Certification of a reference material of metal content in atmospheric particles deposited on filters.

Air quality is one of the areas in Europe where a series of EU Directives have been published with the aim of achieving improved long-term and harmonised air quality objectives across the European Union. This paper describes the production of a certified reference material, aiming to support QA/QC programmes of analytical laboratories in the framework of the air quality monitoring activities. The certified values are the As, Cd, Ni and Pb masses in PM10 particles deposited on quartz filters (CRM SL-MR-2-PSF-01). All the steps of the certification, i.e. the material characterisation, homogeneity and stability evaluation and uncertainty calculation, were performed according to the ISO guide 35 guidelines. The certification was conducted using the characterisation by a single method approach based on isotope dilution for cadmium, nickel, and lead and gravimetric standard addition calibration for arsenic associated with inductively coupled mass spectrometry (ICP-MS). The amounts of the four elements are in the range of the target values regulated by EU Directives.

Application of TDCR-Geant4 modeling to standardization of 63Ni.

As an alternative to the classical TDCR model applied to liquid scintillation (LS) counting, a stochastic approach based on the Geant4 toolkit is presented for the simulation of light emission inside the dedicated three-photomultiplier detection system. To this end, the Geant4 modeling includes a comprehensive description of optical properties associated with each material constituting the optical chamber. The objective is to simulate the propagation of optical photons from their creation in the LS cocktail to the production of photoelectrons in the photomultipliers. First validated for the case of radionuclide standardization based on Cerenkov emission, the scintillation process has been added to a TDCR-Geant4 modeling using the Birks expression in order to account for the light-emission nonlinearity owing to ionization quenching. The scintillation yield of the commercial Ultima Gold LS cocktail has been determined from double-coincidence detection efficiencies obtained for (60)Co and (54)Mn with the 4π(LS)ß-γ coincidence method. In this paper, the stochastic TDCR modeling is applied for the case of the standardization of (63)Ni (pure ß(-)-emitter; E(max)=66.98 keV) and the activity concentration is compared with the result given by the classical model.

The critical review of methodologies and approaches to assess the inherent skin sensitization potential (skin allergies) of chemicals. Part II.

To identify specific cases, classes or specific use situations of chemicals for which 'safety thresholds' or 'safety limits' were set (in regulations, standards, in scientific research/clinical work, etc.) and critically review the scientific and methodological parameters used to set those limits.

The critical review of methodologies and approaches to assess the inherent skin sensitization potential (skin allergies) of chemicals. Part III.

For those chemicals identified in point 2 above, to collect and critically analyse clinical and statistical evidence on the incidence and morbidity (clinical picture) of skin contact allergy (contact dermatitis) cases in the EU before (at least 3 years) and after the limits were set, so as to allow an assessment of the possible effect of the limits in the reduction/prevention of the incidence and morbidity of contact dermatitis.

Image analysis for maintenance of coating quality in nickel electroplating baths--real time control.

The aim of this paper is to show how it is possible to extract analytical information from images acquired with a flatbed scanner and make use of this information for real time control of a nickel plating process. Digital images of plated steel sheets in a nickel bath are used to follow the process under degradation of specific additives. Dedicated software has been developed for making the obtained results accessible to process operators. This includes obtaining the RGB image, to select the red channel data exclusively, to calculate the histogram of the red channel data and to calculate the mean colour value (MCV) and the standard deviation of the red channel data. MCV is then used by the software to determine the concentration of the additives Supreme Plus Brightner (SPB) and SA-1 (for confidentiality reasons, the chemical contents cannot be further detailed) present in the bath (these two additives degrade and their concentration changes during the process). Finally, the software informs the operator when the bath is generating unsuitable quality plating and suggests the amount of SPB and SA-1 to be added in order to recover the original plating quality.

Fluctuations in the prevalence of nickel and cobalt allergy in eczema patients patch tested after implementation of the nickel regulation in Denmark.

