A study was conducted to investigate and quantify the effects of corrosion inhibitors on metal release within a pilot distribution system while varying the source water. The pilot distribution system consisted of pre-existing facilities from Taylor et al (2005). Iron, copper, and lead release data were collected during four separate phases of operation. Each phase was characterized by the particular blend ratios used during the study. A blended source water represented a water that had been derived from a consistent proportion of three different source waters. These source waters included (1) surface water treated through enhanced coagulation/sedimentation/filtration, (2) conventionally treated groundwater, and (3) finished surface water treated using reverse osmosis membranes. The corrosion inhibitors used during the study were blended orthophosphate (BOP), orthophosphate (OP), zinc orthophosphate (ZOP), and sodium silicate (Si). This document was intended to cite the findings from the study associated with corrosion treatment using various doses of sodium silicate. The doses were maintained to 3, 6, and 12 mg/L as SiO2 above the blend-dependent background silica concentration. Sources of iron release within the pilot distribution system consisted of, in the following order of entry, (1) lined cast iron, (2) un-lined cast iron, and (3) galvanized steel. Iron release data from these materials was not collected for each individual iron source. Instead, iron release data represented the measurement of iron upon exposure to the pilot distribution system in general. There was little evidence to suggest that iron release was affected by sodium silicate. Statistical modeling of iron release suggested that iron release could be described by the water quality parameters of alkalinity, chlorides, and pH. The R2 statistic implied that the model could account for only 36% of the total variation within the iron release data set (i.e. R2 = 0.36). The model implies that increases in alkalinity and pH would be expected to decrease iron release on average, while an increase in chlorides would increase iron release. The surface composition of cast iron and galvanized steel coupons were analyzed using X-ray photoelectron spectroscopy (XPS). The surface analysis located binding energies consistent with Fe2O3, Fe3O4, and FeOOH for both cast iron and galvanized steel. Elemental scans detected the presence of silicon as amorphous silica; however, there was no significant difference between scans of coupons treated with sodium silicate and coupons simply exposed to the blended source water. The predominant form of zinc found on the galvanized steel coupons was ZnO. Thermodynamic modeling of the galvanized steel system suggested that zinc release was more appropriately described by Zn5(CO3)2(OH)6. The analysis of the copper release data set suggested that treatment with sodium silicate decreased copper release during the study. On average the low, medium, and high doses decreased copper release, when compared to the original blend source water prior to sodium silicate addition, by approximately 20%, 30%, and 50%, respectively. Statistical modeling found that alkalinity, chlorides, pH, and sodium silicate dose were significant variables (R2 = 0.68). The coefficients of the model implied that increases in pH and sodium silicate dose decreased copper release, while increases in alkalinity and chlorides increased copper release. XPS for copper coupons suggested that the scale composition consisted of Cu2O, CuO, and Cu(OH)2 for both the coupons treated with sodium silicate and those exposed to the blended source water. Analysis of the silicon elemental scan detected amorphous silica on 3/5 copper coupons exposed to sodium silicate. Silicon was not detected on any of the 8 control coupons. This suggested that sodium silicate inhibitor varied the surface composition of the copper scale. The XPS results seemed to be validated by the visual differences of the copper coupons exposed to sodium silicate. Copper coupons treated with sodium silicate developed a blue-green scale, while control coupons were reddish-brown. Thermodynamic modeling was unsuccessful in identifying a controlling solid that consisted of a silicate-based cupric solid. Lead release was generally decreased when treated with sodium silicate. Many of the observations were recorded below the detection limit (1 ppb as Pb) of the instrument used to measure the lead concentration of the samples during the study. The frequency of observations below the detection limit tended to increase as the dose of sodium silicate increased. An accurate