Chemical Elements of Human Bone Tissue Investigated by Nuclear Analytical and Related Methods

The mass fractions (in milligrams per kilogram given on a dry mass basis) of 69 chemical elements in the intact rib bone of 84 apparently healthy 15- to 58-year-old citizens (38 females and 46 males) of a nonindustrial region were investigated using five instrumental analytical methods: neutron activation analysis with high-resolution spectrometry of short- and of long-lived radionuclides, particle-induced gamma-ray emission spectrometry, inductively coupled plasma atomic emission, and mass spectrometry. The mass fractions of chemical elements were measured for rib bone of both males and females, taken separately and together. The present results indicate that rib bone can be used as exposure monitors in occupational medicine and environmental health studies to assess, or indicate, the body burden of Al, B, Ba, Be, Ca, Cr, F, Li, Mg, Na, Ni, P, Pb, rare-earth elements (REEs), Sr, and Zn. Our data show an exponential increase with the age of the content of REEs in the rib of people living in an ecologically safe region.     

The Effect of Age and Gender on Al, B, Ba, Ca, Cu, Fe, K, Li, Mg, Mn, Na, P, S, Sr, V, and Zn Contents in Rib Bone of Healthy Humans

The effect of age and gender on major, minor, and trace element contents in the intact rib bone of 80 relatively healthy 15–55-year-old women and men was investigated. Contents or upper limit of contents of 16 chemical elements in the rib bone were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES). Mean values (M?±?SΕΜ) for the mass fraction of Ba, Ca, Cu, Fe, K, Li, Mg, Na, P, S, Sr, and Zn (milligram per kilogram of dry bone) were as follows: 2.54?±?0.16, 171,400?±?4,050, 1.35?±?0.22, 140?±?11, 1,874?±?71, 0.049?±?0.011, 2,139?±?38, 5,378?±?88, 75,140?±?1,660, 1,881?±?51, 291?±?20, and 92.8?±?1.5, respectively. The upper limits of contents of Al, B, Mn, and V were <7.20, <0.65, <0.36, and <0.03, respectively. Statistically significant tendency for the Ca, Mg, and P content to decrease with age was found in the human rib bone, regardless of gender. The mass fraction of Fe in the male rib bone increases with age. It was shown that higher Ca, Mg, Na, P, and Sr mass fractions as well as lower Fe content were typical of female ribs as compared to those in male ribs.     

Accumulation of rare earth elements in human bone within the lifespan

For the first time, the contents of rare earth elements (REEs) in a rib bone of a healthy human were determined. The mean value of the contents of Ce, Dy, Er, Gd, La, Nd, Pr, Sm, Tb, and Yb (10 elements out of 17 total REEs), as well as the upper limit of means for Ho, Lu, Tm, and Y (4 elements) were measured in the rib bone tissue of 38 females and 42 males (15 to 55 years old) using inductively coupled plasma mass spectrometry (ICP-MS). We found age-related accumulation of REEs in the bone tissue of healthy individuals who lived in a non-industrial region. It was calculated that during a lifespan the content of REEs in a skeleton of non-industrial region residents may increase by one to two orders of magnitude. Using our results as indicative normal values and published data we estimated relative Gd accumulation in the bone tissue of patients according to magnetic resonance imaging with contrast agent and La accumulation in the bone tissue of patients receiving hemodialysis after treatment with lanthanum carbonate as a phosphate binder. It was shown that after such procedures contents of Gd and La in the bone tissue of patients are two to three orders of magnitude higher than normal levels. In our opinion, REEs incorporation may affect bone quality and health similar to other potentially toxic trace metals. The impact of elevated REEs content on bone physiology, biochemistry and morphology requires further investigation.     

Inductively coupled atomic emission spectrometry and neutron activation analysis for the determination of element reference values in human lung tissue

An investigation was undertaken in order to assess the performance of neutron activation analysis and inductively coupled plasma atomic emission spectrometry techniques for determining reference values for minor and trace elements in human lungs of urban subjects. Results show that in both instances experimental conditions must be carefully optimized to guarantee reliability of experimental data. Strict criteria for tissue sampling and pretreatment also had to be set. Provisional reference values for ca. 50 elements could thus be established.

     

Human biomonitoring of 73 elements in blood,serum, erythrocytes and urine

BackgroundHuman biomonitoring studies of trace elements in biological fluids are mostly limited to a certain number of elements or biological materials. In this study, we describe the significant extension of a biomonitoring to 73 elements being present in concentration ranges from ng/L to g/L in clinically relevant specimens such as blood, serum, erythrocytes and urine.MethodsThe samples were collected from 102 occupationally non-exposed inhabitants of northern Germany. The elements were determined either by inductively coupled plasma tandem mass spectrometry (ICP-MS/MS) in the low concentration range or by inductively coupled plasma optical emission spectrometry (ICP-OES) for essential trace elements and electrolytes.ResultsMean values and selected percentiles of element concentrations are presented for all sample materials. From the results, we calculated the distribution of elements between plasma and blood cells. Application of ICP-MS/MS improves selectivity and accuracy in the determination of elements that are strongly spectrally interfered, such as Cr, Ge, Pd or Ti in blood samples.ConclusionsThis publication provides very valuable information for occupational or environmental hygienists, toxicologists and clinical chemists due to the particularly high number of determined elements and presented concentration ranges.     

