Gunilla Herting

A Comparison of Release Rates of Cr, Ni, and Fe from Stainless Steel Alloys and the Pure Metals Exposed to Simulated Rain Events

With increasing environmental awareness, the desire to protect human beings and the environment from adverse effects induced by dispersed metals has become an issue of great concern and interest. New policies, such as REACH (Registration, Evaluation, Authorisation and Restriction of Chemicals) within the European Community, have been implemented to reduce hazards posed by the use of chemicals on producers and downstream users. The generation of exposure assessment data and relevant test procedures able to simulate realistic scenarios are essential in such legislative actions. This doctoral study was initiated to fill knowledge gaps related to the metal release process of stainless steels. A wide range of stainless steel grades, fourteen in total, were investigated. They cover a very broad range of applications, and the focus in the thesis was to simulate a few selected exposure scenarios: precipitation, the human body and food intake. Comparisons were made between metal release from stainless steel alloys and the pure metals that constitute each stainless steel in order to explore the differences between alloys and pure metals, and to provide quantitative data on metal release rates of different alloy constituents. Because of similar surface properties between stainless steel and pure chromium, this metal exhibits similar release rates, whereas iron and nickel exhibit significantly lower release rates as alloy components than as pure metals. Detailed studies were also performed to elucidate possible relations between metal release and steel surface properties. Key parameters turned out to be chromium enrichment of the self-passivating surface film, surface roughness, the electrochemically active surface area and the microstructure of the steel substrate. The degree of metal release increased with decreasing chromium content in the surface oxide, increasing surface roughness, and increasing presence of inhomogeneities in the bulk matrix. More detailed studies were initiated to possibly correlate the nucleation of metastable pits and the extent of metal release. Evidence was given that metastable pits exist even when the stainless steel is passive, and may cause extremely short-lived bursts of released metal before the surface film repassivates again.

Adsorption and protein-induced metal release from chromium metal and stainless steel.

A research effort is undertaken to understand the mechanism of metal release from, e.g., inhaled metal particles or metal implants in the presence of proteins. The effect of protein adsorption on the metal release process from oxidized chromium metal surfaces and stainless steel surfaces was therefore examined by quartz crystal microbalance with energy dissipation monitoring (QCM-D) and graphite furnace atomic absorption spectroscopy (GFAAS). Differently charged and sized proteins, relevant for the inhalation and dermal exposure route were chosen including human and bovine serum albumin (HSA, BSA), mucin (BSM), and lysozyme (LYS). The results show that all proteins have high affinities for chromium and stainless steel (AISI 316) when deposited from solutions at pH 4 and at pH 7.4 where the protein adsorbed amount was very similar. Adsorption of albumin and mucin was substantially higher at pH 4 compared to pH 7.4 with approximately monolayer coverage at pH 7.4, whereas lysozyme adsorbed in multilayers at both investigated pH. The protein-surface interaction was strong since proteins were irreversibly adsorbed with respect to rinsing. Due to the passive nature of chromium and stainless steel (AISI 316) surfaces, very low metal release concentrations from the QCM metal surfaces in the presence of proteins were obtained on the time scale of the adsorption experiment. Therefore, metal release studies from massive metal sheets in contact with protein solutions were carried out in parallel. The presence of proteins increased the extent of metals released for chromium metal and stainless steel grades of different microstructure and alloy content, all with passive chromium(III)-rich surface oxides, such as QCM (AISI 316), ferritic (AISI 430), austentic (AISI 304, 316L), and duplex (LDX 2205).

Metal release rate from AISI 316L stainless steel and pure Fe, Cr and Ni into a synthetic biological medium- a comparison

Metal release rates from stainless steel grade 316L were investigated in artificial lysosomal fluid (ALF), simulating a human inflammatory cell response. The main focus was placed on release rates of main alloying elements using graphite furnace atomic absorption spectroscopy, and changes in surface oxide composition by means of X-ray photoelectron spectroscopy. To emphasise that alloys and pure metals possess totally different intrinsic properties, comparative studies were performed on the pure alloying constituents: iron, nickel and chromium. Significant differences in release rates were observed due to the presence of a passive surface film on stainless steel. Iron and nickel were released at rates more than 300 times lower from the 316L alloy compared with the pure metals whereas the release rate of chromium was similar. Iron was preferentially released compared with nickel and chromium. Immersion in ALF resulted in the gradual enrichment of chromium in the surface film, a small increase of nickel, and the reduction of oxidized iron with decreasing release rates of alloy constituents as a result. As expected, released metals from stainless steel grade 316L were neither in proportion to the bulk alloy composition nor to the surface film composition.

