Soil-Geochemical Factors controlling the Distribution and Oral Bioaccessibility of Nickel, Vanadium and Chromium in Northern Ireland Soils

Geogenic nickel (Ni), vanadium (V) and chromium (Cr) are present at elevated levels in soils in Northern Ireland. Whilst Ni, V and Cr total soil concentrations share common geological origins, their respective levels of oral bioaccessibility are influenced by different soil-geochemical factors. Oral bioaccessibility extractions were carried out on 145 soil samples overlying 9 different bedrock types to measure the bioaccessible portions of Ni, V and Cr. Principal component analysis identified two components (PC1 and PC2) accounting for 69% of variance across 13 variables from the Northern Ireland Tellus Survey geochemical data. PC1 was associated with underlying basalt bedrock, higher bioaccessible Cr concentrations and lower Ni bioaccessibility. PC2 was associated with regional variance in soil chemistry and hosted factors accounting for higher Ni and V bioaccessibility. Eight per cent of total V was solubilised by gastric extraction on average across the study area. High median proportions of bioaccessible Ni were observed in soils overlying sedimentary rock types. Whilst Cr bioaccessible fractions were low (max = 5.4%), the highest measured bioaccessible Cr concentration reached 10.0 mg kg-1, explained by factors linked to PC1 including high total Cr concentrations in soils overlying basalt bedrock.

Oral rehabilitation for partially dentate elders: a qualitative analysis

Aims: This study aimed to gain insight into patient’s perceptions of natural tooth loss and explored their experiences of oral rehabilitation according to a functionally orientated approach (SDA) and Removable Partial Dentures (RPD).
Study Design: For this qualitative study, a purposive sample of 15 partially dentate older patients
were recruited from Cork Dental School and Hospital. These patients had previously participated in a randomised controlled clinical trial (RCT) where they were provided with either SDA treatment using adhesive bridgework or provided with Cobalt Chromium framework RPDs. In- depth interviews were undertaken and thematic analysis was utilised to interpret the data.
Results: The findings of this study indicated strong satisfaction with SDA treatment. Patients referred to the ease in which they adapted to the adhesive prostheses as they were “lightweight”, “neat” and “fixed”. Irrespective of treatment option, patients indicated that they felt
their new prostheses were durable and an improvement on previous treatments. Most patients indicated that, previous to the RCT, they had not attended a general dentist for a number of years and only then for acute issues. They had concerns that treatment which was provided to them as part of the RCT would not be available to them in primary care. Interestingly, although they do not want their condition to dis-improve, if their prostheses failed they stated that they would not seek alternative treatment but would revert back
to adopting previous coping mechanisms.
Conclusion: This study illustrates that partially dentate older patients were very satisfied with oral rehabilitation according to a functionally orientated approach. Unfortunately they did not believe that this treatment would currently be made available to them in a primary care setting.

Compositonal Analysis of Potentially harmful Elements in Soils: Implications for Epidemiology and Kidney Disease

A substantial proportion of aetiological risks for many cancers and chronic diseases remain unexplained. Using geochemical soil and stream water samples collected as part of the Tellus Project studies, current research is investigating naturally occurring background levels of potentially toxic elements (PTEs) in soils and stream sediments and their possible relationship with progressive chronic kidney disease (CKD). The Tellus geological mapping project, Geological Survey Northern Ireland, collected soil sediment and stream water samples on a grid of one sample site every 2 km2 across the rural areas of Northern Ireland resulting in an excess of 6800 soil sampling locations and more than 5800 locations for stream water sampling. Accumulation of several PTEs including arsenic, cadmium, chromium, lead and mercury have been linked with human health and implicated in renal function decline. The hypothesis is that long-term exposure will result in cumulative exposure to PTEs and act as risk factor(s) for cancer and diabetes related CKD and its progression. The ‘bioavailable’ fraction of total PTE soil concentration depends on the ‘bioaccessible’ proportion through an exposure pathway. Recent work has explored this bioaccessible fraction for a range of PTEs across Northern Ireland. In this study the compositional nature of the multivariate geochemical PTE variables and bioaccessible data is explored to augment the investigation into the potential relationship between PTEs, bioaccessibility and disease data.

