[show abstract][hide abstract] ABSTRACT: Mechanisms for the onset of diabetes and the development of diabetic complications remain under extensive investigations. One of these mechanisms is abnormal homeostasis of metals, as either deficiency or excess of metals, can contribute to certain diabetic outcomes. Therefore, this paper will report the blood levels of chromium (Cr), copper (Cu), iron (Fe), manganese (Mn), mercury (Hg), nickel (Ni), lead (Pb), selenium (Se), and zinc (Zn) in subjects with type 1 diabetes (n = 192, mean age 48.8 years, mean disease duration 20.6 years), type 2 diabetes (n = 68, mean age 68.4 years, mean disease duration 10.2 years), and in control subjects (n = 59, mean age 57.2 years), and discuss the results indicating their possible role in diabetes. The metal concentrations were measured by sector field inductively coupled plasma mass spectrometry after microwave-induced acid digestion of blood samples. The accuracy was checked using a blood-based certified reference material, and recoveries of all elements were in the range of 92-101 % of certified values. Type 1 diabetes was found to be associated with Cr (p = 0.02), Mn (p < 0.001), Ni (p < 0.001), Pb (p = 0.02), and Zn (p < 0.001) deficiency, and type 2 diabetes with Cr (p = 0.014), Mn (p < 0.001), and Ni (p < 0.001) deficiency. These deficiencies were appreciated also subdividing the understudied patients for gender and age groups. Furthermore, in type 1 diabetes, there was a positive correlation between Pb and age (p < 0.001, ρ = 0.400) and Pb and BMI (p < 0.001, ρ = 0.309), while a negative correlation between Fe and age (p = 0.002, ρ = -0.218). In type 2 diabetes, there was a negative correlation between Fe and age (p = 0.017, ρ = -0.294) and Fe and BMI (p = 0.026, ρ = -0.301). Thus, these elements may play a role in both forms of diabetes and combined mineral supplementations could have beneficial effects.
Biological trace element research 11/2013; · 1.92 Impact Factor
[show abstract][hide abstract] ABSTRACT: This study investigates the uptake of iron and aluminium by apoferritin. In particular, we provide the first evidence that
apoferritin is able to bind in vitro the physiological form of aluminium, Al(OH)4
−, to reach an Al/Fe atomic ratio of about 0.15. Mass spectrometry analysis shows that the Al content increases linearly as
a function of Al concentration in solution. These findings provide a better understanding of the Al uptake in vivo, confirming
that the metal content of ferritin depends on the metal bio-availability.
Journal of Nanoparticle Research 08/2013; · 2.18 Impact Factor
[show abstract][hide abstract] ABSTRACT: Many experimental evidences point out the correlation between the presence of aluminum-ferritin complex and neursopathological disorders. In these complexes, two different ranges of Aluminium (Al) atoms are usually found, i.e., just few atoms or several hundreds. Here, we investigated the in-vitro Al-apoferritin binding, with the aim to elucidate the mechanism behind the formation of Al-ferritin complexes in-vivo. To this purpose, we studied the mineralization of Al in its ionic and complexed form with citrate demonstrating that high Al levels found in clinical studies can be obtained only conveying Al by small physiological ligands.
[show abstract][hide abstract] ABSTRACT: A method based on microwave digestion and high resolution mass spectrometry was developed for the determination of Cd, Co, Cr, Ni and Pb in powder cosmetic samples. The procedure was validated in-house at the native concentration found in the cosmetic and at three fortification levels. Measurement uncertainties were calculated using data generated from repeatability, recovery and calibration linearity studies. The mean repeatability estimates were ≤11% for Cd, Co, Ni and Pb and ≤25% for Cr. The average recoveries ranged between 70% (Cr) and 112% (Pb). The expanded uncertainties (k = 2) of the method were between 34% (Cd) and 63% (Cr) at the native concentration and from 14% (Cd and Pb) to 34% (Cr) at the highest fortification level. The results accompanied by their uncertainty statements in the powder cosmetic were as follows (in mg kg−1): Cd, 0.026 ± 0.009; Co, 1.61 ± 0.60; Cr, 3.00 ± 1.88; Ni, 6.87 ± 2.53; Pb, 0.25 ± 0.09.