quantification of the effect of sodium silicate was complicated by the observations recorded below detection limit. If the lead concentration of a sample was below detection limit, then the observation was recorded as 1 ppb. Statistical modeling suggested that temperature, alkalinity, chlorides, pH, and sodium silicate dose were important variables associated with lead release (R2 = 0.60). The exponents of the non-linear model implied that an increase in temperature, alkalinity, and chlorides increased lead release, while an increase in pH and sodium silicate dose were associated with a decrease in lead release. XPS surface characterization of lead coupons indicated the presence of PbO, PbO2, PbCO3, and Pb3(OH)2(CO3)2. XPS also found evidence of silicate scale formation. Thermodynamic modeling did not support the possibility of a silicate-based lead controlling solid. A solubility model assuming Pb3(OH)2(CO3)2 as the controlling solid was used to evaluate lead release data from samples in which lead coupons were incubated for long stagnation times. This thermodynamic model seemed to similarly describe the lead release of samples treated with sodium silicate and samples exposed to the blended source water. The pH of each sample was similar, thus sodium silicate, rather than the corresponding increase in pH, would appear to be responsible if a difference had been observed. During the overall study, the effects of BOP, OP, ZOP, and Si corrosion inhibitors were described by empirical models. Statistically, the model represented the expected value, or mean average, function. If these models are to be used to predict a dose for copper release, then the relationship between the expected value function and the 90th percentile must be approximated. The USEPA Lead and Copper Rule (LCR) regulates total copper release at an action level of 1.3 mg/L. This action level represents a 90th percentile rather than a mean average. Evaluation of the complete copper release data set suggested that the standard deviation was proportional to the mean average of a particular treatment. This relationship was estimated using a linear model. It was found that most of the copper data sub-sets (represented by a given phase, inhibitor, and dose) could be described by a normal distribution. The information obtained from the standard deviation analysis and the normality assumption validated the use of a z-score to relate the empirical models to the estimated 90th percentile observations. Since an analysis of the normality and variance (essentially contains the same information as the standard deviation) are required to assess the assumptions associated with an ANOVA, an ANOVA was performed to directly compare the effects of the inhibitors and corresponding doses. The findings suggested that phosphate-based inhibitors were consistently more effective than sodium silicate when comparing the same treatment levels (i.e. doses). Among the phosphate-based inhibitors, the effectiveness of each respective treatment level was inconsistent (i.e. there was no clear indication that any one phosphate-based inhibitor was more effective than the other). As the doses increased for each inhibitor, the results generally suggested that there was a corresponding tendency for copper release to decrease.

This study evaluated the effects of orthophosphate (OP) inhibitor addition on iron, copper, and lead corrosion on coupons exposed to different blends of groundwater, surface water, and desalinated seawater. The effectiveness of OP inhibitor addition on iron, copper, and lead release was analyzed by statistical comparison between OP treated and untreated pilot distribution systems (PDS). Four different doses of OP inhibitor, ranging from zero (control) to 2 mg/L as P, were investigated and non-linear empirical models were developed to predict iron, copper, and lead release from the water quality and OP doses. Surface characterization evaluations were conducted using X-ray Photoelectron Spectroscopy (XPS) analyses for each iron, galvanized steel, copper, and lead/tin coupon tested. Also, a theoretical thermodynamic model was developed and used to validate the controlling solid phases determined by XPS. A comparison of the effects of phosphate-based corrosion inhibitor addition on iron, copper, and lead release from the PDSs exposed to the different blends was also conducted. Three phosphate-based corrosion inhibitors were employed; blended orthophosphate (BOP), orthophosphate (OP), and zinc orthophosphate (ZOP). Non-linear empirical models were developed to predict iron, copper, and lead release from each PDS treated with different