BACKGROUND: A recent Danish study showed that the prevalence of nickel allergy decreased among young female patients and increased among older female patients with dermatitis patch tested between 1985 and 2007 at Gentofte Hospital, Denmark. The prevalence of cobalt allergy remained unchanged. OBJECTIVES: To examine fluctuations in the prevalence of nickel and cobalt allergy after implementation of the nickel regulation, by analysing patch test results from male and female patients with dermatitis tested between 1992 and 2009 at Odense University Hospital, Denmark. METHODS: A retrospective analysis of patch test data was performed (female, n = 5821; male, n = 3317). Comparisons were made using the chi-square test for trend. Logistic regression analyses were used to test for associations. RESULTS: The prevalence of nickel allergy decreased significantly among the 2-30-year-old female patients, from 29.8% in 1992-1997 to 19.6% in 2004-2009 (p < 0.001), whereas it increased significantly, from 6.9% in 1992-1997 to 11.1% in 2004-2009 (p = 0.04), among the >60-year-old female patients. The overall prevalence of cobalt allergy increased significantly, from 3.7% in 1992-1997 to 5.1% in 2004-2009 (p = 0.03). The overall prevalence of nickel and cobalt allergy among male patients during the test period was 5.2% and 2.2%, respectively, and no significant change across the test years was detected. CONCLUSIONS: The prevalence of nickel allergy decreased among young female patients and increased among older female patients with dermatitis, probably because of a cohort effect. The overall prevalence of cobalt allergy increased from 1992 to 2009. No significant trend in the prevalence of nickel and cobalt allergy among male patients was found.

The EU Nickel Directive revisited--future steps towards better protection against nickel allergy.

In July 2001, the EU Nickel Directive came into full force to protect European citizens against nickel allergy and dermatitis. Prior to this intervention, Northern European governments had already begun to regulate consumer nickel exposure. According to part 2 of the EU Nickel Directive and the Danish nickel regulation, consumer items intended to be in direct and prolonged contact with the skin were not allowed to release more than 0.5 µg nickel/cm2/week. It was considered unlikely that nickel allergy would disappear altogether as a proportion of individuals reacted below the level defined by the EU Nickel Directive. Despite this, the EU Nickel Directive part 2 was expected to work as an operational limit that would sufficiently protect European consumers against nickel allergy and dermatitis. This review presents the accumulation of epidemiological studies that evaluated the possible effect of this major public health intervention. Also, it evaluates recent exposure assessment studies that have been performed using the dimethyl glyoxime test. It is concluded that the EU Nickel Directive has started to change the epidemiology of nickel allergy in Europe but it should be revisited to better protect consumers and workers since nickel allergy and dermatitis remain very frequent.

Patch test reactivity to metal allergens following regulatory interventions: a 33-year retrospective study.

BACKGROUND: Contact allergy epidemics to chromate and nickel were addressed in Denmark in 1983 and 1990 by regulatory interventions. OBJECTIVES: To evaluate whether regulatory interventions on nickel and chromate exposure have reduced the proportion of strong patch test reactions. METHODS: 22 506 patients with dermatitis aged 4-99 years were patch tested with nickel sulfate, potassium dichromate, or cobalt chloride between 1977 and 2009. RESULTS: The proportion of 3+ reactions to nickel sulfate was reduced and almost disappeared after the mid- and late 1980s (P-trend = 0.001). Today, 1+ and 2+ nickel reactions occur equally frequent. Cobalt chloride patch test reactivity reflected the nickel development to some degree. The proportion of 3+ reactions to potassium dichromate was reduced during the 1980s (P-trend = 0.13), whereas the proportion of 2+ reactions to potassium dichromate have increased in recent years. CONCLUSIONS: The decrease in nickel sulfate and cobalt chloride 3+ patch test reactivity began long before the Danish nickel regulation came into effect. This could be because of research activity at the time as well as political attention in Northern Europe. The chromate content in cement regulation may have changed the epidemiology of patch test reactivity; however, in recent years, 2+ reactions to chromate have increased markedly, a development that should be carefully followed.

