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Metal Particles – Hazard or Risk? Elaboration and Implementation of a Research Strategy from a Surface and Corrosion Perspective
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Corrosion Science. (Division of surface and corrosion science)
2009 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Do metal particles (including particles of pure metals, alloys, metal oxides and compounds) pose a hazard or risk to human health? In the light of this question, this thesis summarizes results from research conducted on metal particles, and describes the elaboration and implementation of an in vitro test methodology to study metal release from particles through corrosion and dissolution processes in synthetic biological media relevant for human exposure through inhalation/ingestion and dermal contact.

Bioaccessible metals are defined as the pool of released metals from particles that potentially could be made available for absorption by humans or other organisms. Studies of bioaccessible metals from different metal particles within this thesis have shown that the metal release process is influenced by material properties, particle specific properties, size distribution, surface area and morphology, as well as the chemistry of synthetic biological test media simulating various human exposure scenarios. The presence of metal particles in proximity to humans and the fact that metals can be released from particles to a varying extent is the hazard referred to in the title.

The bioavailable metal fraction of the released metals (the fraction available for uptake/absorption by humans through different exposure routes) is usually significantly smaller than the bioaccessible pool of released metals, and is largely related to the chemical form and state of oxidation of the released metals. Chemical speciation measurements of released chromium for instance revealed chromium to be complexed to its non-available form in simulated lung fluids. Such measurements provide an indirect measure of the potential risk for adverse health effects, when performed at relevant experimental conditions.

A more direct way to assess risks is to conduct toxicological in-vitro testing of metal particles, for instance on lung cell cultures relevant for human inhalation. Induced toxicity of metal particles on lung cells includes both the effect of the particles themselves and of the released metal fraction (including bioaccessible and bioavailable metals), the latter shown to be less predominant. The toxic response was clearly influenced by various experimental conditions such as sonication treatment of particles and the presence of serum proteins.

Thorough characterization of metal particles assessing parameters including chemical surface composition, degree of agglomeration in solution, size distribution, surface area and morphology was performed and discussed in relation to generated results of bioaccessibility, bioavailability and induced toxicity. One important conclusion was that neither the surface composition nor the bulk composition can be used to assess the extent of metals released from chromium-based alloy particles. These findings emphasize that information on physical-chemical properties and surface characteristics of particles is essential for an in-depth understanding of metal release processes and for further use and interpretation of bioaccessibility data to assess hazard and reduce any risks induced by human exposure to metal particles.

Place, publisher, year, edition, pages
Stockholm: KTH , 2009. , xiv, 69 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2009:56
Keyword [en]
ferro-chromium alloy, metal particles, bioaccessibility, chemical speciation, dermal contact, surface oxide, in-vitro testing, chemical speciation, cu, copper, comet assay, intracellular, ultrafine, in vitro, A549, cytotoxicity, DNA damage, nanoparticles, particle characterization, artificial sweat, nickel release, nickel powder particles, particle loadings, release kinetics, surface area, copper release, powder particles, synthetic body fluids, simulation of interstitial lung conditions, skin contact, metal release, stainless steel, particles, test method
National Category
Physical Chemistry Analytical Chemistry Analytical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-11695ISBN: 978-91-7415-472-6 (print)OAI: oai:DiVA.org:kth-11695DiVA: diva2:279517
Public defence
2009-12-14, F3, Lindstedtsvägen 26, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Note
QC 20100803Available from: 2009-12-04 Created: 2009-12-03 Last updated: 2010-08-03Bibliographically approved
List of papers
1. Elaboration of a test method for the study of metal release from stainless steel particles in artificial biological media
Open this publication in new window or tab >>Elaboration of a test method for the study of metal release from stainless steel particles in artificial biological media
2006 (English)In: Corrosion Science, ISSN 0010-938X, E-ISSN 1879-0496, Vol. 48, no 9, 2855-2866 p.Article in journal (Refereed) Published
Abstract [en]