Lung cancer risk associated with occupational exposure to nickel, chromium VI, and cadmium in two population-based case-control studies in Montreal.

Cancer du poumon associé à l’exposition au nickel, au chrome VI et au cadmium dans le milieu de travail utilisant deux études populationnelles cas-témoins à Montréal. Au début des années 1990, le nickel, le chrome VI et le cadmium ont été classés en tant qu’agents cancérigènes de classe 1 par le CIRC (Centre International de Recherche sur le Cancer). Cependant, les résultats des études ayant permis la classification de ces métaux n’ont pas toujours été reproduits, et d’importantes questions demeurent quant aux effets de ces métaux à de faibles niveaux d’exposition. Un plus grand nombre de recherches empiriques est donc nécessaire afin de réaffirmer la cancérogénicité de ces agents, et d’identifier les circonstances dans lesquelles ils peuvent être néfastes. L'objectif de cette étude était d'explorer la relation entre l’exposition à un des métaux (soit le nickel, le chrome VI, ou le cadmium) et les risques subséquents de développer un cancer du poumon chez des travailleurs provenant de différents milieux de travail qui sont exposés à ces métaux à de différents degrés. Deux études cas-témoins de base populationnelle menées à Montréal ont fourni les données nécessaires pour examiner la cancérogénicité de ces métaux. La première étude était menée entre 1979 et 1986 chez des hommes âgés de 35 à 70 ans ayant un cancer dans l’un de 19 sites anatomiques de cancer sélectionnés. La seconde étude était menée entre 1996 et 2001 chez des hommes et des femmes âgés de 35 à 75 ans, avec un diagnostic de tumeur maligne au poumon. Dans ces deux études, les cas ont été recensés dans tous les hôpitaux de l'île de Montréal, tandis que les contrôles populationnels appariés par âge et stratifiés par sexe, ont été sélectionnés des listes électorales. Une entrevue avec chaque sujet a permis d'obtenir un historique d'emploi détaillé ainsi que des informations précises sur les facteurs de risques socio-économiques et personnels. Les descriptions de poste ont été évaluées par une équipe d'experts chimistes et hygiénistes afin de déterminer si le sujet a été exposé à chaque agent, et pour mesurer à la fois la concentration et la durée de chaque exposition, ainsi que l’exposition cumulative tout au long de la vie de chaque participant. Pour déterminer si une exposition à l’un des trois métaux en cause était associée à une augmentation de l'incidence du cancer du poumon, des données ont été analysées par régression logistique : des ajustements ont été effectués pour des facteurs de confusion pertinents incluant un historique détaillé du tabagisme. Des mesures catégoriques d'exposition cumulée ont été également analysées, ainsi que la modification des effets par le tabagisme. Les deux études ont été analysées séparément, puis par la suite combinées afin d'augmenter la puissance statistique. Les niveaux d'exposition mesurés dans cette population ne semblaient pas poser un excès de risque de cancer du poumon pour les travailleurs exposés au chrome VI. Cependant, ceux qui ont été exposés au nickel ont subi une augmentation significative du risque, et ce, quel que soit leur niveau d'exposition. Le risque de développer un cancer du poumon suite à une exposition au cadmium était élevé, mais pas de manière significative. Pour chacun des trois métaux, le risque de cancer du poumon était très élevé parmi les non-fumeurs, mais pas parmi les fumeurs. L’effet combiné du tabagisme et de l’exposition aux métaux était compatible avec un excès de risque additif. Cependant, les intervalles de confiance dans cette étude tendaient à être larges, et une faiblesse de puissance statistique peut limiter l’interprétation de certains résultats. Cette étude est unique dans la mesure où elle a fourni des preuves empiriques sur les risques de développer le cancer du poumon liés aux faibles niveaux d’exposition au nickel, au chrome VI, ou au cadmium provenant de divers contextes de travail. Dans la plupart des autres études, la majorité des expositions pertinentes n’ont pas été bien contrôlées. À l'inverse, cette étude a bénéficié de la collecte et de la disponibilité d'information détaillée concernant le tabagisme et d’autres facteurs de risque. Les résultats de cette étude ont d'importantes conséquences pour la santé publique, tant au niveau de la détermination des risques pour les travailleurs actuellement exposés à ces métaux, qu'au niveau de l’évaluation des risques pour la population en général, elle-même exposée à ces métaux par le biais de la pollution et de la fumée de cigarette. Cette analyse contribuera fort probablement à une réévaluation par le CIRC de la cancérogénicité de ces métaux. L'exploration de la relation entre les risques de cancer du poumon et l'exposition au nickel, au chrome VI et au cadmium est donc opportune et pertinente.