Characterization and assessment of dermal and inhalable nickel exposures in nickel production and primary user industries.

The aim of this study was to measure the levels of nickel in the skin contaminant layer of workers involved in specific processes and tasks within the primary nickel production and primary nickel user industries. Dermal exposure samples were collected using moist wipes to recover surface contamination from defined areas of skin. These were analysed for soluble and insoluble nickel species. Personal samples of inhalable dust were also collected to determine the corresponding inhalable nickel exposures. The air samples were analysed for total inhalable dust and then for soluble, sulfidic, metallic, and oxidic nickel species. The workplace surveys were carried out in five different workplaces, including three nickel refineries, a stainless steel plant, and a powder metallurgy plant, all of which were located in Europe. Nickel refinery workers involved with electrolytic nickel recovery processes had soluble dermal nickel exposure of 0.34 microg cm(-2) [geometric mean (GM)] to the hands and forearms. The GM of soluble dermal nickel exposure for workers involved in packing nickel salts (nickel chloride hexahydrate, nickel sulphate hexahydrate, and nickel hydroxycarbonate) was 0.61 microg cm(-2). Refinery workers involved in packing nickel metal powders and end-user powder operatives in magnet production had the highest dermal exposure (GM = 2.59 microg cm(-2) soluble nickel). The hands, forearms, face, and neck of these workers all received greater dermal nickel exposure compared with the other jobs included in this study. The soluble nickel dermal exposures for stainless steel production workers were at or slightly above the limit of detection (0.02 microg cm(-2) soluble nickel). The highest inhalable nickel concentrations were observed for the workers involved in nickel powder packing (GM = 0.77 mg m(-3)), although the soluble component comprised only 2% of the total nickel content. The highest airborne soluble nickel exposures were associated with refineries using electrolytic processes for nickel recovery (GM = 0.04 mg m(-3) total nickel, containing 82% soluble nickel) and those jobs involving contact with soluble nickel compounds (GM = 0.02 mg m(-3) total nickel content, containing 76% soluble nickel). The stainless steel workers were exposed to low concentrations of relatively insoluble airborne nickel species (GM = 0.03 mg m(-3) total nickel, containing 1% soluble nickel). A statistically significant correlation was observed between dermal exposures for all anatomical areas across all tasks. In addition, the dermal and inhalable (total) nickel exposures were similarly associated. Overall, dermal exposures to nickel, nickel compounds, and nickel alloys were relatively low. However, exposures were highly variable, which can be explained by the inconsistent use of personal protective equipment, varying working practices, and different standards of automation and engineering controls within each exposure category.

Determination of nickel, calcium and magnesium in xylem sap by flame atomic absorption spectrometry using a microsampling technique.

INTRODUCTION: Knowledge of xylem sap chemical composition is important to the understanding of translocation, detoxification and tolerance mechanisms. However, the small amount of sample available often hampers its characterisation. Hence, low volume consumption techniques are needed for xylem sap analysis. OBJECTIVE: To develop a microsampling technique for the determination of elements in xylem sap from different plants by flame atomic absorption spectrometry (FAAS). METHODOLOGY: The microsampling device was optimised in terms of sample volume and integration time. The analytical characteristics of the microsampling technique (micro-FAAS) were established and compared with those of FAAS with traditional continuous nebulisation. The method was validated by means of an independent technique. RESULTS: Ca, Mg and Ni were determined in a 50 microL aliquot of xylem sap solution/element that was introduced directly into the flame via the microsampling accessory. Good precision was obtained with relative standard deviations of 1.1, 0.6 and 2.3% for Ca, Mg and Ni, respectively. Matrix effects resulting from the physical characteristics of the samples and possible chemical interferences caused by phosphate and/or sulphate were ruled out. CONCLUSION: A simple, rapid and reproducible microsampling technique coupled to FAAS was developed and successfully applied in the determination of Ca, Mg and Ni in xylem sap.

