Chromium and cobalt in leather: A Danish market survey.

INTRODUCTION: Leather has been a significant source of chromium (Cr) allergy in Denmark since the 1990s. More recently, cobalt (Co) allergy has been identified in leather as a source of allergic contact dermatitis. OBJECTIVES: To measure Cr and Co levels in Danish leather goods. METHODS: A total of 87 leather samples were collected, all tanned in Europe. Handheld X-ray fluorescence (XRF) device was used to screen for the presence of Cr and Co. The 20 leather samples with the highest concentrations of Co and Co were tested using International Organization for Standardization (ISO)-standards. RESULTS: XRF analysis showed Cr in 78/87 (83.9%) samples and Co in 52/87 (59.7%), with average concentrations of 41 mg/kg (range: 0.0-77 mg/kg) and 0.22 mg/kg (range: 0.0-2.9 mg/kg), respectively. ISO 10195 and 17 075-1 testing identified Cr (VI) in 7 out of 20 samples (1.4; 0.3-4.2 mg/kg), while ISO 17072-1 detected Co in 6 of 20 samples, averaging 3.95 mg/kg (range: 0.22-7.9 mg/kg). CONCLUSION: Most leather samples contained Cr, which was expected, while Cr (VI) was detectable in seven out of twenty tested samples but only detected in one product above the regulatory limit of 3 mg/kg. A potentially significant concentration was found for Co.

Influence of Proteins and Building Direction on the Corrosion and Tribocorrosion of CoCrMo Fabricated by Laser Powder Bed Fusion.

Cobalt-chromium-molybdenum (CoCrMo) alloys are common wear-exposed biomedical alloys and are manufactured in multiple ways, increasingly using additive manufacturing processes such as laser powder bed fusion (LPBF). Here, we investigate the effect of proteins and the manufacturing process (wrought vs LPBF) and building orientation (LPBF-XY and XZ) on the corrosion, metal release, tribocorrosion, and surface oxide composition by means of electrochemical, mechanical, microscopic, diffractive, and spectroscopic methods. The study was conducted at pH 7.3 in 5 g/L NaCl and 5 mM 2-(N-morpholino) ethanesulfonic acid (MES) buffer, which was found to be necessary to avoid metal phosphate and metal-protein aggregate precipitation. The effect of 10 g/L bovine serum albumin (BSA) and 2.5 g/L fibrinogen (Fbn) was studied. BSA and Fbn strongly enhanced the release of Co, Cr, and Mo and slightly enhanced the corrosion (still in the passive domain) for all CoCrMo alloys and most for LPBF-XZ, followed by LPBF-XY and the wrought CoCrMo. BSA and Fbn, most pronounced when combined, significantly decreased the coefficient of friction due to lubrication, the wear track width and severity of the wear mechanism, and the tribocorrosion for all alloys, with no clear effect of the manufacturing type. The wear track area was significantly more oxidized than the area outside of the wear track. In the reference solution without proteins, a strong Mo oxidation in the wear track surface oxide was indicative of a pH decrease and cell separation of the anodic and cathodic areas. This effect was absent in the presence of the proteins.

Serum Albumin Aggregation Facilitated by Cobalt and Chromium Metal Ions.

The interaction of serum proteins with cobalt (Co) and chromium (Cr) ions is poorly understood, but it is suspected to result in protein aggregation, which may alter the corrosion process of biomedical CoCr alloys or result in adverse health effects. Here, we study the aggregation ability and mechanism of bovine serum albumin (BSA) induced or accelerated by aqueous Co(II) and Cr(III) ions. The metal salts were selected by chemical speciation modeling, and they did not affect the pH or precipitate under simulated physiological conditions (150 mM NaCl and pH 7.3). The counterion of Cr(III) influenced the binding to BSA only at physiologically irrelevant low ionic strength. This study used a variety of spectroscopic and light scattering methods. It was determined that both metal ions and an equimolar mixture of metal ions have the potential to induce protein aggregation. Melting curves collected by circular dichroism spectroscopy indicate that Co(II) significantly reduced BSA's melting temperature when compared with Cr(III) or an equimolar mixture of Co(II) and Cr(III), both of which increased the melting temperature of BSA. The metal ions in solution preferentially interacted with BSA, resulting in the depletion of metal ions from the surrounding protein-free solution. Finally, this study suggests that the likely mechanism for Co(II)- and Cr(III)-induced BSA aggregation is salt bridging between protein molecules.