Data on metal release from stainless steel particles can be used in the assessment and quantification of the potential impact of stainless steel on health and the environment. To elaborate a test method suitable for the study of metal release from particles, the experimental parameters particle loading, agitation and separation of particles from the solution were investigated through exposure of 316L powder particles in two artificial biological media. The results suggest that a small particle loading, bi-linear shaking and centrifugation for separation of particles from the solution give the most reproducible results. They also show that metal release rates are strongly influenced by the physico-chemical properties of the test medium and the effective surface area of particles during exposure

Keyword
Metal release, Particles, Stainless steel, Surface area, Test method
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-5959 (URN)10.1016/j.corsci.2005.10.005 (DOI)000240767300031 ()
Note
QC 20100803Available from: 2006-06-07 Created: 2006-06-07 Last updated: 2017-12-14Bibliographically approved
2. In-vitro studies of copper release from powder particles in synthetic biological media
Open this publication in new window or tab >>In-vitro studies of copper release from powder particles in synthetic biological media
2007 (English)In: Environmental Pollution, ISSN 0269-7491, E-ISSN 1873-6424, Vol. 145, 51-59 p.Article in journal (Refereed) Published
Abstract [en]

The aim of this paper is to provide quantitative data on copper release from powder particles of different copper materials, including artificial copper patina, Cu2O and metallic Cu, when exposed to different synthetic biological media to simulate an inhalation scenario and/or skin contact. Generated data may contribute in risk assessment of potential health effects following exposure to and handling of various copper materials. All tests were performed in vitro to determine total copper concentrations, release rates of total copper, and to elucidate its time-dependence. The copper release process was interpreted in terms of specific surface area, surface morphology-, and composition. All powder materials show a time-dependent release process with total copper release rates less than 3 μg/cm2 per hour at steady state conditions, for all media investigated. The importance of using relevant test media when simulating different interstitial lung conditions and difficulties encountered when comparing powder particles of essentially different properties are thoroughly discussed.

Keyword
Copper release; In vitro tests; Powder particles; Simulation of interstitial lung conditions; Skin contact; Synthetic body fluids
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-5960 (URN)10.1016/j.envpol.2006.03.041 (DOI)000242348600007 ()
Note
QC 20100803Available from: 2006-06-07 Created: 2006-06-07 Last updated: 2017-12-14Bibliographically approved
3. Metal release from stainless steel particles in vitro-influence of particle size.
Open this publication in new window or tab >>Metal release from stainless steel particles in vitro-influence of particle size.
2007 (English)In: Journal of Environmental Monitoring, ISSN 1464-0325, E-ISSN 1464-0333, Vol. 9, no 1, 74-81 p.Article in journal (Refereed) Published
Abstract [en]

Human inhalation of airborne metallic particles is important for health risk assessment. To study interactions between metallic particles and the human body, metal release measurements of stainless steel powder particles were performed in two synthetic biological media simulating lung-like environments. Particle size and media strongly influence the metal release process. The release rate of Fe is enhanced compared with Cr and Ni. In artificial lysosomal fluid (ALF, pH 4.5), the accumulated amounts of released metal per particle loading increase drastically with decreasing particle size. The release rate of Fe per unit surface area increases with decreasing particle size. Compared with massive sheet metal, fine powder particles (<4 microm) show similar release rates of Cr and Ni, but a higher release rate of Fe. Release rates in Gamble's solution (pH 7.4), for all powders investigated, are significantly lower compared to ALF. No clear trend is seen related to particle size in Gamble's solution.

Keyword
particulate matter; air-pollution; oxidative stress; health; toxicity; airborne; carcinogenicity; dissolution; chromium; cells
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-11693 (URN)10.1039/b613919a (DOI)000243565300009 ()17213945 (PubMedID)2-s2.0-33846072406 (Scopus ID)
Note
QC 20100803Available from: 2009-12-03 Created: 2009-12-03 Last updated: 2017-12-12Bibliographically approved
4. Nickel release from nickel particles in artificial sweat.
Open this publication in new window or tab >>Nickel release from nickel particles in artificial sweat.
Show others...
2007 (English)In: Contact Dermatitis, ISSN 0105-1873, E-ISSN 1600-0536, Vol. 56, no 6, 325-30 p.Article in journal (Refereed) Published
Abstract [en]