A review of effects of particulate matter-associated nickel and vanadium species on cardiovascular and respiratory systems.

Many epidemiological investigations indicate that excess risks of mortality and morbidity may vary among specific PM(2.5) components. Nickel (Ni) and vanadium (V) particulate metal species may potentially be related to increasing respiratory and cardiovascular mortality and morbidity. This review focuses on exposure concentrations of these two species in various settings, their health effects based on epidemiological and toxicological studies and the underlying mechanisms. The evidence shows that environmental exposure concentrations of Ni and V in general setting are lower than the World Health Organization standard (V, 1 microg/m(3)/day) in 2000, or the European Environment Agency standard (Ni, 1 microg/m(3)/day) in 2003, but their associations with cardiopulmonary diseases can still be found. The toxicological mechanism can be explained by laboratory-based studies. Updated safe guidelines on environmental and human exposure of Ni and V are necessary in order to clarify the associations between them and cardiopulmonary diseases and provide environmental intervention policies.

Angular deflection of rotary nickel titanium files: a comparative study.

A new manufacturing method of twisting nickel titanium wire to produce rotary nickel titanium (RNT) files has recently been developed. The aim of the present study was to evaluate whether the new manufacturing process increased the angular deflection of RNT files, by comparing instruments produced using the new manufacturing method (Twisted Files) versus instruments produced with the traditional grinding process. Testing was performed on a total of 40 instruments of the following commercially available RNT files: Twisted Files (TF), Profile, K3 and M2 (NRT). All instruments tested had the same dimensions (taper 0.06 and tip size 25). Test procedures strictly followed ISO 3630-1. Data were collected and statistically analyzed by means ANOVA test. The results showed that TF demonstrated significantly higher average angular deflection levels (P<0.05), than RNT manufactured by a grinding process. Since angular deflection represent the amount of rotation (and consequently deformation) that a RNT file can withstand before torsional failure, such a significant improvement is a favorable property for the clinical use of the tested RNT files.

Simultaneous determination of nickel and copper by H-point standard addition method-first-order derivative spectrophotometry in plant samples after separation and preconcentration on modified natural clinoptilolite as a new sorbent.

For the simultaneous determination of nickel(ll) and copper(ll) in plant samples, a rapid and accurate method was developed. In this method, solid-phase extraction (SPE) and first-order derivative spectrophotometry (FDS) are combined, and the result is coupled with the H-point standard addition method (HPSAM). Compared with normal spectrophotometry, derivative spectrophotometry offers the advantages of increased selectivity and sensitivity. As there is no need for carrying out any pretreatment of the sample, the spectrophotometry method is easy, but because of a high detection limit, it is not so practical. In order to decrease the detection limit, it is suggested to combine spectrophotometry with a preconcentration method such as SPE. In the present work, after separation and preconcentration of Ni(ll) and Cu(ll) on modified clinoptilolite zeolite that is loaded with 2-[1-(2-hydroxy-5-sulforphenyl)-3-phenyl-5-formaza-no]-benzoic acid monosodium salt (zincon) as a selective chromogenic reagent, FDS-HPSAM, which is a simple and selective spectrophotometric method, has been applied for simultaneous determination of these ions. With optimum conditions, the detection limit in original solutions is 0.7 and 0.5 ng/mL, respectively, for nickel and copper. The linear concentration ranges in the proposed method for nickel and copper ions in original solutions are 1.1 to 3.0 x 10(3) and 0.9 to 2.0 x 10(3) ng/mL, respectively. The recommended procedure is applied to successful determination of Cu(ll) and Ni(ll) in standard and real samples.

An in vitro comparison of the force decay generated by different commercially available elastomeric chains and NiTi closed coil springs.