doses of inhibitor ranging from zero (control) to 2 mg/L as P. The predictive models were developed using water quality parameters as well as the inhibitor dose. Using these empirical models, simulation of the water quality of different blends with varying alkalinity and pH were used to compare the inhibitors performance for remaining in compliance for iron, copper and lead release. OP inhibitor addition was found to offer limited improvement of iron release for the OP dosages evaluated for the water blends evaluated compared to pH adjustment alone. Empirical models showed increased total phosphorus, pH, and alkalinity reduced iron release while increased silica, chloride, sulfate, and temperature contributed to iron release. Thermodynamic modeling suggested that FePO4 is the controlling solid that forms on iron and galvanized steel surfaces, regardless of blend, when OP inhibitor is added for corrosion control. While FePO4 does not offer much control of the iron release from the cast iron surfaces, it does offer protection of the galvanized steel surfaces reducing zinc release. OP inhibitor addition was found to reduce copper release for the OP dosages evaluated for the water blends evaluated compared to pH adjustment alone. Empirical models showed increases in total phosphorus, silica, and pH reduced copper release while increased alkalinity and chloride contributed to copper release. Thermodynamic modeling suggested that Cu3(PO4)2·2H2O is the controlling solid that forms on copper surfaces, regardless of blend, when OP inhibitor is added for corrosion control. OP inhibitor addition was found to reduce lead release for the OP dosages evaluated for the water blends evaluated compared to pH adjustment alone. Empirical models showed increased total phosphorus and pH reduced lead release while increased alkalinity, chloride, and temperature contributed to lead release. Thermodynamic modeling suggested that hydroxypyromorphite is the controlling solid that forms on lead surfaces, regardless of blend, when OP inhibitor is added for corrosion control. The comparison of phosphate-based inhibitors found increasing pH to reduce iron, copper, and lead metal release, while increasing alkalinity was shown to reduce iron release but increase copper and lead release. The ZOP inhibitor was not predicted by the empirical models to perform as well as BOP and OP at the low dose of 0.5 mg/L as P for iron control, and the OP inhibitor was not predicted to perform as well as BOP and ZOP at the low dose of 0.5 mg/L as P for lead control. The three inhibitors evaluated performed similarly for copper control. Therefore, BOP inhibitor showed the lowest metal release at the low dose of 0.5 mg/L as P for control of iron, copper, and lead corrosion.

At present the automotive industry is due to an EU directive, replacing hexavalent chrome on vehicles. This is an extensive job as hexavalent chrome is used all over the vehicle and to large extent on fasteners (screws, nuts, rivets etc.). Chrome (VI) is used as a passivating layer on mainly zinc-iron. When replacing the hexavalent chrome with a chrome (VI) free product, the passivating properties are reduced. One of the alternatives is to replace the zinc-iron coating with a zinc-nickel coating. This coating shows great promise from the corrosion resistance point of view. Zinc-nickel is a cathodically protecting coating, and will in principle dissolve to protect the substrate from corrosion. It is therefore important to understand how, and at what rates nickel is released from zinc-nickel coatings when exposed to a chloride-rich automotive environment. The potential environmental impact of nickel needs to be evaluated before Scania can introduce this alternative as corrosion protection. Tests by Scania have previously shown that contact allergy is not an issue for zinc-nickel coatings with Cr (III) passivation. Nickel release rates corresponding to 0,12 mg m-2yr-1 for zinc-15 % nickel coatings at a pH of 4,2 were determined from an accelerated corrosion test. Based on these values, less than 1 kg of nickel per year would be released from the Scania rolling stock if Scania were to introduce zinc-nickel coatings preferably on fasteners. This value is low compared to other sources of nickel release. In order to evaluate the toxicity of the released nickel, information about the chemical speciation, i.e. chemical forms, is needed. Total or dissolved metal are not good predictors of ecotoxicity of metals. Chemical speciation and bioavailability must be incorporated in toxicity testing. Total or dissolved metal may be used as a worst case approximation.

