Biomedical materials made of cobalt-chromium-molybdenum (CoCrMo) alloys are commonly used in artificial prostheses and dental implants, which are exposed to friction and load. The release of Co, Cr, and Mo from these surfaces is governed by physical and chemical processes. The extent of measured metal release from biomedical CoCrMo alloys into mixed protein solutions may be influenced by protein aggregation and metal precipitation effects. Metal release from, and the surface composition of, a CoCrMo alloy was investigated in physiological relevant solutions (phosphate buffered saline, PBS, with varying concentrations of fibrinogen from bovine plasma and/or bovine serum albumin) at pH 7.3 in static and sliding conditions for time periods between 1 and 24 h. Cr was strongly enriched in the surface oxide of CoCrMo in all solutions, which corresponded to metal release dominated by Co. PBS and the proteins could induce significant precipitation of metals and protein aggregates, which resulted in strongly underestimated released amounts of Co and Cr, but not Mo, especially under sliding conditions. Protein aggregates were found to precipitate on the surface of CoCrMo under static conditions. The friction coefficient was greater in PBS containing physiologically relevant concentrations of fibrinogen as compared to PBS alone. 

Welders are daily exposed to various levels of welding fumes containing several metals. This exposure can lead to an increased risk for different health effects which serves as a driving force to develop new methods that generate less toxic fumes. The aim of this study was to explore the role of released metals for welding particle-induced toxicity and to test the hypothesis that a reduction of Cr(VI) in welding fumes results in less toxicity by comparing the welding fume particles of optimized Cr(VI)-reduced flux-cored wires (FCWs) to standard FCWs. The welding particles were thoroughly characterized, and toxicity (cell viability, DNA damage and inflammation) was assessed following exposure to welding particles as well as their released metal fraction using cultured human bronchial epithelial cells (HBEC-3kt, 5-100 mu g/mL) and human monocyte-derived macrophages (THP-1, 10-50 mu g/mL). The results showed that all Cr was released as Cr(VI) for welding particles generated using standard FCWs whereas only minor levels (< 3% of total Cr) were released from the newly developed FCWs. Furthermore, the new FCWs were considerably less cytotoxic and did not cause any DNA damage in the doses tested. For the standard FCWs, the Cr(VI) released in cell media seemed to explain a large part of the cytotoxicity and DNA damage. In contrast, all particles caused rather similar inflammatory effects suggesting different underlying mechanisms. Taken together, this study suggests a potential benefit of substituting standard FCWs with Cr(VI)-reduced wires to achieve less toxic welding fumes and thus reduced risks for welders.

Welding fumes have been found to be carcinogenic and stainless steel welders may be at higher risk due to increased formation of hexavalent chromium (Cr(VI)). The slag-shielded methods, identified to generate most airborne particles and Cr(VI), would potentially be most harmful. With ever-stricter limits set to protect workers, measures to minimize human exposure become crucial. Austenitic stainless steel flux-cored wires of 316L type have been developed with the aim to reduce the toxicity of the welding fume without compromised usability. Collected particles were compared with fumes formed using solid, metal-cored, and standard flux-cored wires. The size, morphology, and composition were characterized with scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS). Total metal concentrations and released amounts of metals (Cr, Cr(VI), Ni, Mn, Fe) were investigated after complete digestion in aqua regia and after incubation in phosphate buffered saline (PBS) by means of flame furnace atomic absorption spectroscopy (AAS), inductively coupled plasma mass spectroscopy (ICP-MS), and UV–vis spectroscopy. The cytotoxicity of the particles was assessed with the Alamar blue assay for cell viability using cultured human bronchial epithelial cells (HBEC-3kt). The findings correlate well with previous in vitro toxicity studies for standard and experimental wires. The new optimized 316L-type flux-cored wires showed improved weldability and generated less Cr(VI) in wt.-% than with solid wire. The respirable particles were confirmed to be less acute toxic in HBEC-3kt cells as compared to standard flux-cored wires. The highest cell viability (survival rate) was observed for the metal-cored wire.

Welding fumes have been found to be carcinogenic and stainless steel welders may be at higher risk due to increased formation of hexavalent chromium (Cr(VI)). The slag-shielded methods, identified to generate most airborne particles and Cr(VI), would potentially be most harmful. With ever-stricter limits set to protect workers, measures to minimize human exposure become crucial. Austenitic stainless steel flux-cored wires of 316L type have been developed with the aim to reduce the toxicity of the welding fume without compromised usability. Collected particles were compared with fumes formed using solid, metal-cored, and standard flux-cored wires. In part 1, the new wires were concluded to have improved weldability, to generate even less Cr(VI) in wt.-% than with solid wire and to be less acute toxic in cultured human bronchial epithelial cells as compared to standard flux-cored wires. In part 2, two additional institutes created fume emission datasheets for the same wires for correlation with the fume data obtained in part 1. The reported values showed large variations between the three laboratories, having a significant effect on the standard deviation. This is suggested to be the result of different welding parameters and various ways to collect and analyze the fume. More stringent specifications on parameter settings and fume collection would be required to increase the accuracy. This means that at present, it may not be possible to compare fume data on datasheets from two different wire producers and care should be taken in interpretation of values given in the available literature. Nevertheless, the laboratories confirmed the same trends for Cr(VI) as presented in part 1.