This in vitro study was designed to compare the forces generated by commercially available elastomeric chains and NiTi closed coil springs, and to determine their force decay pattern. Forty elastomeric chains and forty NiTi closed coil springs were divided into 4 groups according to the following manufacturers: (1) Morelli, (2) Abzil, (3) TP Orthodontics and (4) American Orthodontics. The specimens were extended to twice their original length and stored in artificial saliva at 37 degrees C. Initial force was measured by means of an Instron universal testing machine and then at 1, 4, 7, 14, 21, and 28 days. The results revealed that the elastomeric chains delivered a mean initial force of 347 g for Morelli, 351 g for American Orthodontics, 402 g for Abzil, and 404 g for TP Orthodontics. The NiTi closed coil springs generated a mean initial force of 196 g for American Orthodontics, 208 g for TP Orthodontics, 216 g for Abzil, and 223 g for Morelli. The mean percentage of force decay observed after 28 days for the elastomeric chains was 37.4% for TP Orthodontics(R), 48.1% for American Orthodontics, 65.4% for Morelli, and 71.6% for Abzil. After 28 days, the NiTi closed coil springs presented a mean percentage of force decay of 22.6% for American Orthodontics, 29.8% for Abzil, 30.6% for Morelli, and 45.8% for TP Orthodontics. At the end of the study, significant differences were observed between the elastomeric chains and the NiTi closed coil springs. The results indicated that the studied NiTi closed coil springs are more adequate for dental movement than the elastomeric chains.

An in vitro comparison of the force decay generated by different commercially available elastomeric chains and NiTi closed coil springs

This in vitro study was designed to compare the forces generated by commercially available elastomeric chains and NiTi closed coil springs, and to determine their force decay pattern. Forty elastomeric chains and forty NiTi closed coil springs were divided into 4 groups according to the following manufacturers: (1) Morelli®, (2) Abzil®, (3) TP Orthodontics® and (4) American Orthodontics®. The specimens were extended to twice their original length and stored in artificial saliva at 37°C. Initial force was measured by means of an Instron universal testing machine and then at 1, 4, 7, 14, 21, and 28 days. The results revealed that the elastomeric chains delivered a mean initial force of 347 g for Morelli®, 351 g for American Orthodontics®, 402 g for Abzil®, and 404 g for TP Orthodontics®. The NiTi closed coil springs generated a mean initial force of 196 g for American Orthodontics®, 208 g for TP Orthodontics®, 216 g for Abzil®, and 223 g for Morelli®. The mean percentage of force decay observed after 28 days for the elastomeric chains was 37.4 percent for TP Orthodontics®, 48.1 percent for American Orthodontics®, 65.4 percent for Morelli®, and 71.6 percent for Abzil®. After 28 days, the NiTi closed coil springs presented a mean percentage of force decay of 22.6 percent for American Orthodontics®, 29.8 percent for Abzil®, 30.6 percent for Morelli®, and 45.8 percent for TP Orthodontics®. At the end of the study, significant differences were observed between the elastomeric chains and the NiTi closed coil springs. The results indicated that the studied NiTi closed coil springs are more adequate for dental movement than the elastomeric chains.