[show abstract][hide abstract] ABSTRACT: A human blood biomonitoring campaign to detect the environmental exposure to metals (Cd, Cu, Cr, Mn, Pb and Zn) in 265 subjects was performed in the South-Western part of Sardinia (an Italian island) that is a particular area with a great history of coal and metal mining (Pb/Zn mainly) activities and large industrial structures (as metallurgy). Subjects living near the industrial plant area had geometric means (GM) of blood Cd (0.79 μg/l), Cu (971 μg/l), Mn (12.2 μg/l), and Pb (55.7 μg/l) significantly higher than controls (Cd, 0.47 μg/l; Cu, 900 μg/l; Mn 9.98 μg/l; Pb, 26.5 μg/l) and than people living nearby the past mining sites. Subjects living next to one dismissed mine were statistically higher in blood Cu (GM, 1,022 μg/l) and Pb (GM, 41.4 μg/l) concentrations than controls. No differences were observed in people living in the different mining sites, and this might be related to the decennial disclosure of mines and the adoption of environmental remediation programmes. Some interindividual variables influenced blood biomonitoring data, as smoke and age for Cd, gender for Cu, age, sex and alcohol for Pb, and age for Zn. Moreover, blood metal levels of the whole population were similar to reference values representative of the Sardinian population and acceptably safe according to currently available health guidelines.
Environmental Monitoring and Assessment 11/2012; · 1.59 Impact Factor
[show abstract][hide abstract] ABSTRACT: Tattoo-induced pseudolymphoma is a cutaneous inflammatory response, the pathogenesis of which is still unknown. The objective of the present work was to find a possible causal relationship between pseudolymphomatous reactions on the red areas of tattoos and the metals contained in tattoo pigments and skin biopsies. Three individuals with cutaneous lesions on the red areas of tattoos were observed. Clinical and immunohistochemical examinations of the lesions were performed, and the concentrations of Cd, Co, Cr, Hg, Ni and Pb were measured in pigments and biopsy samples. Pseudolymphomas in the red areas were diagnosed in all three cases; one showed the prevalence of B-lymphocytes, whereas the other two showed a prevalence of T cells with a lichenoid pattern. Patch tests were negative. Corticosteroid therapy was ineffective. Cadmium, Co, Hg and Pb in the pigments were probably present as impurities, whereas Cr and Ni were the main components. Chromium and Ni had the highest concentrations, also in the biopsy samples. Permanent tattoos appear to be unsafe, considering the increasing number of diagnosed pseudolymphomas. It can be excluded that Hg was responsible for the reactions, given that the concentration in the red dyes and biopsies was very low. Significant levels of Cr and Ni should be considered as the causes of possible dermal reactions.
[show abstract][hide abstract] ABSTRACT: OBJECTIVES: Ferritin is the main iron-storage protein capable of containing thousands iron atoms. However, ferritin can bind in vitro other atoms such as aluminium and it has been shown that also in vivo atoms other than iron, as aluminium and zinc, are present in large amounts in ferritin. Since aluminum appears to be involved in the development of Alzheimer's disease, in the present study the specific content of aluminium in ferritin of Alzheimer's patients was analysed and compared with other control groups. DESIGN AND METHODS: The content of Fe, Al and Zn of blood ferritin was measured by mass spectrometry in patients with Alzheimer's disease and compared with other clinical and control groups. RESULTS: The results obtained confirm the hypothesis of a functional role of ferritin as a regulatory protein of toxic metals and clearly indicate that ferritin from Alzheimer's patients has a content of aluminium higher than that of controls. CONCLUSIONS: The specific aluminium content of ferritin seems to be related to different disease stages of Alzheimer's disease. This results confirms the hypothesis of aluminium ss a possible factor inducing the Alzheimer's disease and opens the ways to possible new diagnostic tests.