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. / QC 20100810

Fundamental understanding of atmospheric corrosion mechanisms requires an in-depth understanding on the dynamic interaction between corrosive constituents and metal/alloy surfaces. This doctoral study comprises field and laboratory investigations that assess atmospheric corrosion and metal release processes for two different groups of alloys exposed in chloride-rich environments. These groups comprise two commercial Zn-Al alloy coatings on steel, Galfan™ (Zn5Al) and Galvalume™ (Zn55Al), and four copper-based alloys (Cu4Sn, Cu15Zn, Cu40Zn and Cu5Zn5Al). In-depth laboratory investigations were conducted to assess the role of chloride deposition and alloy microstructure on the initial corrosion mechanisms and subsequent corrosion product formation. Comparisons were made with long-term field exposures at unsheltered marine conditions in Brest, France. A multitude of surface sensitive and non-destructive analytical methods were adopted for detailed in-situ and ex-situ analysis to assess corrosion product evolution scenarios for the Zn-Al and the Cu-based alloys. Scanning electron microscopy and energy dispersive spectroscopy (SEM/EDS) were employed for morphological investigations and scanning Kelvin probe force microscopy (SKPFM) for nobility distribution measurements and to gain microstructural information. SEM/EDS, infrared reflection-absorption spectroscopy (IRAS), confocal Raman micro-spectroscopy (CRM) and grazing incidence x-ray diffraction (GIXRD) were utilized to gain information on corrosion product formation and possibly their lateral distribution upon field and laboratory exposures. The multi-analytical approach enabled the exploration of the interplay between the microstructure and corrosion initiation and corrosion product evolution. A clear influence of the microstructure on the initial corrosion product formation was preferentially observed in the zinc-rich phase for both the Zn-Al and the Cu-Zn alloys, processes being triggered by microgalvanic effects. Similar corrosion products were identified upon laboratory exposures with chlorides for both the Zn-Al and the Cu-based alloys as observed after short and long term marine exposures at field conditions. For the Zn-Al alloys the sequence includes the initial formation of ZnO, ZnAl2O4 and/or Al2O3 and subsequent formation of Zn6Al2(OH)16CO3·4H2O, and Zn2Al(OH)6Cl·2H2O and/or Zn5(OH)8Cl2·H2O. The patina of Cu sheet consists of two main layers with Cu2O predominating in the inner layer and Cu2(OH)3Cl in the outer layer, and with a discontinuous presence of CuCl in-between. Additional patina constituents of the Cu-based alloys include SnO2, Zn5(OH)6(CO3)2, Zn6Al2(OH)16CO3·4H2O and Al2O3. General scenarios for the evolution of corrosion products are proposed as well as a corrosion product flaking mechanism for some of the Cu-based alloys upon exposure in chloride-rich atmospheres. The tendency for corrosion product flaking was considerably more pronounced on Cu sheet and Cu4Sn compared with Cu15Zn and Cu5Al5Zn. This difference is explained by the initial formation of zinc- and zinc-aluminum hydroxycarbonates Zn5(OH)6(CO3)2 and Zn6Al2(OH)16CO3·4H2O on Cu15Zn and Cu5Al5Zn, corrosion products that delay the formation of CuCl, a precursor of Cu2(OH)3Cl. As a result, the observed volume expansion during transformation of CuCl to Cu2(OH)3Cl, and the concomitant flaking process of corrosion products, was less severe on Cu15Zn and Cu5Al5Zn compared with Cu and Cu4Sn in chloride-rich environments. The results confirm the barrier effect of poorly soluble zinc and zinc-aluminum hydroxycarbonates Zn5(OH)6(CO3)2 and Zn6Al2(OH)16CO3·4H2O, which results in a reduced interaction between chlorides and surfaces of Cu-based alloys, and thereby reduced formation rates of easily flaked off corrosion products. From this process also follows reduced metal release rates from the Zn-Al alloys. / Bättre molekylär förståelse för metallers atmosfäriska korrosion kräver en fördjupad kunskap i det dynamiska samspelet mellan atmosfärens korrosiva beståndsdelar och metallytan. Denna doktorsavhandling omfattar