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The purpose of the present study is twofold: (i) to assess the salivary nickel, chromium, and iron concentrations and (ii) to characterize the surface microstructure of the typical commercially available Ni-containing metallic appliances during the first 12-week orthodontic treatment period. A total of 85 unstimulated saliva samples were collected from patients before treatment, after 2 days, and after 1, 4, and 12 weeks. Salivary ion concentrations were determined by inductively coupled plasma optical emission spectroscopy, and data were analyzed with the Statistical Package for Social Sciences (IBM SPSS) software. The recorded mean metal concentrations were in the ranges of 132–175 µg/L for Ni, 171–192 µg/L for Cr, and 826–1023 µg/L for Fe. No statistically significant variations were observed between the different study times, and the null hypothesis (the concentrations of metallic ions in patients’ saliva did not significantly change after the placement of the orthodontic appliances) was accepted (p > 0.05). Mean salivary metallic ions were below toxic levels, and no adverse clinical reactions were registered. The intraoral surface degradation of the fixed components was corroborated by optical microscopy, scanning electron microscopy, and energy dispersive spectrometry. Microstructural analysis after complete orthodontic procedure confirmed different corrosion types, from pitting to biocorrosion.

Hazard classification of metal alloys is today generally based on their bulk content, an approach that seldom reflects the extent of metal release for a given environment. Such information can instead be achieved via bioelution testing under simulated physiological conditions. The use of bioelution data instead of bulk contents would hence refine the current hazard classification of alloys and enable grouping. Bioelution data have been generated for nickel (Ni) and cobalt (Co) released from several stainless steel grades, one low-alloyed steel, and Ni and Co metals in synthetic sweat, saliva and gastric fluid, for exposure periods from 2 to 168 h. All stainless steel grades with bulk contents of 0.11–10 wt% Ni and 0.019–0.24 wt% Co released lower amounts of Ni (up to 400-fold) and Co (up to 300-fold) than did the low-alloyed steel (bulk content: 0.034% Ni, 0.015% Co). They further showed a relative bioaccessibility of Ni and Co considerably less than 1, while the opposite was the case for the low-alloyed steel. Surface oxide- and electrochemical corrosion investigations explained these findings in terms of the high passivity of the stainless steels related to the Cr(III)-rich surface oxide that readily adapted to the fluid acidity and chemistry.

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., Graphical Abstract

Investigations of metal ecotoxicity in life cycle assessment (LCA) and life cycle impact assessment (LCIA) are becoming important tools for evaluating the environmental impact of a product or process. There is, however, improvement needed for LCIA of metal ecotoxicity in order to make this assessment more relevant and robust. In this work, three issues within the LCIA of metal ecotoxicity are investigated, mainly focusing on topics related to stainless steel manufacturing. The first issue is the importance of considering regional water chemistry when constructing the characterization factor (CF). A model freshwater of relevance for stainless steel manufacturing in a region of Sweden was created with chemistry different from available options. The second issue is related to the lack of consideration on changes in speciation of Cr(VI) in freshwater for a given emission, as Cr(VI) to some extent will be reduced to Cr(III). Two new options are suggested based on relationships between the Cr(VI)&ndash, total Cr ratio as a way to improve the relevancy of LCIA for Cr(VI) in freshwater. The last issue is how to treat metal release from slags in LCIA. Metal release from slags was shown to vary significantly between different ways of modelling slag emissions (differences in total metal content, slag leaching tests, estimated emissions to groundwater).

Differences in surface oxide characteristics and extent of nickel release have been investigated in two thoroughly characterized micron-sized (mainly

The aim of the study was to evaluate the serum and urine levels of cobalt (Co), chromium (Cr), manganese (Mn), molybdenum (Mo) and nickel (Ni) in patients who had undergone metal-on-metal hybrid surface arthroplasties on the supposition that a release of metals would occur due to the large head size of this type of implant. Metal levels were determined by using an analytical method based on sector field inductively coupled plasma mass spectrometry. Results showed a significant difference between patients and control subjects in mean levels of Co and Cr in serum ( p 0.0 0 0 1 and p = 0.0 2 , respectively) and in urine ( p 0.0 0 0 1 for both). No significant differences were observed in mean serum and urinary levels of Mn, Mo and Ni. Although the clinical consequences of these changes, if any, are unknown, further studies could be performed in a larger number of subjects implanted with a total surface arthroplasty at follow-up times over different periods.

INTRODUCTION With increasing use of Indian made orthodontic materials, need was felt to know nickel and chromium release from these material. MATERIALS AND METHODS This study was conducted on simulated appliances consisting of brackets (022″Roth, Modern orthodontics, Ludhiana, India), from second premolar to central incisor, buccal tube and 0.019×0.025- inch SS arch wires secured with SS ligatures. Immersion was done in artificial saliva. Samples were analysed to using Atomic Absorption Photospectrometer (GVC ScientificEquipment Pvt. Ltd Australia) at AES Laboratories (P) Ltd., Noida India on 1(st), 7(th), 14(th) and 28(th) day. RESULTS SPSS (ver 17, Inc., Chicago, Illinois, USA) was used toperform the statistical analysis. Descriptive statistics i.e. median and 25 and75 percentiles were used. Peak nickel release was on 7(th) day and subsequently declined over 14(th) and 28(th) day. The peak level of chromium concentration was on 14(th) day, which declined thereafter. CONCLUSION Average daily release of nickel and chromium over a period of one month was 97.368 μg/day and 47.664 μg/day respectively. The estimated release rates were approximately 32% and 16% of the reported average daily dietary.

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

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.