[show abstract][hide abstract] ABSTRACT: A protocol based on microwave digestion with oxidizing agents (HNO3, H2O2) followed by detection with sector field inductively coupled plasma mass spectrometry (SF ICP MS) was developed and in-house
validated to measure As, Cd, and Pb content in milk powder. The limits of detection (LoD) and quantification (LoQ) were 3.04
and 9.12 ng g−1 for As, 0.49 and 1.46 ng g−1 for Cd, 0.62 and 1.85 ng g−1 for Pb. The signal response was linear up to two orders of magnitude of concentration. The average recovery from the certified
skim milk powder reference material was 100.6% for Cd and 97.6% for Pb, whereas spiked samples provided a mean recovery of
102% for As. Repeatability and reproducibility respectively were equal to 3.5 and 4.3% for As, 4.9 and 5.0% for Cd, and 5.7
and 5.1% for Pb. Validation data were used to calculate the method’s uncertainty, and relative expanded uncertainties were
8.6% for As, 12% for Cd and 10% for Pb. The method was robust when critical procedural parameters were changed and when applied
to cow’s milk and infant formulas. Arsenic level was <LoD in all samples, Cd ranged 2.3–4.5 ng g−1 in cow’s milk and 2.3–7.8 ng g−1 in infant formulas, and Pb ranged 8.9–15.9 ng g−1 in cow’s milk and was <LoQ-12.1 ng g−1 in infant formulas.
[show abstract][hide abstract] ABSTRACT: Iridium tissue distribution and excretion in female Wistar rats following oral exposure to iridium (III) chloride hydrate in drinking water (from 1 to 1000 ng/ml) in a sub-chronic oral study were determined. Samples of urine, feces, blood and organs (kidneys, liver, lung, spleen and brain) were collected at the end of exposure. The most prominent fractions of iridium were retained in kidney and spleen; smaller amounts were found in lungs, liver and brain. Iridium brain levels were lower than those observed in other tissues but this finding can support the hypothesis of iridium capability to cross the blood brain barrier. The iridium kidney levels rose significantly with the administered dose. At the highest dose, important amounts of the metal were found in serum, urine and feces. Iridium was predominantly excreted via feces with a significant linear correlation with the ingested dose, which is likely due to low intestinal absorption of the metal. However, at the higher doses iridium was also eliminated through urine. These findings may be useful to help in the understanding of the adverse health effects, particularly on the immune system, of iridium dispersed in the environment as well as in identifying appropriate biological indices of iridium exposure.
[show abstract][hide abstract] ABSTRACT: As a part of the activities of the first Italian human biomonitoring survey (PROBE - PROgramme for Biomonitoring general population Exposure), a reference population of adolescents, aged 13-15 years, was examined for their exposure to metals. The study included 252 adolescents living in urban areas, representative of Latium Region (Italy) and blood specimens were analyzed for metals (As, Be, Cd, Co, Cr, Hg, Ir, Mn, Mo, Ni, Pb, Pd, Pt, Rh, Sb, Sn, Tl, U, V and W) by sector field inductively coupled plasma mass spectrometry. The results obtained will improve the knowledge about the body burden in adolescents and are tentative reference values for Italian young people as a basis for risk evaluation deriving from urban/environmental exposure to metals.
International journal of hygiene and environmental health 10/2011; 215(2):185-90. · 2.64 Impact Factor
[show abstract][hide abstract] ABSTRACT: The artificial-turf granulates made from recycled rubber waste are of health concern due the possible exposure of users to dangerous substances present in the rubber, and especially to PAHs. In this work, we determined the contents of PAHs, metals, non-dioxin-like PCBs (NDL-PCBs), PCDDs and PCDFs in granulates, and PAH concentrations in air during the use of the field. The purposes were to identify some potential chemical risks and to roughly assess the risk associated with inhalation exposure to PAHs. Rubber granulates were collected from 13 Italian fields and analysed for 25 metals and nine PAHs. One further granulate was analysed for NDL-PCBs, PCDDs, PCDFs and 13 PAHs. Air samples were collected on filter at two fields, using respectively a high volume static sampler close to the athletes and personal samplers worn by the athletes, and at background locations outside the fields. In the absence of specific quality standards, we evaluated the measured contents with respect to the Italian standards for soils to be reclaimed as green areas. Zn concentrations (1 to 19 g/kg) and BaP concentrations (0.02 to 11 mg/kg) in granulates largely exceeded the pertinent standards, up to two orders of magnitude. No association between the origin of the recycled rubber and the contents of PAHs and metals was observed. The sums of NDL-PCBs and WHO-TE PCDDs+PCDFs were, respectively, 0.18 and 0.67×10(-5) mg/kg. The increased BaP concentrations in air, due to the use of the field, varied approximately from <0.01 to 0.4 ng/m(3), the latter referring to worst-case conditions as to the release of particle-bound PAHs. Based on the 0.4 ng/m(3) concentration, an excess lifetime cancer risk of 1×10(-6) was calculated for an intense 30-year activity.