The ability of sweat and buffer solutions to reduce hexavalent chromium of relevance for leather extraction.

The European Union restricted the amount of hexavalent chromium (Cr(VI)) in leather in 2015, but skin allergy cases due to Cr-tanned leather are not declining. Standardized extraction methods have been criticized to both over- and underestimate the expected amount of bioavailable Cr(VI) in leather. This study aims to evaluate the ability of four extraction solutions to reduce or preserve Cr(VI): artificial sweat solutions (ASWs) of pH 4.7, 6.5, and 8.0, and phosphate buffer (PB) of pH 8.0. This was investigated by incubating each solution with added Cr(VI) as a function of time, and then measuring the recovered Cr(VI). All solutions, especially PB, preserved Cr(VI) for 24 h. These solutions were also pre-exposed to Cr-free vegetable-tanned leather (VTL) before incubation with Cr(VI). Released vegetable tannin species strongly reduced Cr(VI), with up to 4000 µg/L added Cr(VI) reduced in all solutions after 24 h. However, after 1 h, Cr(VI) was still detectable in extraction solutions at pH 6.5 and above. The reduction of Cr(VI) in relevant extraction solutions is hence a process dependent on time, pH, and the presence of co-released leather species. All extraction solutions, but least PB, have the potential to underestimate any Cr(VI) present on the surface of leather.

Skin permeation of nickel, cobalt and chromium salts in ex vivo human skin, visualized using mass spectrometry imaging.

Skin permeation and distribution of three of the most common skin sensitizers was investigated using a previously developed animal-free exposure method combined with imaging mass spectrometry. Nickel, cobalt, and chromium (III) salts were dissolved in a buffer and exposed to human skin ex vivo, to be analyzed using time of flight secondary ion mass spectrometry (ToF-SIMS). Our findings demonstrate that metal haptens mainly accumulated in the stratum corneum, however all three metal sensitizers could also be detected in the epidermis. Cobalt and chromium (III) species penetrated into the epidermis to a larger extent than nickel species. The degree of penetration into the epidermis is suggested to be affected by the sensitization potency of the metal salts, as well as their speciation, i.e. the amount of the respective metal present in the solution as bioaccessible and solubilised ions. Our method provided permeation profiles in human skin for known sensitizers, on a level of detail that is not possible to achieve by other means. The findings show that the permeation profiles are different, despite these sensitizers being all metal ions and common causes of contact allergy. Studying skin uptake by only considering penetration through the skin might therefore not give accurate results.

Genotoxicity and inflammatory potential of stainless steel welding fume particles: an in vitro study on standard vs Cr(VI)-reduced flux-cored wires and the role of released metals.

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 µg/mL) and human monocyte-derived macrophages (THP-1, 10-50 µg/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.

Analytical survey of tattoo inks-A chemical and legal perspective with focus on sensitizing substances.

BACKGROUND: Tattoo inks have been reported to elicit allergic contact dermatitis. OBJECTIVES: To investigate the labels and the contents of metals and pigments in tattoo inks, considering restrictions within the European Union. METHODS: Seventy-three tattoo inks currently available on the market, either bought or donated (already used), were investigated for trace metals and pigments by inductively coupled plasma mass spectrometry and by matrix-assisted laser desorption/ionization time of flight tandem mass spectrometry. RESULTS: Ninety-three percent of the bought tattoo inks violated European, legal requirements on labeling. Fifty percent of the tattoo inks declared at least one pigment ingredient incorrectly. Sixty-one percent of the inks contained pigments of concern, especially red inks. Iron, aluminium, titanium, and copper (most in green/blue inks) were the main metals detected in the inks. The level of metal impurities exceeded current restriction limits in only a few cases. Total chromium (0.35-139 µg/g) and nickel (0.1-41 µg/g) were found in almost all samples. The levels of iron, chromium, manganese, cobalt, nickel, zinc, lead, and arsenic were found to covary significantly. CONCLUSIONS: To prevent contact allergy and toxic reactions among users it is important for tattoo ink manufacturers to follow the regulations and decrease nickel and chromium impurities.