Nickel is widely used in a broad range of products, primarily made of alloys, used by humans on a daily basis. Previous assessments have shown that skin contact with some such products may cause nickel allergic contact dermatitis, induced by the release of nickel. However, data on nickel release from small nickel particles in artificial sweat for assessment of potential risks of workers in nickel-producing and nickel-using facilities are not available. The objective of this study was to fill this knowledge gap by determining nickel release from fine nickel powder ( approximately 4 microm diameter) of different loadings varying from 0.1 to 5 mg/cm(2), when immersed in artificial sweat. The amount of nickel released increased with increasing particle loading, whereas the highest release rate per surface area of particles was observed for the medium particle loading, 1 mg/cm(2), at current experimental conditions. All particle loadings showed time-dependent release rates, reaching a relative steady-state level of less than 0.1 microg/cm(2)/hr after 12 hr of immersion, whereby less than 0.5% of the nickel particle loading was released. Nickel release from particles was influenced by the surface composition, the active surface area for corrosion, particle size, and loading.

Keyword
artificial sweat; nickel release; nickel powder particles; particle loadings; release kinetics; surface area
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-11692 (URN)10.1111/j.1600-0536.2007.01115.x (DOI)000246695000004 ()17577373 (PubMedID)2-s2.0-34250622749 (Scopus ID)
Note
QC 20100803Available from: 2009-12-03 Created: 2009-12-03 Last updated: 2017-12-12Bibliographically approved
5. Surface characteristics, copper release, and toxicity of nano- and micrometer-sized copper and copper(II) oxide particles: a cross-disciplinary study.
Open this publication in new window or tab >>Surface characteristics, copper release, and toxicity of nano- and micrometer-sized copper and copper(II) oxide particles: a cross-disciplinary study.
Show others...
2009 (English)In: Small (Weinheim an der Bergstrasse, Germany), ISSN 1613-6829, Vol. 5, no 3, 389-99 p.Article in journal (Refereed) Published
Abstract [en]

An interdisciplinary and multianalytical research effort is undertaken to assess the toxic aspects of thoroughly characterized nano- and micrometer-sized particles of oxidized metallic copper and copper(II) oxide in contact with cultivated lung cells, as well as copper release in relevant media. All particles, except micrometer-sized Cu, release more copper in serum-containing cell medium (supplemented Dulbecco's minimal essential medium) compared to identical exposures in phosphate-buffered saline. Sonication of particles for dispersion prior to exposure has a large effect on the initial copper release from Cu nanoparticles. A clear size-dependent effect is observed from both a copper release and a toxicity perspective. In agreement with greater released amounts of copper per quantity of particles from the nanometer-sized particles compared to the micrometer-sized particles, the nanometer particles cause a higher degree of DNA damage (single-strand breaks) and cause a significantly higher percentage of cell death compared to cytotoxicity induced by micrometer-sized particles. Cytotoxic effects related to the released copper fraction are found to be significantly lower than the effects related to particles. No DNA damage is induced by the released copper fraction.

Keyword
copper; cytotoxicity; DNA damage; nanoparticles; particle characterization
National Category
Physical Chemistry Other Chemistry Topics
Identifiers
urn:nbn:se:kth:diva-11691 (URN)10.1002/smll.200801220 (DOI)000263503700017 ()19148889 (PubMedID)2-s2.0-60849117522 (Scopus ID)
Note

QC 20100803

Available from: 2009-12-03 Created: 2009-12-03 Last updated: 2016-05-25Bibliographically approved
6. Effect of sonication and serum proteins on copper release from copper nanoparticles and the toxicity towards lung epithelial cells
Open this publication in new window or tab >>Effect of sonication and serum proteins on copper release from copper nanoparticles and the toxicity towards lung epithelial cells
Show others...
2011 (English)In: Nanotoxicology, ISSN 1743-5390, Vol. 5, no 2, 269-281 p.Article in journal (Refereed) Published
Abstract [en]