Science of The Total Environment 09/2011; 409(23):4950-7. · 3.26 Impact Factor
[show abstract][hide abstract] ABSTRACT: Studies suggested the intake of Cd from diet can be approximately equivalent to that from smoking. Moreover, a mutual metabolic influence between Cd and nutrients has been reported. The purpose of this study was to evaluate the relationship between blood cadmium concentration (BCdC) and food consumption, nutrients intake (Ca, Fe, Zn, vitamin C, and vitamin D), tobacco smoking, and some other variables (age, body mass index, and residence) in 243 adults living in the Italian island of Sardinia (Sassari Province). Specifically, we hypothesized that offal consumption contributes to Cd intakes and blood levels. The BCdC was quantified by graphite furnace atomic absorption spectrometry, and information on personal data was collected through questionnaires. Smoke significantly contributed to the BCdC (P < .001). Nonsmoker subjects who eat offal showed significantly higher BCdC (P = .04). Moreover, slightly higher BCdCs were also observed in nonsmoker subjects who eat rice, fish, and bread. The BCdC positively correlated with age of subjects (r = 0.144; P = .025) and offal daily intake in nonsmokers (r = 0.393; P < .001). The intake of Ca was negatively correlated (r = -0.281; P = .001) with the BCdC in females. The multiple linear regression analysis showed smoking > consumption of offal > body mass index ≈ age as the most important risk factors for the BCdC in the selected population.
Nutrition research (New York, N.Y.) 09/2011; 31(9):691-7. · 1.20 Impact Factor
[show abstract][hide abstract] ABSTRACT: Lichen, Usnea barbata, transplants taken from Tierra del Fuego (south Patagonia, Argentina) were tested as potential biomonitors of atmospheric airborne deposition in an apparently pristine environment. In 2005, lichens were sampled in a reference site (n = 31) and transplanted in the northern Region of Tierra del Fuego. After, respectively, 1 month and 1 year of exposure, we collected them. The aim of the study was to determine the bioaccumulation of 26 elements in order to evaluate the background levels in the selected area. Samples were analyzed by the sector field inductively coupled plasma mass spectrometry. Discriminant analysis on principal component analysis factors was applied in order to explore the relationship among the different elements as far as time and spatial variation in transplants regards. The analysis was tested by Monte Carlo test based on 999 replicates. The most important contamination source resulted to be the atmospheric soil particle deposition. Furthermore, the results were compared with those obtained from the lichens collected in central and southern Tierra del Fuego. This study confirms the ability of U. barbata to reflect the background levels of the 26 elements in that environment. Compared with other background sites in the world, we did confirm that Tierra del Fuego lichens have a low content of the studied elements. Tierra del Fuego turned out not to be a pristine environment as supposed, but it can be considered as a reference basal ecosystem for useful comparisons among different geographical areas. These findings can be very relevant and useful for environmental conservation programs.
Environmental Monitoring and Assessment 03/2011; 184(1):527-38. · 1.59 Impact Factor
[show abstract][hide abstract] ABSTRACT: Metals are suspected of being involved in the pathogenesis of various neurologic diseases. We previously found a complex imbalance in serum chemical elements and oxidative status in patients with clinically definite multiple sclerosis (CDMS).
To understand whether this imbalance affects people with clinically isolated syndrome (CIS) and, if so, whether it predicts conversion to CDMS.
We studied 22 chemical elements and the oxidative status in 49 patients with CIS, 49 patients with CDMS, and 49 healthy donors (HD). Univariate and multivariate approaches were used to identify profiles for each group. A logistic regression analysis was used to identify the predictive potential of baseline data (elements, oxidative status, and MRI findings) for conversion to CDMS over 36 months.