Using chemical speciation modelling to discuss variations in patch test reactions to different aluminium and chromium salts.

BACKGROUND: Allergic contact dermatitis to metals is diagnosed by applying a metal salt in a patch test. The bioavailability of the metal salt might depend on the choice of metal salt, the concentration, sweat composition, and pH. OBJECTIVES: The main purpose of this study was to apply chemical speciation modelling, which is based on experimentally derived input data and calculates the concentrations of chemical forms (species) in solutions, to reproduce and discuss clinical patch test results of aluminium and chromium. METHODS: Joint Expert Speciation System (JESS), Hydra/Medusa, and Visual MINTEQ were employed to study the bioavailable fraction and chemical form of clinically applied aluminium and chromium salts as a function of salt type, applied concentration, sweat composition, and pH. RESULTS: Investigated aluminium and chromium salts can have a very low bioavailability with a large dependency on sweat composition, pH, metal salt, and concentration. Both aluminium and chromium ions could shift the pH towards acidic or basic values based on their chemical form. CONCLUSIONS: Reported seasonal and interpatient variability in positive reactions to aluminium is likely related to sweat pH and composition. Potassium dichromate increases the pH, whereas aluminium and trivalent chromium chloride strongly decrease the pH, possibly increasing skin diffusion.

Patch testing with aluminium Finn Chambers could give false-positive reactions in patients with contact allergy to aluminium.

BACKGROUND: Earlier laboratory studies have shown that sodium tetrachloropalladate, Myroxylon pereirae, caine mix II, and palladium chloride trigger the release of aluminium (Al) from Finn Chambers (FC). OBJECTIVES: To investigate whether aluminium realease from FC could influence the diagnostic outcome of patch testing with FC. METHOD: A retrospective analysis of patch test results from 2010 to 2019 was performed. A two-sided Fisher's exact test was used to calculate any overrepresentation of contact allergy to Al among patients with positive reactions to sodium tetrachloropalladate, Myroxylon pereirae, caine mix II, and palladium chloride. RESULTS: A total of 5446 patients had been tested with FC during the study period. There was a significant overrepresentation of contact allergy to Al among patients with positive reactions to sodium tetrachloropalladate, Myroxylon pereirae, caine mix II, and palladium chloride. Patients with a strong Al allergy had significantly higher amounts of concomitant reactions to sodium tetrachloropalladate, Myroxylon pereirae, caine mix II, and palladium chloride compared to patients with weak Al allergy. These results were not seen for patients tested with Finn Chambers AQUA. CONCLUSION: In patients with contact allergy to Al, patch testing with Finn chambers could give false-positive reactions to sodium tetrachloropalladate, Myroxylon pereirae, caine mix II, and palladium chloride.

Detection of gold cysteine thiolate complexes on gold nanoparticles with time-of-flight secondary ion mass spectrometry.

Gold (Au) nanoparticles (NPs) are widely used in nanomedical applications as a carrier for molecules designed for different functionalities. Previous findings suggested that biological molecules, including amino acids, could contribute to the dissolution of Au NPs in physiological environments and that this phenomenon was size-dependent. We, therefore, investigated the interactions of L-cysteine with 5-nm Au NPs by means of time-of-flight secondary ion mass spectrometry (ToF-SIMS). This was achieved by loading Au NPs on a clean aluminum (Al) foil and immersing it in an aqueous solution containing L-cysteine. Upon rinsing off the excessive cysteine molecules, ToF-SIMS confirmed the formation of gold cysteine thiolate via the detection of not only the Au-S bond but also the hydrogenated gold cysteine thiolate molecular ion. The presence of NaCl or a 2-(N-morpholino)ethanesulfonic acid buffer disabled the detection of Au NPs on the Al foil. The detection of larger (50-nm) Au NPs was possible but resulted in weaker cysteine and gold signals, and no detected gold cysteine thiolate signals. Nano-gold specific adsorption of L-cysteine was also demonstrated by cyclic voltammetry using paraffine-impregnated graphite electrodes with deposited Au NPs. We demonstrate that the superior chemical selectivity and surface sensitivity of ToF-SIMS, via detection of elemental and molecular species, provide a unique ability to identify the adsorption of cysteine and formation of gold-cysteine bonds on Au NPs.