Atmospheric corrosion of brass in outdoor applications: Patina evolution, metal release and aesthetic appearance at urban exposure conditions

Short (days, weeks) and long-term (months, years) non-sheltered field exposures of brass (15, and 20 wt.% Zn) and copper sheet have been conducted in three European cities (Milan, Stockholm, Madrid) to generate an in-depth time-dependent understanding of patina evolution, corrosion rates, aesthetic appearance, metal release and degree of dezincification in relation to detailed bulk and surface characteristics prior to exposure. This has been accomplished by using a multitude of surface and bulk analytical tools, chemical analysis and colorimetric investigations. Small differences in surface finish and local variations in nobility observed for the non-exposed brass alloys resulted in slight differences in corrosion initiation. Despite different kinetic behaviour and relative surface distributions of zinc- and copper-rich patina constituents, similar phases were identified with copper-rich phases rapidly dominating the outermost patina layer in Milan, compared to Madrid and Stockholm showing both copper- and zinc-rich phases. As a consequence of differences in surface coverage of copper- and zinc-rich corrosion products at the different sites, the release ratios of copper to zinc varied concordantly. The released amount of zinc to copper (Zn/Cu) was for both alloys and test sites always higher compared to the bulk composition showing a preferential release of zinc. The amount of released copper from the brass alloys was on an average 30-40% lower compared to copper sheet at all test sites investigated. Significantly lower annual total release rates of copper and zinc compared with annual corrosion rates were evident for both brass alloys at all sites.

Corrosion and runoff rates of Cu and three Cu-alloys in marine environments with increasing chloride deposition rate

Bare copper sheet and three commercial Cu-based alloys, Cu15Zn, Cu4Sn and Cu5Al5Zn, have been exposed to four test sites in Brest, France, with strongly varying chloride deposition rates. The corrosion rates of all four materials decrease continuously with distance from the coast, i.e. with decreasing chloride load, and in the following order: Cu4Sn>Cu sheet>Cu15Zn>Cu5Al5Zn. The patina on all materials was composed of two main layers, Cu2O as the inner layer and Cu2(OH)3Cl as the outer layer, and with a discontinuous presence of CuCl in between. Additional minor patina constituents are SnO2 (Cu4Sn), Zn5(OH)6(CO3)2 (Cu15Zn and Cu5Al5Zn) and Zn6Al2(OH)16CO3·4H2O/Zn2Al(OH)6Cl·2H2O/Zn5Cl2(OH)8·H2O and Al2O3 (Cu5Al5Zn). The observed Zn- and Zn/Al-containing corrosion products might be important factors for the lower sensitivity of Cu15Zn and Cu5Al5Zn against chloride-induced atmospheric corrosion compared with Cu sheet and Cu4Sn. Decreasing corrosion rates with exposure time were observed for all materials and chloride loads and attributed to an improved adherence with time of the outer patina to the underlying inner oxide. Flaking of the outer patina layer was mainly observed on Cu4Sn and Cu sheet and associated with the gradual transformation of CuCl to Cu2(OH)3Cl of larger volume. After three years only Cu5Al5Zn remains lustrous because of a patina compared with the other materials that appeared brownish-reddish. Significantly lower release rates of metals compared with corresponding corrosion rates were observed for all materials. Very similar release rates of copper from all four materials were observed during the fifth year of marine exposure due to an outer surface patina that with time revealed similar constituents and solubility properties.

New UK nickel-plated steel coins constitute an increased allergy and eczema risk.

Nickel‐plated steel coins have recently been introduced in the United Kingdom.