Several elements and oxidative status values differed significantly among the 3 groups. Discriminant analysis revealed a major contribution of Ca, Fe, Sn, Zn, serum antioxidant capacity, and serum oxidative status, which resulted in distinct profiles (the prediction of group membership was 96% [cross-validated 92%] for HD, 92% [cross-validated 92%] for CDMS, and 90% [cross-validated 86%] for CIS). A weighted combination of element concentrations and oxidative status values, adjusting for all other predictors, would predict a reduction in the risk of conversion to CDMS within 3 years (odds ratio 0.37; 95% confidence interval 0.18-0.76; p = 0.007), thereby proving more effective than MRI at baseline.
The peculiar imbalance in serum elements and oxidative status that characterizes patients with CIS and may predict conversion to CDMS warrants studies on larger sample sizes.
[show abstract][hide abstract] ABSTRACT: This protocol was developed to estimate the uncertainty of measurements in the sector field inductively coupled plasma mass spectrometry analysis of As, Co, Cr, Mn, Mo, Ni, Sn and V in human serum by utilizing in-house validation data. The approach is outlined in the Eurachem/Citac Guide and other relevant publications. The results generated were the followings: (i) coefficients of regression >0.9995 over two orders of magnitude of metal concentration; (ii) method quantification limits between 0.05 µg/L (Cr, Mn) and 0.49 µg/L (As); (iii) mean trueness checked against a certified reference material between 95.4% (As) and 107.7% (Ni); (iv) repeatability better than 10.2% over the range 0.1-2.0 µg/L; (v) reproducibility better than 12.0% over the range 0.1-2.0 µg/L; and (vi) expanded uncertainty budget comprised between 14.7% (Mn) and 27.9% (Cr) over the range 0.1-2.0 µg/L.
Rapid Communications in Mass Spectrometry 02/2011; 25(3):453-8. · 2.51 Impact Factor
[show abstract][hide abstract] ABSTRACT: The reference ranges for blood Cu, Mn, Se and Zn of 215 adult subjects non-occupationally exposed and living in the Nuoro province (Sardinia, insular Italy) were assessed. Metals were determined by sector field inductively coupled plasma mass spectrometry after microwave-assisted acid digestion of blood. The blood reference ranges estimated as P5-P95 percentiles (geometric mean, GM) were 776-1495μg/L (1036μg/L) for Cu; 4.73-17.0μg/L (8.91μg/L) for Mn; 106-185μg/L (140μg/L) for Se and 4686-8585μg/L (6418μg/L) for Zn. These results were then stratified for sex, age, alcohol consumption, smoking habit and living area. The GM value of Cu was significantly higher in females (1127μg/L) than in males (957μg/L). Age, alcohol intake, smoking habit and residential area did not influence blood Cu. The GM of Mn was significantly higher in females (9.98μg/L) respect to males (8.01μg/L) and in drinkers (9.67μg/L) compared to non-drinkers (8.38μg/L). The other variables did not change the Mn data. Selenium concentrations did not differ significantly as a function of individuals factors. With reference to Zn, males had GM of 6804μg/L and females of 6031μg/L, and more blood Zn was found in subjects consuming alcohol (6618μg/L) respect to abstainers (6155μg/L). In addition, blood Zn was not affected by age, smoking habit and place of living.
Journal of Trace Elements in Medicine and Biology 01/2011; 25(1):19-26. · 1.96 Impact Factor
[show abstract][hide abstract] ABSTRACT: Lichen samples of Usnea barbata were used as possible biomonitors of the atmospheric background level of iridium (Ir), platinum (Pt) and rhodium (Rh) in the remote region of Tierra del Fuego (South Patagonia, Argentina). Lichens were collected in 2006 at 53 sites covering 7 different areas of the region (24 transplanted lichens of the northern region and 29 native lichen samples of the central-southern region). A microwave acidic digestion procedure was used to mineralize the samples and a sector field inductively coupled plasma mass spectrometry method was developed to quantify the elements. The study of the influence of interferences on analyte signals and a quality control procedure were carried out. The analytical protocol was further applied to evaluate Ir, Pt and Rh bioaccumulation in lichens. The detection limits obtained were 0.010 ng g⁻¹, 0.013 ng g⁻¹ and 0.030 ng g⁻¹ for Ir, Pt and Rh, respectively. Recoveries at different fortification levels were between 96.3% and 106% and precision was 3.3% on average. The metals concentration (as dry weight) spanned the following ranges: Ir, <0.010-1.011 ng g⁻¹; Pt, 0.016-2.734 ng g⁻¹; and Rh, 0.063-1.298 ng g⁻¹. Data on 7 areas were similar suggesting that no specific source, for example traffic or anthropogenic activity, influenced directly the metal concentrations in Tierra del Fuego. Values detected are more likely influenced by the long-range atmospheric transport of these pollutants and, in comparison with densely populated areas in the world, they can represent the baseline for low impacted areas.