Quantification of aluminium release from Finn chambers under different in vitro test conditions of relevance for patch testing.

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.

Bioaccessibility of Nickel and Cobalt Released from Occupationally Relevant Alloy and Metal Powders at Simulated Human Exposure Scenarios.

Nickel (Ni) and cobalt (Co) release from chromium-alloy powders (different stainless steels and a nickel-based Inconel alloy) compared with Ni and Co metal powders was investigated at simulated human exposure scenarios (ingestion, skin contact, and inhalation) between 2 and 168 h. All investigated powders consisted of particles sized within the respirable range. The powder particles and their surface reactivity were studied by means of nitrogen adsorption and electrochemical, spectroscopic (X-ray photoelectron spectroscopy and atomic absorption spectroscopy), light scattering, and microscopic techniques. The release of both Ni and Co was highest in the acidic and complexing fluids simulating the gastric environment and an inhalation scenario of small powders (artificial lysosomal fluid). Relatively high corrosion resistance and lower levels of released Ni and Co were observed in all fluids for all alloy powders compared with the corresponding pure metals. The extent of released metals was low for powders with a passive surface oxide. This study strongly emphasizes the importance of considering alloying effects in toxicological classification and/or regulation of Ni and Co in alloys and metals.

Metals in used and unused metalworking fluids: X-ray fluorescence spectrometry as a screening test.

BACKGROUND: Exposure to metalworking fluids (MWFs) is a well-known cause of occupational contact dermatitis. OBJECTIVES: We aimed to (1) determine the amount of nickel, chromium, and cobalt in large samples of used and unused MWFs collected from metalworking plants in Denmark, and (2) evaluate a handheld x-ray fluorescence (XRF) device as a screening instrument for metals in MWFs. METHODS: A handheld XRF device was used to screen for metals in MWFs. All samples were also analyzed for concentrations of nickel, chromium, and cobalt using graphite furnace atomic absorption spectroscopy (GFAAS). RESULTS: GFAAS analysis showed that 13 of 80 samples (16.3%) contained >1 mg/kg (ppm) nickel (range: 6.4-17.7 mg/kg), 3 of 80 (3.8%) contained >1 (range: 1.4-3.1) mg/kg chromium, and 1 of 80 (1.3%) contained 1.3 mg/kg cobalt. XRF-screening detected nickel in eight samples (range: 2.5-15.5 mg/kg), but only one sample with 3.0 (±0.5) mg/kg was found subsequently to contain 9.9 (0.02) mg/kg nickel by GFAAS. Although no chromium was found by XRF analysis, cobalt was found in two samples with 6 (±1.5) mg/kg and 5 (±1.5) mg/kg, subsequently found to contain 0.1 (±0.01) mg/kg and 0.08 (±0.01) mg/kg by GFAAS. Similar concentrations of nickel were found in used (N = 6, range: 6.4-17.7 mg/kg) and unused MWFs (N = 7, range: 9.1-17.3 mg/kg). CONCLUSION: Considerable levels of nickel, chromium, and cobalt were found in some used and unused MWFs indicating that these might represent a source of metal allergy. The XRF device is a poor screening test for these metals in MWFs.

Release of hexavalent chromium from cement collected in Honduras and Sweden.

Hexavalent chromium in cement 5-8 mg/kg hexavalent chromium (Cr(VI)) was found in Honduran cement samples, which was slightly higher than in Swedish samples. Variable amounts of Cr(VI) (0.4 and 4.7 mg/kg) found in Swedish cement samples that were older than 1 year. There are still many countries that do not have a compulsory reduction of Cr(VI) in cement. Several measures can be employed to reduce risks related to Cr(VI) in cement.