Exploring chromium (VI) dioxodihalides chemistry: is density functional theory the most suitable tool?

A comparative systematic study of the CrO2F2 compound has been performed using different conventional ab initio methodologies and density functional procedures. Two points have been analyzed: first, the accuracy of results yielded by each method under study, and second, the computational cost required to reach such results. Weighing up both aspects, density functional theory has been found to be more appropriate than the Hartree-Fock (HF) and the analyzed post-HF methods. Hence, the structural characterization and spectroscopic elucidation of the full CrO2X2 series (X=F,Cl,Br,I) has been done at this level of theory. Emphasis has been given to the unknown CrO2I2 species, and specially to the UV/visible spectra of all four compounds. Furthermore, a topological analysis in terms of charge density distributions has revealed why the valence shell electron pair repulsion model fails in predicting the molecular shape of such CrO2X2 complexes

Structure determination, magnetic and optical properties of a new chromium(II) thioantimonate, [Cr((NH2CH2CH2)(3)N)]Sb4S7

The chromium(II) antimony(III) sulphicle, [Cr((NH2CH2CH2)(3)N)]Sb4S7, was synthesised under solvothermal conditions from the reaction of Sb2S3. Cr and S dissolved in tris(2-aminoethyl)amine (tren) at 438 K. The products were characterised by single-crystal X-ray diffraction. elemental analysis, SQUID magnetometry and diffuse reflectance spectroscopy. The compound crystallises in the monoclinic space group P2(1)/n with a = 7.9756(7), b = 10.5191(9), c = 25.880(2) angstrom and beta = 90.864(5)degrees. Alternating SbS33- trigonal pyramids and Sb36 semi-cubes generate Sb4S72- chains which are directly bonded to Cr(tren pendant units. The effective magnetic moment of 4.94(6)mu(B) shows a negligible orbital contribution, in agreement with expectations for Cr(II):d(4) in a (5)A ground state. The measured band gap of 2.14(3) eV is consistent with a correlation between optical band gap and framework density that is established from analysis of a wide range of antimony sulphides. (C) 2007 Elsevier Ltd. All rights reserved.

[Cr(C6H18N4)(SbS3)], a chromium complex containing an unusual bidentate SbS33- ligand

A new chromium-antimony-sulfide, [Cr(C6H18N4)(SbS3)], has been synthesised under solvothermal conditions from CrCl3. 6H(2)O, Sb2S3 and S in the presence of triethylenetetramine at 433 K and characterised by single-crystal X-ray diffraction, thermogravimetry, elemental analysis and SQUID magnetometry. The structure of [Cr(C6H18N4)(SbS3)] consists of neutral mononuclear chromium-centred complexes, in which the Cr3+ is chelated by one tetradentate triethylenetetramine molecule and a bidentate SbS33- ligand, yielding distorted octahedral coordination. Intermolecular hydrogen bonds link individual molecules into layers within the ac plane. Within a layer, molecules occur in pairs with each member related by a centre of inversion. The Cr...Cr separation within a pair is approximately 6.5 Angstrom. Magnetic susceptibility data reveal Curie-Weiss behaviour with mu(eff) = 3.819(3)/mu(B) and a negligible Weiss constant, indicative of non-interacting Cr3+ ions. (C) 2003 Elsevier Science Ltd. All rights reserved.

Synthesis, properties, and X-ray crystal and molecular structures of homoleptic alkenyls of tin and chromium

Reaction of Li(CPhCMe2) with SnCl4 or CrCl3·3thf (thf = tetrahydrofuran) affords the isoleptic compounds Sn(CPhCMe2)4 or [Cr(CPhCMe2)4] respectively. The mode of formation and chemical properties are reported for the chromium species, and the structures of the new compounds, both of which have been determined by single-crystal X-ray analysis, are described.

