magna is postponed in the presence of natural biological degradation products (eco-corona biomolecules). For Daphnia exposed to WC–Co NPs the survival time increased with 20–25% and for Co NPs with 30–47% after mixing the particles with a solution of eco-corona biomolecules before exposure. This suggests that an eco-corona, composed of biomolecules always present in natural ecosystems, reduces the toxic potency of both studied NPs. Further, the eco-coronas did not affect the particle uptake, suggesting that the reduction in toxicity was related to the particle-organism interaction after eco-corona formation. In a broader context, this implies that although the increasing use and production of NPs may constitute a novel, global environmental threat, the acute toxicity and long-term effects of some NPs will, at least under certain conditions, be reduced as they enter natural ecosystems

Location of cobalt impurities in the surface oxide of stainless steel 316L and metal release in synthetic biological fluids

Since 2021, cobalt (Co) is in Europe classified as carcinogen in quantities exceeding 0.1 wt-%. This affects nickel-rich stainless steels, which contain about 0.2 wt-% Co impurities. Previous findings show the bioaccessibility of Co in stainless steel to be primarily determined by the corrosion resistance. It has been unclear whether Co is distributed heterogeneously in the alloy and the outermost surface and whether a specific location would pose a risk for Co release under specific exposure conditions. This study aimed at locating Co in stainless steel 316L (0.2 wt-% Co) surfaces prior to and after exposure to different synthetic body fluids for 24 h at 37 °C. Time-of-flight secondary ion mass spectrometry (ToF-SIMS), X-ray photoelectron spectroscopy (XPS), and inductively coupled plasma mass spectrometry (ICPMS) investigated the location of Co in the surface oxide and extent of release along with other metals (iron, chromium, nickel, and manganese) into synthetic biological fluids (gastric fluid, pH 1.5; lysosomal fluid, pH 4.5; phosphate buffered saline-PBS, pH 7.4). Co was homogeneously distributed along with metallic nickel beneath the surface oxide and co-released with other metals upon surface reformation and passivation. Exposure in PBS resulted in the incorporation of both Co and phosphate in the oxide