In the last decennia, there is an increasing interest in pulsed electric field (PEF) treatment. The product is often treated in a continuous flow treatment chamber with stainless steel electrodes and exposed to short pulsed electric fields, typically 2-4 kV mm-1 during 1-10 μs. Due to direct contact of the treatment chamber electrodes with the food product, the main elements of these stainless steel electrodes are able to dissolve in the treated product. The magnitude of the material transfer depends on many factors such as current magnitude, pulse duration, pulse shape, and product constitution. In this contribution, the effect of metal dissolving during a monopolar pulse shape, generated by a pulse forming network, is investigated. Experiments are carried out with single and repeated PEF treatments in orange juice. These experiments showed that, due to PEF treatment, dissolved metals are present in the juice. The four main elements of stainless steel, iron, chromium, nickel, and manganese, have been considered in particular. The metal concentrations found do not exceed the legislation values for fruit juices and the EU Drinking Water Directive [EU Drinking Water Directive, http://www.europe.eu.int/. for human consumption. From the experiments, a relationship between dissolved metals in orange juice and the transferred charge is derived. In addition, a lifetime prediction of the treatment chamber caused by release of metals has been made. © 2005 Elsevier Ltd. All rights reserved.

In the last decennia, there is an increasing interest in pulsed electric field (PEF) treatment. The product is often treated in a continuous flow treatment chamber with stainless steel electrodes and exposed to short pulsed electric fields, typically 2-4 kV mm-1 during 1-10 μs. Due to direct contact of the treatment chamber electrodes with the food product, the main elements of these stainless steel electrodes are able to dissolve in the treated product. The magnitude of the material transfer depends on many factors such as current magnitude, pulse duration, pulse shape, and product constitution. In this contribution, the effect of metal dissolving during a monopolar pulse shape, generated by a pulse forming network, is investigated. Experiments are carried out with single and repeated PEF treatments in orange juice. These experiments showed that, due to PEF treatment, dissolved metals are present in the juice. The four main elements of stainless steel, iron, chromium, nickel, and manganese, have been considered in particular. The metal concentrations found do not exceed the legislation values for fruit juices and the EU Drinking Water Directive [EU Drinking Water Directive, http://www.europe.eu.int/. for human consumption. From the experiments, a relationship between dissolved metals in orange juice and the transferred charge is derived. In addition, a lifetime prediction of the treatment chamber caused by release of metals has been made. © 2005 Elsevier Ltd. All rights reserved.

This study has been triggered by the fact that stainless steel is being increasingly used in new applications, where possible environmental effects may be a matter of concern. When stainless steel is exposed to a given environment, a key issue is the release of small amounts of the main alloying elements iron, chromium, nickel and molybdenum. Published release rate data of these elements turned out to be sparse. Furthermore, only little was known about the role of different parameters that may affect the release rate, such as degree of alloying, exposure time and surface finish. Hence, the aim of this study was to develop methodological means and to provide accurate metal release rates of alloying constituents from different grades of stainless steels- austenitic, ferritic and duplex- when exposed to selected environments: artificial rain and synthetic body fluids. The results and discussion have been summarised in this thesis by formulating and answering ten questions, all believed to be crucial for the understanding of possible environmental effects of stainless steels. Some common conclusions could be drawn, independent of stainless steel grade and exposure condition. Iron was always preferentially released, and the release rates of chromium, nickel and molybdenum (when measured) were significantly lower than of iron, also when considering the bulk proportion of these elements. The release rate of all elements was initially high and decreased with exposure time, mainly because of an observed enrichment of chromium in the passive film formed. The release rates of iron (2 μgcm-2week-1) and nickel (0.08 μgcm-2week-1) from stainless steel from grades 304 and 316 exposed to artificial rain were much lower than corresponding rates for the pure metals (750 μgcm-2week-1 released Fe and 15 μgcm-2week-1 released Ni), whereas chromium exhibited similar release rates from stainless steel and the pure metal (0.1 μgcm-2week-1). This implies that the common procedure to calculate release rates, based on the pure metals and the nominal steel composition, significantly overestimates release rates of iron and nickel from stainless steel, but not of chromium. Total release rates from seven stainless steel grades in synthetic body fluid were found to decrease with increasing alloy content in the following release rate order: grade 409 >> grade 430 > grades 316L ≈ 201 ≈ 2205 ≈ 304 > grade 310. The release rate was highly sensitive to pH of the synthetic body fluid but only slightly sensitive to stainless steel surface finish. QC 20120217

Orthopaedic implants are mostly fabricated by Stainless Steel, Titanium, and Ni-Cr Alloys that consist of Chromium (Cr), Cobalt (Co), Nickel (Ni) and Molybdenum (Mo). 10-15% of population are affected by metals (Ni, Co, Cr, Mo) hypersensitivity reaction. Multilayer coating by Physical Vapour Deposition (PVD) has been applied onto orthopedic implants to prevent metallic ions leaching into human body. This paper aims to study the metal ions leaching of Cr, Ni, Mo, and Co from multilayer coatings of Chromium (Cr), Chromium Nitride (CrN), Chromium Carbonitride (CrCN) and Zirconium Nitride (ZrN) by Physical Vapour Deposition (PVD). Cr, CrN, CrCN and ZrN have been successfully deposited onto stainless steel substrates by CAPVD. XRD analysis detected major peak in preferred orientation of (200) and other peaks with (111), (220), (311) for CrN cubic phase. For CrCN, XRD analysis detected only low intensity peaks of Cr7C3 and ZrN peaks with preferred orientation of (111), (200) with other peak (220), (311) and (222). A seven days metal released test by ICP-MS showed that generally all ions concentration for Ni, Co, Mo decreased from uncoated substrate to multilayer coatings except for Cr. Metal released showed higher concentration for coatings deposition with longer deposition time at 10 minutes.