Comparison of different surface disinfection treatments of drinking water facilities from a corrosion and environmental perspective.

Surface disinfection of water facilities such as water wells requires measures that can remove pathogens from the walls to ensure a high drinking water quality, but many of these measures might increase corrosion of the contact surfaces (often highly pure steel) and affect the environment negatively due to disinfectant-contaminated waste sludge and wastewater. Today, most treatments worldwide are based on hypochlorites. We investigated the extent of corrosion during treatments of steel at relevant conditions of ozone, sodium, and calcium hypochlorite for drinking water preparation, utilizing weight loss, electrochemical, solution analytical, and surface analytical methods. The ozone treatment caused significantly less corrosion as compared with sodium or calcium hypochlorite with 150-250 mg/L active chlorine. Hypochlorite or other chlorine-containing compounds were trapped in corrosion products after the surface disinfection treatment with hypochlorite, and this risked influencing subsequent corrosion after the surface disinfection treatment. A life cycle impact assessment suggested ozone treatment to have the lowest negative effects on human health, ecosystems, and resources. Calcium hypochlorite showed the highest negative environmental impact due to its production phase. Our study suggests that ozone surface disinfection treatments are preferable as compared with hypochlorite treatments from corrosion, economic, and environmental perspectives.

High variability in toxicity of welding fume nanoparticles from stainless steel in lung cells and reporter cell lines: the role of particle reactivity and solubility.

Millions of people in the world perform welding as their primary occupation resulting in exposure to metal-containing nanoparticles in the fumes generated. Even though health effects including airway diseases are well-known, there is currently a lack of studies investigating how different welding set-ups and conditions affect the toxicity of generated nanoparticles of the welding fume. The aim of this study was to investigate the toxicity of nine types of welding fume particles generated via active gas shielded metal arc welding (GMAW) of chromium-containing stainless steel under different conditions and, furthermore, to correlate the toxicity to the particle characteristics. Toxicological endpoints investigated were generation of reactive oxygen species (ROS), cytotoxicity, genotoxicity and activation of ToxTracker reporter cell lines. The results clearly underline that the choice of filler material has a large influence on the toxic potential. Fume particles generated by welding with the tested flux-cored wire (FCW) were found to be more cytotoxic compared to particles generated by welding with solid wire or metal-cored wire (MCW). FCW fume particles were also the most potent in causing ROS and DNA damage and they furthermore activated reporters related to DNA double- strand breaks and p53 signaling. Interestingly, the FCW fume particles were the most soluble in PBS, releasing more chromium in the hexavalent form and manganese compared to the other fumes. These results emphasize the importance of solubility of different metal constituents of the fume particles, rather than the total metal content, for their acute toxic potential.

Bioaccessibility of nickel and cobalt in powders and massive forms of stainless steel, nickel- or cobalt-based alloys, and nickel and cobalt metals in artificial sweat.

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.

Chromium(III), chromium(VI) and cobalt release from leathers produced in Nicaragua.

BACKGROUND: Leather exposure has been associated with chromium (Cr) and cobalt (Co) contact dermatitis. Cr(VI) in leather is now restricted to <3 mg/kg in the EU. Cr(III) is not restricted. OBJECTIVES: To analyse 29 differently coloured Cr-tanned leather samples from two Nicaraguan tanneries, and to compare their release of Cr, Cr(VI) and Co with that of leathers produced in Europe. METHODS: Cr, Cr(VI) and Co were extracted in phosphate buffer for 3 hours at 25°C according to EN ISO 17075. Atomic absorption spectroscopy and spectrophotometry were used for detection of the metals in phosphate buffer. RESULTS: There was no difference in total Cr or Cr(VI) release between European and Nicaraguan leathers. There was no association between Cr(VI) and total Cr release. Co was released primarily from leathers of one tannery. Cr(III) was released in significantly higher amounts than Cr(VI). CONCLUSIONS: Future investigations and regulations should focus on Cr(III) and Co as well as on Cr(VI).