Different methodological settings can influence particle characteristics and toxicity in nanotoxicology. The aim of this study was to investigate how serum proteins and sonication of Cu nanoparticle suspensions influence the properties of the nanoparticles and toxicological responses on human lung epithelial cells. This was investigated by using methods for particle characterization (photon correlation spectroscopy and TEM) and Cu release (atomic absorption spectroscopy) in combination with assays for analyzing cell toxicity (MTT-, trypan blue- and Comet assay). The results showed that sonication of Cu nanoparticles caused decreased cell viability and increased Cu release compared to non-sonicated particles. Furthermore, serum in the cell medium resulted in less particle agglomeration and increased Cu release compared with medium without serum, but no clear difference in toxicity was detected. Few cells showed intracellular Cu nanoparticles due to fast release/dissolution processes of Cu. In conclusion; sonication can affect the toxicity of nanoparticles.

Keyword
Nanoparticles, nanomedicine, nanotoxicology, particle toxicology
National Category
Engineering and Technology
Identifiers
urn:nbn:se:kth:diva-14310 (URN)10.3109/17435390.2010.536268 (DOI)000290936000014 ()2-s2.0-79957839345 (Scopus ID)
Funder
Formas
Note
QC 20100803 Uppdaterad från submitted till published (20110627).Available from: 2010-08-03 Created: 2010-08-03 Last updated: 2011-06-27Bibliographically approved
7. Bioaccessibility studies of ferro-chromium alloy particles for a simulated inhalation scenario: A comparative study with the pure metals and stainless steel
Open this publication in new window or tab >>Bioaccessibility studies of ferro-chromium alloy particles for a simulated inhalation scenario: A comparative study with the pure metals and stainless steel
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2010 (English)In: Integrated Environmental Assessment and Management, ISSN 1551-3777, E-ISSN 1551-3793, Vol. 6, no 3, 441-455 p.Article in journal (Refereed) Published
Abstract [en]

The European product safety legislation, REACH, requires that companies that manufacture, import, or use chemicals demonstrate safe use and high level of protection of their products placed on the market from a human health and environmental perspective. This process involves detailed assessment of potential hazards for various toxicity endpoints induced by the use of chemicals with a minimum use of animal testing. Such an assessment requires thorough understanding of relevant exposure scenarios including material characteristics and intrinsic properties and how, for instance, physical and chemical properties change from the manufacturing phase, throughout use, to final disposal. Temporary or permanent adverse health effects induced by particles depend either on their shape or physical characteristics, and/or on chemical interactions with the particle surface upon human exposure. Potential adverse effects caused by the exposure of metal particles through the gastrointestinal system, the pulmonary system, or the skin, and their subsequent potential for particle dissolution and metal release in contact with biological media, show significant gaps of knowledge. In vitro bioaccessibility testing at conditions of relevance for different exposure scenarios, combined with the generation of a detailed understanding of intrinsic material properties and surface characteristics, are in this context a useful approach to address aspects of relevance for accurate risk and hazard assessment of chemicals, including metals and alloys and to avoid the use of in vivo testing. Alloys are essential engineering materials in all kinds of applications in society, but their potential adverse effects on human health and the environment are very seldom assessed. Alloys are treated in REACH as mixtures of their constituent elements, an approach highly inappropriate because intrinsic properties of alloys generally are totally different compared with their pure metal components. A large research effort was therefore conducted to generate quantitative bioaccessibility data for particles of ferro-chromium alloys compared with particles of the pure metals and stainless steel exposed at in vitro conditions in synthetic biological media of relevance for particle inhalation and ingestion. All results are presented combining bioaccessibility data with aspects of particle characteristics, surface composition, and barrier properties of surface oxides. Iron and chromium were the main elements released from ferro-chromium alloys upon exposure in synthetic biological media. Both elements revealed time-dependent release processes. One week exposures resulted in very small released particle fractions being less than 0.3% of the particle mass at acidic conditions and less than 0.001% in near pH-neutral media. The extent of Fe released from ferro-chromium alloy particles was significantly lower compared with particles of pure Fe, whereas Cr was released to a very low and similar extent as from particles of pure Cr and stainless steel. Low release rates are a result of a surface oxide with passive properties predominantly composed of chromium(III)-rich oxides and silica and, to a lesser extent, of iron(II,III)oxides. Neither the relative bulk alloy composition nor the surface composition can be used to predict or assess the extent of metals released in different synthetic biological media. Ferro-chromium alloys cannot be assessed from the behavior of their pure metal constituents