Influence of chromium concentration on the optical-electronic properties of ruby microstructures

Films of amorphous aluminium nitride (AlN) were prepared by conventional radio frequency sputtering of an Al + Cr target in a plasma of pure nitrogen. The Cr-to-Al relative area determines the Cr content, which remained in the similar to 0-3.5 at% concentration range in this study. Film deposition was followed by thermal annealing of the samples up to 1050 degrees C in an atmosphere of oxygen and by spectroscopic characterization through energy dispersive x-ray spectrometry, photoluminescence and optical transmission measurements. According to the experimental results, the optical-electronic properties of the Cr-containing AlN films are highly influenced by both the Cr concentration and the temperature of the thermal treatments. In fact, thermal annealing at 1050 degrees C induces the development of structures that, because of their typical size and distinctive spectral characteristics, were designated by ruby microstructures (RbMSs). These RbMSs are surrounded by a N-rich environment in which Cr(3+) ions exhibit luminescent features not present in other Cr(3+)-containing systems such as ruby, emerald or alexandrite. The light emissions shown by the RbMSs and surroundings were investigated according to the Cr concentration and temperature of measurement, allowing the identification of several Cr(3+)-related luminescent lines. The main characteristics of these luminescent lines and corresponding excitation-recombination processes are presented and discussed in view of a detailed spectroscopic analysis.

Anomalous content of chromium in a Cretaceous sandstone aquifer of the Bauru Basin, state of Sao Paulo, Brazil

Anomalous and natural concentrations of Cr(6+), occasionally exceeding the permitted limit for human consumption (0.05 mg/L), have been detected in groundwater in the northwestern region of the state of Sao Paulo. As part of a water-rock interaction investigation, this article describes the chemical and mineralogical characterization of rock samples taken from boreholes in the municipality of Urania, with the objective of identifying Cr-bearing minerals and determining how chromium is associated with these minerals. Rock sample analysis were performed using X-ray Fluorescence, X-ray Diffraction, Scanning Electron Microscopy, electron microprobe and sequential extraction techniques. Chemical analyses indicated that the quartzose sandstones show a geochemical anomaly of chromium, with an average content of 221 ppm, which is higher than the reported chromium content of generic sandstones (35 ppm). Diopside was identified as the primary Cr-bearing mineral potentially subject to weathering processes, with a chromium content of up to 1.2% as Cr(2)O(3). Many of the diopside grains showed dissolution features, confirming the occurrence of weathering. Sequential extraction experiments indicated that 99.3% of the chromium in samples is tightly bonded to minerals, whereas 0.24% is weakly bonded via adsorption. Assuming hypothetically that all adsorbed chromium is released via desorption, the theoretical Cr concentration in water would be one order of magnitude higher than the concentrations of Cr(6+) detected in groundwater. (C) 2010 Elsevier Ltd. All rights reserved.

Simultaneous determination of chromium and manganese in alumina by slurry sampling graphite furnace atomic absorption spectrometry using NbC and NaF as modifiers

This paper reports a method for the direct and simultaneous determination of Cr and Mn in alumina by slurry sampling graphite furnace atomic absorption spectrometry (SiS-SIMAAS) using niobium carbide (NbC) as a graphite platform modifier and sodium fluoride (NaF) as a matrix modifier. 350 mu g of Nb were thermally deposited on the platform surface allowing the formation of NbC (mp 3500 degrees C) to minimize the reaction between aluminium and carbon of the pyrolytic platform, improving the graphite tube lifetime up to 150 heating cycles. A solution of 0.2 mol L(-1) NaF was used as matrix modifier for alumina dissolution as cryolite-based melt, allowing volatilization during pyrolysis step. Masses (c.a. 50 mg) of sample were suspended in 30 ml of 2.0% (v/v) of HNO(3). Slurry was manually homogenized before sampling. Aliquots of 20 mu l of analytical solutions and slurry samples were co-injected into the graphite tube with 20 mu l of the matrix modifier. In the best conditions of the heating program, pyrolysis and atomization temperatures were 1300 degrees C and 2400 degrees C, respectively. A step of 1000 degrees C was optimized allowing the alumina dissolution to form cryolite. The accuracy of the proposed method has been evaluated by the analysis of standard reference materials. The found concentrations presented no statistical differences compared to the certified values at 95% of the confidence level. Limits of detection were 66 ng g(-1) for Cr and 102 ng g(-1) for Mn and the characteristic masses were 10 and 13 pg for Cr and Mn, respectively.