Este estudo in vitro foi delineado para comparar a força gerada por cadeias elastoméricas e por molas fechadas de NiTi comercialmente disponíveis e para determinar seu padrão de degradação de forças. Para tal, 40 segmentos de cadeia elastomérica e 40 molas fechadas de NiTi foram divididas em 4 grupos de acordo com a marca comercial: (1) Morelli®, (2) Abzil®, (3) TP Orthodontics® e (4) American Orthodontics®. As amostras foram distendidas ao dobro de seu comprimento original e imersas em solução de saliva artificial a 37°C. Uma máquina de ensaio (Instron) foi utilizada para aferir a força inicial e em 1, 4, 7, 14, 21 e 28 dias. Os resultados mostraram que as cadeias elastoméricas liberaram uma força média inicial de 404 g para a marca TP Orthodontics®, 402 g para Abzil®, 351 g para American Orthodontics® e 347 g para Morelli®. As molas fechadas de NiTi geraram uma força média inicial de 223 g para a marca Morelli®, 216 g para Abzil®, 208 g para TP Orthodontics® e 196 g para American Orthodontics®. A percentagem média de degradação da força após 28 dias para as cadeias elastoméricas foi de 37,4 por cento para TP Orthodontics®, 48,1 por cento para American Orthodontics®, 65,4 por cento para Morelli® e 71,6 por cento para Abzil®. A percentagem média de degradação da força após 28 dias para as molas fechadas de NiTi foi de 22,6 por cento para American Orthodontics®, 29,8 por cento para Abzil®, 30,6 por cento para Morelli® e 45,8 por cento para TP Orthodontics®. Ao final do experimento, observaram-se diferenças significantes entre as cadeias elastoméricas e as molas fechadas de NiTi. Os resultados permitem recomendar as molas fechadas de NiTi estudadas como dispositivos mais adequados para movimentação dentária do que as cadeias elastoméricas.

Fracture of Ni-Ti superelastic alloy under sustained tensile load in physiological saline solution containing hydrogen peroxide.

The fracture of Ni-Ti superelastic alloy has been investigated by a sustained tensile-loading test in physiological saline solution containing hydrogen peroxide (0.15M NaCl + 0.3M H(2)O(2)). The fracture always occurs when the applied stress exceeds the critical stress for martensite transformation. In contrast, under a low applied stress, the fracture does not always occur within 1000 h. The fracture is probably mainly caused by localized corrosion associated with the preferential dissolution of nickel ions. In 0.3M H(2)O(2) solution without NaCl, the fracture does not occur even under a high applied stress. The results of the present study imply that one reason for the fracture of the Ni-Ti superelastic alloy in vivo is localized corrosion due to the synergistic effects of hydrogen peroxide and sodium chloride under applied stress.

Species-specific inhalable exposures in the nickel industry: a new approach for deriving inhalation occupational exposure limits.

The American Conference of Governmental Industrial Hygienists (ACGIH) and some regulatory authorities have revised their exposure limits for nickel and nickel compounds in workplaces based upon new sampling standards for inhalable nickel exposures. Others may be in the process of doing so. Safe standards for workplace exposures should utilize the most up-to-date health data on individual nickel species and should incorporate the principles of new sampling conventions that have been developed over the recent decades. The purpose of this paper is to review the basis for setting inhalable occupational exposure standards for the principal inorganic nickel species. It is hoped that this paper will (1) prompt companies in various nickel industry sectors to begin collecting the necessary inhalable aerosol measurements, speciation data, and particle-size information required to implement health-based sampling programs in the future, and (2) encourage regulators to derive species-specific, inhalable-based workplace standards for nickel and its inorganic compounds.

Effects of water chemistry on the bioavailability of metals in sediment to Hyalella azteca: implications for sediment quality guidelines.

Risk assessments of metals in sediments are often based on sediment-quality guidelines (SQGs) and do not take into account the chemistry of the overlying water. To determine the effects of water chemistry on the toxicity of metals in sediments, both water and sediment were collected from five metal-contaminated lakes with widely differing water chemistry near Canadian smelters. Metal bioaccumulation by Hyalella azteca was measured in laboratory exposures with each sediment and with overlying water from several different sources. The effect of water chemistry on Ni bioaccumulation from sediment was minimal. However, the effect was substantial for Cd because the effect of water chemistry on sediment-water partitioning was opposite to, and augmented, the effect of water chemistry on the Hyalella/water accumulation ratio. The effect of overlying water must be considered when conducting risk assessments for some metals in sediment (e.g., Cd). Examples are provided of equations that can be used to adjust cause-and-effect-based SQGs for water chemistry (e.g., using calcium concentrations or pH).