laboratorie- och fältundersökningar av korrosions- och metallfrigöringsprocesser av två grupper av legeringar som exponerats i kloridrika atmosfärsmiljöer: två kommersiella Zn-Al beläggningar på stål, Galfan™ (Zn med 5% Al, förkortat Zn5Al) och Galvalume™ (Zn55Al), samt fyra kopparbaserade legeringar (Cu4Sn, Cu15Zn, Cu40Zn och Cu5Zn5Al). Undersökningar har genomförts i renodlade laboratorie-miljöer med för-deponerade NaCl-partiklar i en atmosfär av varierande relativ fuktighet. Syftet har varit att utvärdera betydelsen av kloriders deposition och legeringarnas mikrostruktur på korrosionsmekanismen samt bildandet av korrosionsprodukter. Jämförelser av korrosionsmekanismer har även gjorts efter flerårsexponeringar av samma legeringar i en marin fältmiljö i Brest, Frankrike. Undersökningarna har baserats på ett brett spektrum av analysmetoder för detaljerade studier dels under pågående atmosfärisk korrosion (in-situ), och dels efter avslutad korrosion (ex-situ). Legeringarnas mikrostruktur och tillhörande variation i ädelhet hos olika faser har undersökts med svepelektronmikroskopi och energidispersiv röntgenmikroanalys (SEM/EDS) samt med en variant av atomkraftsmikroskopi (engelska: scanning Kelvin probe force microscopy, SKPFM). Korrosionsprodukternas tillväxt har analyserats in-situ med infraröd reflektions-absorptionsspektroskopi (IRAS), samt morfologi och sammansättning av bildade korrosionsprodukter ex-situ med SEM/EDS, konfokal Raman mikro-spektroskopi (CRM) samt röntgendiffraktion vid strykande ifall (GIXRD). Det multi-analytiska tillvägagångssättet har medfört att det komplexa samspelet mellan de skilda legeringarnas mikrostruktur, korrosionsinitiering och bildandet av korrosionsprodukter kunnat studeras i detalj. En tydlig påverkan av mikrostruktur på det initiala korrosionsförloppet har kunnat påvisas. Korrosionsinitieringen sker företrädesvis i mer zinkrika faser för såväl Zn-Al- som Cu-Zn-legeringar och orsakas av mikro-galvaniska effekter mellan de mer zinkrika, mindre ädla, faserna och omgivande faser. Deponerade NaCl-partiklar påskyndar den lokala korrosionen oberoende av mikrostruktur. Snarlika sekvenser av korrosionsprodukter har kunnat påvisas såväl efter laboratorie- som fältexponeringar. För Zn-Al-legeringar bildas först ZnO, ZnAl2O4 och/eller Al2O3, därefter Zn6Al2(OH)16CO3·4H2O och Zn2Al(OH)6Cl·2H2O och/eller Zn5(OH)8Cl2·H2O. På ren koppar bildas ett inre skikt dominerat av Cu2O, ett mellanskikt av CuCl och ett yttre skikt med i huvudsak Cu2(OH)3Cl. Beroende på legeringstillsats har även SnO2 och Zn5(OH)6(CO3)2 kunnat identifieras. En mekanism för flagning av korrosionsprodukter på kopparbaserade legeringar i kloridrika atmosfärer har utvecklats. Tendensen för flagning har visat sig vara mycket mer uttalad på ren Cu och Cu4Sn än på Cu15Zn och Cu5Al5Zn. Skillnaden kan förklaras med hjälp av det tidiga bildandet av Zn5(OH)6(CO3)2 och Zn6Al2(OH)16CO3·4H2O på Cu15Zn och Cu5Al5Zn som fördröjer bildandet av CuCl, en föregångare till Cu2(OH)3Cl. Därigenom hämmas även den observerade volymexpansionen som sker när CuCl omvandlas till Cu2(OH)3Cl, en process som visar sig vara den egentliga orsaken till att korrosionsprodukterna flagar. Resultaten bekräftar barriäreffekten hos de mer svårlösliga faserna Zn5(OH)6(CO3)2 och Zn6Al2(OH)16CO3·4H2O, vilken dels resulterar i en minskad växelverkan mellan klorider och de legeringsytor där dessa faser kan bildas, och dels i en reducerad metallfrigöringshastighet. / <p>QC 20140915</p> / Autocorr, RFSR-CT-2009-00015 Corrosion of heterogeneous metal-metal assemblies in the automotive industry / Atmospheric corrosion and environmental metal dispersion from outdoor construction materials