Journal of Environmental Monitoring 10/2010; 12(10):1857-63. · 2.09 Impact Factor
[show abstract][hide abstract] ABSTRACT: The reference values (RVs) for blood Cd and Pb of 215 adult subjects non-occupationally exposed and living in Sardinia (insular Italy) were assessed. Age, sex, smoking, alcohol drinking and living area were used to stratify the reference group. After collection from volunteers, samples were acid digested in a microwave oven and metals were determined by sector field inductively coupled plasma mass spectrometry. The RVs expressed as 5th-95th percentiles (geometric mean, GM) were 0.24-1.82 μg/l (0.53 μg/l) for blood Cd and 13.2-87.3 μg/l (33.4 μg/l) for blood Pb. Females had GM levels of Cd (0.58 μg/l) higher than males (0.49 μg/l); subjects aged <40 years had less Cd (0.44 μg/l) than old subjects (>60 years; 0.56 μg/l); Cd in smokers (1.23 μg/l) was 3-times higher than in non-smokers (0.42 μg/l) and correlated with the number of cigarettes per day. The alcohol intake and place of living did not influence blood Cd. The GM values of blood Pb in males (44.4 μg/l) were higher than in females (24.7 μg/l); subjects less than 40 years-old (27.5 μg/l) showed lower Pb than elderly individuals (>60 years, 41.2 μg/l); drinkers (42.2 μg/l) had Pb 2-times higher than non-drinkers (24.4 μg/l). Blood Pb was not significantly affected by smoking and place of living. As revealed by multiple linear regression, the predictor variables were, in order of weight, smoke ≫ age for blood Cd levels, and sex = age ≫ alcohol for blood Pb levels.
International journal of hygiene and environmental health 10/2010; 214(2):102-9. · 2.64 Impact Factor
[show abstract][hide abstract] ABSTRACT: A protocol that utilises data (trueness/recovery, precision and robustness) from validation tests to calculate measurement uncertainty was described and applied to a sector field inductively coupled plasma mass spectrometry (SF-ICP-MS)-based method for the determination of Be, Cd, Hg, Ir, Pb, Pd, Pt, Rh, Sb, U, Tl and W in human serum. The method was validated according to criteria issued by international bodies such as AOAC, Eurachem and ISO and the uncertainty in the analytical measurements was estimated following the Eurachem/Citac guide. The methodology was based on dilution of human serum with water and analysis by serum-matched standard calibration. The method quantification limits ranged 0.02 microg/L (Tl, Ir) to 0.26 microg/L (Hg). The coefficients of regression were greater than 0.9991 over a range of two orders of magnitude of concentration. The mean trueness was 101% and the mean recovery on three levels of fortification (1-, 1.5-, and 2-times the baseline serum level) ranged between 93.3% and 106%. The maximum relative standard deviation values for repeatability and within-laboratory reproducibility were 12.8% and 13.5%. The method was robust to slight variations of some critical factors relevant to the sample preparation and SF-ICP-MS instrumentation. The relative expanded uncertainty over three levels of concentration ranged from 11.6% (Hg) to 27.6% (Pt), and the uncertainty on the within-laboratory reproducibility, which included factors such as time, analyst and calibration, represented the main contribution to the overall uncertainty.
Rapid Communications in Mass Spectrometry 08/2010; 24(16):2363-9. · 2.51 Impact Factor