Keyword
Ferro-chromium alloys, Bioaccessibility, Surface oxide In vitro testing, Chemical speciation
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-14309 (URN)10.1002/ieam.32 (DOI)2-s2.0-77954707280 (Scopus ID)
Note

QC 20100803

Available from: 2010-08-03 Created: 2010-08-03 Last updated: 2017-12-12Bibliographically approved
8. Particles, sweat, and tears: A comparative study on bioaccessibility of ferrochromium alloy and stainless steel particles, the pure metals and their metal oxides, in simulated skin and eye contact
Open this publication in new window or tab >>Particles, sweat, and tears: A comparative study on bioaccessibility of ferrochromium alloy and stainless steel particles, the pure metals and their metal oxides, in simulated skin and eye contact
2010 (English)In: Integrated Environmental Assessment and Management, ISSN 1551-3777, E-ISSN 1551-3793, ISSN 1551-3793, Vol. 6, no 3, 456-468 p.Article in journal (Refereed) Published
Abstract [en]

Ferrochromium alloys are manufactured in large quantities and placed on the global market for use as master alloys (secondary raw materials), primarily for stainless steel production. Any potential human exposure to ferrochromium alloy particles is related to occupational activities during production and use, with 2 main exposure routes, dermal contact and inhalation and subsequent digestion. Alloy and reference particles exposed in vitro in synthetic biological fluids relevant for these main exposure routes have been investigated in a large research effort combining bioaccessibility; chemical speciation; and material, surface, and particle characteristics. In this paper, data for the dermal exposure route, including skin and eye contact, will be presented and discussed. Bioaccessibility data have been generated for particles of a ferrochromium alloy, stainless steel grade AISI 316L, pure Fe, pure Cr, iron(II,III)oxide, and chromium(III)oxide, upon immersion in artificial sweat (pH 6.5) and artificial tear (pH 8.0) fluids for various time periods. Measured released amounts of Fe, Cr, and Ni are presented in terms of average Fe and Cr release rates and amounts released per amount of particles loaded. The results are discussed in relation to bulk and surface composition of the particles. Additional information, essential to assess the bioavailability of Cr released, was generated by determining its chemical speciation and by providing information on its complexation and oxidation states in both media investigated. The effect of differences in experimental temperature, 30 °C and 37 °C, on the extent of metal release in artificial sweat is demonstrated. Iron was the preferentially released element in all test media and for all time periods and ironcontaining particles investigated. The extent of metal release was highly pH dependent and was also dependent on the medium composition. Released amounts of Cr and Fe were very low (close to the limit of detection, <0.008% of particles released or dissolved as iron or chromium) for the alloy particles (ferrochromium alloy and stainless steel), the pure Cr particles, and the metal oxide particles. The released fraction of Cr (Cr/[Cr + Fe]) varied with the material investigated, the test medium, and the exposure time and cannot be predicted from either the bulk or the surface composition. Chromium was released as noncomplexed Cr(III) and in addition in very low concentrations (<3 mg/L). Nickel released was under the limit of detection (0.5 mg/L), except for ultrafine stainless steel particles (<10 mg/L). It is evident that media chemistry and material properties from a bulk and surface perspective, as well as other particle characteristics, and the chemical speciation of released metals have to be considered when assessing any potential hazard or risk induced by sparingly soluble metal or alloy particles.

Keyword
Bioaccessibility, Chemical speciation, Dermal contact, Ferrochromium alloy, Metal particles
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-14307 (URN)10.1002/ieam.66 (DOI)20821707 (PubMedID)2-s2.0-77954692674 (Scopus ID)
Note

QC 20100803

Available from: 2010-08-03 Created: 2010-08-03 Last updated: 2017-12-12Bibliographically approved

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