Vilken påverkan som upprepad rengöring av rostfritt stål 316L inom livsmedelsindustrin har gällande dess ytegenskaper, grad av metallfrisättning och korrosionsbeteende är delvis outforskat. Vid rengöring skapar en förhöjd temperatur, olika pH-värden hos rengöringsmedlen och kloridjoner (Cl-) från kranvatten eller desinfektionsmedel en potentiellt korrosiv miljö. Felaktiga rengöringsmetoder kan öka risken för lokal korrosion, såsom gropkorrosion, vilket även påverkar metallfrisättningen under produktion och transport. Därför är det viktigt för livsmedelsindustrin att ha pålitlig information om hur upprepad rengöring påverkar ytegenskaperna, graden av metallfrisättning och förändringar i korrosionsmotstånd för att säkerställa en säker produktionsmiljö. Syftet med denna studie var att undersökta effekterna av upprepad rengöring av rostfritt stål av typ 316L som används för att processa livsmedel. Genom att undersöka effekter av de individuella rengöringsmedlen, H2O2, NaOH, HNO3, och CH3CO2OH, var för sig samt i en sekvens (relevant för industriellt bruk) tillhandahölls information om förändringar i ytoxiden relaterat till användning av de olika kemikalierna.  Resultaten visar att upprepad rengöring förändrar den kemiska sammansättningen av ytoxiderna på den rostfria stålytan (XPS) efter individuell exponering för NaOH, HNO3 och den sekventiella metoden, men visade på ingen betydande skillnad efter individuell exponering för H2O2 eller CH3CO2OH. Ingen betydande förändring i ytmorfologi kunde heller observeras (LOM). En högre mängd frisatt metall observerades i NaOH, HNO3 och den sekventiella rengöringsmetoden jämfört med H2O2, och CH3CO2OH (AAS).  En uppskattning av de tvättade ytornas korrosionsbeteende i kontakt med livsmedel erhölls genom elektrokemiska tester i citronsyra och artificiellt kranvatten. Resultaten visade att rostfritt stål 316L efter upprepad rengöring hade en högre benägenhet för gropkorrosion vid kontakt med artificiellt tappvatten (PDP). Skillnaden i den passiva ytoxidens elektrokemiska egenskaper hos det rengjorda rostfria stålet 316L var liten vid simulering av livsmedelskontakt (EIS). / The influence of repeated cleaning of 316L stainless steel in the food industry is not fully understood in terms of surface properties, metal migration, and corrosion behavior upon repeated contact with food stuffs during production. During cleaning, high applied temperatures, different pH of the cleaning agents, and presence of chloride ions (Cl-) from e.g. the tap water, food stuff or disinfectants create a potentially corrosive environment. Improper cleaning procedures used to clean 316L stainless steel may increase the susceptibility of localized corrosion, such as pitting corrosion, affecting the metal migration during food production and transport. Improved understanding of how repeated cleaning treatments affect the surface properties, extent of metal migration, and the corrosion performance is, hence, vital for the food industry in order to ensure a safe production environment.  In this study, effects of repeated cleaning through different cleaning procedures provided by the industrial partners were investigated for 316L stainless steel (SS). The surface properties after repeated cleaning using five different cleaning procedures, four single solution procedures H2O2, NaOH, HNO3 and CH3CO2OH, and one sequential procedure including the four solutions in sequence, were further studied in the simulation of food contact using citric acid and artificial tap water.  From the results it was evident that the repeated cleaning procedures changed the surface oxide composition of 316L SS (determined by means of XPS) after exposure to NaOH, HNO3 single solution cleaning and the sequential cleaning procedures but no significant changes could be observed after cleaning in H2O2 and CH3CO2OH separately. No significant difference in surface morphology was observed when comparing samples before and after repeated cleaning (by means of LOM).  A higher amount of released metals was observed in the cleaning solutions from single NaOH solution, single HNO3 solution, and the sequential cleaning procedures (using AAS) compared with H2O2 and CH3CO2OH. After repeated cleaning, the electrochemical test (by means of PDP) results showed a somewhat greater tendency of 316L SS for pitting corrosion in contact with artificial tap water compared with citric acid. The observed differences in electrochemical properties of the passive film on the cleaned 316L SS was minor in the simulation of food contact applications (by means of EIS).

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. / QC 20100803