Welding fume particles are hazardous. Their toxicity likely depends on their composition and reactivity. This study aimed at exploring the role of sodium or other fluorides (NaF), which are intentionally added to flux-cored wire electrodes for stainless steel welding, on the solubility (in phosphate buffered saline) and toxicity of the generated welding fume particles. A multi-analytical particle characterization approach along with in-vitro cell assays was undertaken. The release of Cr(VI) and Mn from the particles was tested as a function of fluoride solution concentration. The welding fume particles containing NaF released significantly higher amounts of Cr (VI) compared with solid wire reference fumes, which was associated with increased cytotoxicity and genotoxicity in-vitro. No crystalline Na or potassium (K) containing chromates were observed. Cr(VI) was incorporated in an amorphous mixed oxide. Solution-added fluorides did not increase the solubility of Cr(VI), but contributed to a reduced Mn release from both solid and flux-cored wire fume particles and the reduction of Cr (VI) release from solid wire fume particles. Chemical speciation modeling suggested that metal fluoride complexes were not formed. The presence of NaF in the welding electrodes did not have any direct, but possibly an indirect, role in the Cr(VI) solubility of welding fumes.

Highly corrosion-resistant alloys are used in sensitive environments such as the human body and food environments. However, even tiny amounts of released metals from these surfaces could potentially cause adverse effects. It is hence important to study the biointerface between corrosion-resistant alloys and protein-rich environments. This licentiate thesis focused on the metal release processes for stainless steels and cobalt-chromium-molybdenum (CoCrMo) alloys in different protein-rich environments. It aimed at investigating the effect of protein displacement (Vroman effect), gamma irradiation, and friction on the metal release processes. Trace metal analysis was the main tool, combined with other solution analytical tools, electrochemical methods, and surface sensitive techniques.

The effect of gamma irradiation, of relevance for cancer radiotherapy, on metal release from CoCrMo and stainless steel 316L was investigated in Paper I. The effect was minor, however the released amount of metals increased after irradiation causing an enhanced surface passivation effect. Whether the displacement of surface proteins (Vroman effect) was playing a role on the metal release and corrosion processes of stainless steels 316L and 303, and of CoCrMo, was investigated in Papers II and III. A Vroman effect influencing the metal release could be observed for stainless steel 316L, but not for CoCrMo and stainless steel grade 303. However, the displacement of the smaller protein bovine serum albumin (BSA) from the surface by the larger protein fibrinogen (Fbn) was observed for both stainless steel grades. The Vroman effect also caused a higher corrosion susceptibility of stainless steel 303, probably due to a thicker layer or patches of adsorbed Fbn. Most probably, protein aggregation and precipitation caused an underestimation of the extent of metal release, especially in the case of CoCrMo. Protein aggregation and precipitation were significantly observed in all studies, especially for solutions with high protein concentrations (Papers II-IV). The effect of friction, by using different setups (stirring with physical contact and sliding in a pin-on-disk machine), on metal release from stainless steel 316L and CoCrMo was investigated in Papers II and IV. Friction induced an increased extent of metal release, increased protein aggregation and precipitation, and enhanced metal precipitation. A combined friction and complexation effect was observed for stainless steel 316L, resulting in an etching effect and relatively high amounts of released metals. Due to enhanced precipitation effects and the experimental setup, it is recommended to strongly consider protein aggregation and metal precipitation events in systems where this could be expected and where friction is present. Otherwise, there is a risk to strongly underestimate the extent of metal release in these protein-rich environments.

Background: Contact allergy to aluminium (Al) might pose a risk of false-positive readings of patch-test results when testing with Finn chambers. Objectives: To quantify the release of Al from empty Al Finn chambers, covered Finn Aqua chambers, and Al Finn chambers containing different baseline patch-test substances. Methods: Al Finn chambers of different conditions and with different patch-test substances were tested in artificial sweat and their Al release was analyzed by atomic absorption spectroscopy and inductively coupled plasma sector field mass spectrometry. Results: The amount of Al released from empty Finn chambers corresponded to a skin dose of 0.03%–0.5% Al chloride hexahydrate applied in plastic chambers. Although most patch-test substances reduced the release of Al from the Finn chambers due to covering the surface, some substances significantly increased the release of Al from the Finn chambers, most notable for Caine mix II 10% pet., Myroxylon pereirae 25% pet., and sodium tetrachloropalladate hydrate 3.0% pet. Conclusions: The release of Al from Finn chambers corresponds in some cases to clinically relevant concentrations of Al for Al-sensitized individuals.

Nickel (Ni)and cobalt (Co)are the most common metal allergens upon skin contact at occupational settings and during consumer handling of metals and alloys. A standardized test (EN, 1811)exists to assess Ni release from articles of metals and alloys in massive forms intended for direct and prolonged skin contact, but no corresponding test exists for other materials such as powders or massive forms of alloys placed on the market or to determine the release of Co, for which only limited data is available. Differences in Ni and Co release from massive forms of a range of common stainless steels and some high-alloyed grades compared to Ni and Co metals were therefore assessed in artificial sweat for 1 week at 30 °C according to EN 1811. A comparable modified test procedure was elaborated and used for powders and some selected massive alloys. All alloys investigated released significantly less amount of Ni (100–5000-fold)and Co (200–400,000-fold)compared with Ni and Co metal, respectively. Almost all alloys showed a lower bioaccessible concentration (0.007–6.8 wt% Ni and 0.00003–0.6 wt% Co)when compared to corresponding bulk alloy contents (0.1–53 wt% Ni, 0.02–65 wt% Co). Observed differences are, among other factors, related to differences in bulk composition and to surface oxide characteristics. For the powders, less Ni and Co were released per surface area, but more per mass, compared to the corresponding massive forms.