Critical Review: Copper Runoff from Outdoor Copper Surfaces at Atmospheric Conditions

This review on copper runoff dispersed from unsheltered naturally patinated copper used for roofing and facades summarizes and discusses influencing factors, available literature, and predictive models, and the importance of fate and speciation for environmental risk assessment. Copper runoff from outdoor surfaces is predominantly governed by electrochemical and chemical reactions and is highly dependent on given exposure conditions (size, inclination, geometry, degree of sheltering, and orientation), surface parameters (age, patina composition, and thickness), and site-specific environmental conditions (gaseous pollutants, chlorides, rainfall characteristics (amount, intensity, pH), wind direction, temperature, time of wetness, season). The corrosion rate cannot be used to assess the runoff rate. The extent of released copper varies largely between different rain events and is related to dry and wet periods, dry deposition prior to the rain event and prevailing rain and patina characteristics. Interpretation and use of copper runoff data for environmental risk assessment and management need therefore to consider site-specific factors and focus on average data of long-term studies (several years). Risk assessments require furthermore that changes in copper speciation, bioavailability aspects, and potential irreversible retention on solid surfaces are considered, factors that determine the environmental fate of copper runoff from outdoor surfaces.

Corrosion-induced release of the main alloying constituents of manganese-chromium stainless steels in different media

The main focus of this paper is the assessment of release rates of chromium, nickel, iron and manganese from manganese-chromium stainless steel grades of low nickel content. The manganese content varied between 9.7 and 1.5 wt% and the corresponding nickel content between 1 and 5 wt%. All grades were exposed to artificial rain and two were immersed in a synthetic body fluid of similar pH but of different composition and exposure conditions. Surface compositional studies were performed using X-ray photoelectron spectroscopy (XPS) in parallel to correlate the metal release process with changes in surface oxide properties. All grades, independent of media, revealed a time-dependent metal release process with a preferential low release of iron and manganese compared to nickel and chromium while the chromium content of the surface oxide increased slightly. Manganese was detected in the surface oxide of all grades, except the grade of the lowest manganese bulk content. No nickel was observed in the outermost surface oxide. Stainless steel grades of the lowest chromium content (approximately 16 wt%) and highest manganese content (approximately 7-9 wt%), released the highest quantity of alloy constituents in total, and vice versa. No correlation was observed between the release rate of manganese and the alloy composition. Released main alloy constituents were neither proportional to the bulk alloy composition nor to the surface oxide composition.

Corrosion induced metal release from copper based alloys compared to their pure elements

Abstract Despite numerous studies on atmospheric corrosion of copper and copper based alloys, the corrosion induced release processes of individual alloy constituents suffer from significant knowledge gaps. This investigation comprises metal release rate measurements of copper, zinc and tin from some copper based alloys including brass (20 wt-%Zn) and bronze (6 wt-%Sn), and their pure alloying metals, copper, zinc and tin. Data have been generated during a 2·5 year urban field exposure in Stockholm, Sweden and parallel laboratory investigations in a specially designed rain chamber using artificial rain. Brass shows significantly lower annual release rates of both copper and zinc compared to pure metal sheets of its alloy constituents. Zinc is preferentially released compared to copper. Dezincification of brass occurs both at field and laboratory conditions, a process influenced by rain characteristics. Alloying with tin does not largely reduce the release rate of copper from bronze compared to pure copper. No measurable amount of tin is released from the bronze surface.

Inter-laboratory validation of bioaccessibility testing for metals

Bioelution assays are fast, simple alternatives to in vivo testing. In this study, the intra- and inter-laboratory variability in bioaccessibility data generated by bioelution tests were evaluated in synthetic fluids relevant to oral, inhalation, and dermal exposure. Using one defined protocol, five laboratories measured metal release from cobalt oxide, cobalt powder, copper concentrate, Inconel alloy, leaded brass alloy, and nickel sulfate hexahydrate. Standard deviations of repeatability (sr) and reproducibility (sR) were used to evaluate the intra- and inter-laboratory variability, respectively. Examination of the sR:sr ratios demonstrated that, while gastric and lysosomal fluids had reasonably good reproducibility, other fluids did not show as good concordance between laboratories. Relative standard deviation (RSD) analysis showed more favorable reproducibility outcomes for some data sets; overall results varied more between- than within-laboratories. RSD analysis of sr showed good within-laboratory variability for all conditions except some metals in interstitial fluid. In general, these findings indicate that absolute bioaccessibility results in some biological fluids may vary between different laboratories. However, for most applications, measures of relative bioaccessibility are needed, diminishing the requirement for high inter-laboratory reproducibility in absolute metal releases. The inter-laboratory exercise suggests that the degrees of freedom within the protocol need to be addressed.