Change search
ReferencesLink to record
Permanent link

Direct link
Adsorption and protein-induced metal release from chromium metal and stainless steel
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry (closed 20110630).
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.ORCID iD: 0000-0003-2145-3650
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.ORCID iD: 0000-0002-2123-2201
Show others and affiliations
2012 (English)In: Journal of Colloid and Interface Science, ISSN 0021-9797, E-ISSN 1095-7103, Vol. 366, no 1, 155-164 p.Article in journal (Refereed) Published
Abstract [en]

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).

Place, publisher, year, edition, pages
2012. Vol. 366, no 1, 155-164 p.
Keyword [en]
Chromium, Protein adsorption, Metal release, Stainless steel, Lysozyme, Albumin, Mucin
National Category
Corrosion Engineering
URN: urn:nbn:se:kth:diva-53387DOI: 10.1016/j.jcis.2011.09.068ISI: 000297385900023ScopusID: 2-s2.0-80655124456OAI: diva2:470417

QC 20111229

Available from: 2011-12-29 Created: 2011-12-28 Last updated: 2012-11-26Bibliographically approved
In thesis
1. Stainless Steel in Biological Environments – Relation between Material Characteristics, Surface Chemistry and Toxicity
Open this publication in new window or tab >>Stainless Steel in Biological Environments – Relation between Material Characteristics, Surface Chemistry and Toxicity
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Triggered by the regulatory need of the industry to demonstrate safe use of their alloy products from an environmental and health perspective, and by the significant lack of metal release data and its correlation to material and surface characteristics for iron- and chromium-based alloys, a highly interdisciplinary in-depth research effort was undertaken to assess the relation between material/surface characteristics and toxicity with main emphasis on stainless steel alloys. This thesis focuses predominantly on studies made on AISI 316L both as massive sheet and as powder particles, but includes also results for other stainless steel grades and reference metals and metal oxides.


The work comprises multi-analytical bulk and surface characterizations combined with particle characterizations and corrosion investigations, all correlated with in-depth kinetic metal release (bioaccessibility) studies as a function of route of manufacture, powder particle characteristics, surface finish, stainless steel grade, solution composition, pH, acidity and complexation capacity, as well as the presence of proteins. Speciation (chemical form) measurements were in addition conducted of released chromium, and of metal species in the surface oxide. Protein interactions were investigated in terms of adsorption, protein-metal complexation both at the surface and in solution, and the relative strength of protein-stainless steel surface interaction was addressed. In vitro and in vivo toxicological studies were conducted for the same inert-gas-atomized 316L powder sized < 4µm.


Bulk and surface oxide properties, such as phase, structure, morphology, chemical and electrochemical stability, protein-surface interactions, bioavailability of released metals, were all clearly evident to largely influence the metal release process and any induced toxicity. The route of manufacture was shown to strongly influence the bulk and surface oxide characteristics of stainless steel powders, hence also their electrochemical and catalytic properties, as well as the release/dissolution of metals from the powders (Papers VIII, XIII, XIV-XVII). The release of metals from both stainless steel sheets and powders was in general low compared to pure iron or nickel metal, and highly dependent on bulk and surface characteristics, the composition, complexation capacity and buffering capacity (and pH) of the solution, as well as on many experimental factors including time and sonication (Papers VI, VIII, XI, and XVII).


Surface-protein interactions strongly enhanced the release of alloy constituents (Papers IX, XI, and XVII). Iron was preferentially released (manganese in the case of inert-gas-atomized stainless steel powders) (Papers VIII, XI, and XVII). Protein-stainless steel surface interactions were most probably governed by chemisorption at given experimental conditions (Papers XI-XII). A strong protein-adsorption was evident for all stainless steel surfaces investigated, independent of protein charge, size or structure (Paper IX). Protein-metal complexes were formed both at the surface and in solution (Papers X-XII). Differences in protein charge and type resulted in varying degrees of interaction with differences in the extent of enhanced metal release as a consequence (Papers XI-XII). The inert-gas-atomized stainless steel powder sized <4 µm induced neither any significant increase of lysis of erythrocytes (rupture of red blood cells) nor any cytotoxicity, but resulted in a slight DNA damage in in vitro toxicity measurements (Paper VI). No adverse effects were however observed in an in vivo 28-day repeated-dose inhalation study on rats using the same powder (Paper VII).


The most important bulk, surface, particle, and experimental factors governing the bioaccessibility properties of stainless steel were identified and mechanistically elucidated. Detailed knowledge of all factors is essential for accurate hazard or risk assessment of metal alloys and enables read-across possibilities with materials of the same or similar characteristics. However, in cases where data is different from known systems for one factor or more, bioaccessibility data should be generated before any risk assessment is made.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2012. XIV, 38 p.
Trita-CHE-Report, ISSN 1654-1081 ; 2012:57
National Category
Other Chemistry Topics
urn:nbn:se:kth:diva-105521 (URN)978-91-7501-521-7 (ISBN)
Public defence
2012-12-14, F3, Lindstedtsvägen 26, KTH, Stockholm, 10:00 (English)

QC 20121126

Available from: 2012-11-26 Created: 2012-11-22 Last updated: 2012-11-26Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full textScopus

Search in DiVA

By author/editor
Lundin, MariaHedberg, YolandaHerting, GunillaThormann, EsbenBlomberg, EvaOdnevall Wallinder, Inger
By organisation
Nuclear Chemistry (closed 20110630)Surface and Corrosion Science
In the same journal
Journal of Colloid and Interface Science
Corrosion Engineering

Search outside of DiVA

GoogleGoogle Scholar
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

Altmetric score

Total: 95 hits
ReferencesLink to record
Permanent link

Direct link