Application of solid sampling device for direct determination of chromium and nickel in lubricating oils by graphite furnace atomic absorption spectrometry

One method using a solid sampling device for the direct determination of Cr and Ni in fresh and used lubricating oils by graphite furnace atomic absorption spectrometry are proposed. The high organic content in the samples was minimized using a digestion step at 400 degrees C in combination with an oxidant mixture 1.0% (v v(-1)) HNO3+15% (v v(-1)) H2O2+0.1% (m v(-1)) Triton X-100 for the in situ digestion. The 3-field mode Zeeman-effect allowed the spectrometer calibration up to 5 ng of Cr and Ni. The quantification limits were 0.86 mu g g(-1) for Cr and 0.82 mg g(-1) for Ni, respectively. The analysis of reference materials showed no statistically significant difference between the recommended values and those obtained by the proposed methods.

Chromic oxide as a digestibility marker for dogs - A comparison of methods of analysis

The study reported compared coefficients of apparent digestibility (CAD) obtained by total collection (TC) and by chromic oxide (Cr2O3) determined by visible absorption spectrometry (VIS) and flame atomic absorption spectrophotometry (FAAS). These quantification methods were also investigated to assess their precision. Nineteen adult dogs housed in individual digestibility cages were fed three commercial diets, each test including five or seven animals. The experiment was carried out in a completely randomized design with three among-subjects factors (foods) and three within-subject factors (methods), and the dogs were the experimental unit. Estimated CAD for all dietary components in the three diets by either chromium quantification methods did not differ and showed fair agreement with TC results (P > 0.05). Coefficients of chromic oxide recoveries in feces were 1.06 +/- 0.044 and 1.01 +/- 0.045 for VIS and FAAS, respectively, values significantly different (P < 0.05), indicating better recovery for FAAS. Significant differences (P<0.05) were found in the mean concentration of Cr2O3 for diets and feces (17 +/- 0.6 and 19 +/- 0.8g/kg for VIS and FAAS, respectively). Coefficient of variation for FAAS was 1.69% and 1.77% for VIS, which did not differ significantly (P > 0.05). Pearson's correlation coefficient (r=0.99; P < 0.01) indicated positive and significant association among the results for VIS and FASS, indicating reasonable precision and agreement of chromic oxide contents determined by these methods. Therefore, FAAS and VIS can be used successfully to determine Cr2O3 in dog foods and feces. (c) 2006 Elsevier B.V. All rights reserved.

Influence of shot peening and hard chromium electroplating on the fatigue strength of 7050-T7451 aluminum alloy

Chromium electrodeposition is a technique for the production of functional coatings on engineering components. These coatings are extensively micro-cracked and present high level of hardness, resistance to corrosion and wear and low coefficient of friction. In this paper the shot peening influence on the fatigue strength of aluminum 7050-T7451 alloy chromium electroplated, was investigated.The shot peening process was carried out to create residual stresses using ceramic and glass shots. A hard chromium electroplated coating of 100 mu m thickness was performed on the base material and the shot peened base material surfaces. S-N curves were obtained in axial and bending fatigue tests and compared with the 7050-T7451 aluminum alloy. In order to study the influence of residual stresses on fatigue life, the behavior of compressive residual stress field was measured by an X-ray tensometry.An increase in the axial fatigue strength of 25% and 50% of ceramic and glass shots, respectively, was observed. The lower performance in fatigue life for ceramic-shot peening may be attributed to higher surface damage, as a consequence of the overpeening intensity performed. However, in bending fatigue the behavior was practically equivalent for both processes. Fracture surface analysis by scanning electron microscopy was used to observe crack origin sites from shot peened and chromium electroplated samples. (C) 2006 Elsevier Ltd. All rights reserved.

Improvement in the fatigue strength of chromium electroplated AISI 4340 steel by shot peening

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