Age-independent constancy of mineral contents in human ribs

On age relationships of mineral contents in human bones, the contents of the sixth rib and a piece of its compact bone were determined by inductively coupled plasma atomic emission spectrometry (ICPS). The ribs were resected from 21 subjects (14 men and 7 women) who died in age ranging from 65 to 93 yr. There were no age-dependent decreases in Ca and P contents of the ribs in the age range on ICPS. It was found that there were no age-dependent decreases in Ca and P in compact bones of ribs.     

Influence of Cultivation Parameters on the Mineral Composition of Kiwi Fruit from Corsica

The effect of four cultivation parameters (postmaturity harvest date, storage period at 0 °C, and input of nitrogen and potassium fertilizers) on the mineral composition of kiwi fruit (Actinidia deliciosa var. H ayward) from Corsica were evaluated. The kiwi fruit were harvested on three dates at two‐week intervals and some fruit were stored for three and four months. The kiwi fruit orchard was fertilized with controlled levels of nitrogen (five levels) and potassium (three levels) during one growing season. The concentrations of 67 elements in kiwi fruit were measured using various analytical methods, such as flow injection spectrophotometry, flame atomic absorption spectrometry, flame atomic emission spectrometry, electrothermal atomic absorption spectrometry, inductively coupled plasma atomic emission spectrometry, inductively coupled plasma mass spectrometry, and filtration. The main elements in kiwi fruit are K, N, Cl, P, and Si and, to a lesser amount, Ca, Mg, Na, and Fe. This study demonstrates a high degree of difference in the amount of 23 mineral elements depending on the harvest date, the time of storage, and the input of fertilizers.     

Clean Chemistry for Elemental Impurities Analysis of Pharmaceuticals in Compliance with USP 232

United States Pharmacopeia updated its 100 years old metal analysis method with inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma optical emission spectrometry (ICP-OES). These sensitive instruments require that sample preparation be at least as sophisticated as the instrumentation used in the analysis. Sample contamination during sample preparation has to be controlled to an acceptable level given the low detection limit of these instruments and the ubiquitous presence of elements. This article focused on sample contamination during sample preparation. Contaminations from environment, reagents, and lab apparatus were investigated for their impact on trace element analysis. Advice on clean lab practice was offered to the pharmaceutical industry in regard to contamination control in elemental analysis labs at a time when the industry is preparing for compliance with elemental impurities in drug products.     

Elemental fingerprinting of tumorous and adjacent non-tumorous tissues from patients with colorectal cancer using ICP-MS, ICP-OES and chemometric analysis

Tumorous and adjacent non-tumorous paired biopsies from 38 patients with colorectal cancer were analyzed by inductively coupled plasma mass spectrometry and inductively coupled plasma optical emission spectrometry after low-volume microwave digestion. 18 elements were investigated: Ag, Al, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Mo, Ni, P, Pb, S, Se and Zn. Different chemometric tools were used for data evaluation: Wilcoxon signed rank test, Hieratical clustering analysis, principal component analysis (PCA) and linear discriminant analysis (LDA). With the exception of Al, tumours were observed to have significantly more elevated concentrations of essential elements as compared to non-tumours. On the contrary, elements considered potentially carcinogenic such as Cr, Ni, Mo or Co do not display significant differences. When PCA was applied, different components were obtained for tumorous and non-tumorous tissues. When LDA was applied for the elements studied (including essential and non-essential elements) about 90% of cases were correctly classified.     

Assessment of Trace Elements in Scalp Hair of a Young Urban Population in Brazil

The aim of this study was to establish background values for toxic and essential elements in hair, interelement correlations and the differences in levels between genders in a healthy young population from Southern Brazil. Hair samples (n = 167) were collected from healthy students aged 12–18 years. Trace element concentrations in hair were determined by inductively coupled plasma mass spectrometry. The study provided relatively low values for toxic elements and balanced concentrations for the essential elements in the adolescents' hair with reliable reference data. Interestingly, this study also demonstrated statistical correlations considered newfound between the elements in hair. Hair mercury levels were influenced by gender; with males presenting higher values. The overall findings of the present study, with respect to the estimated chemical elements, are of prime importance in the evaluation of reference values for determining environmental effects on children living in urban areas.     

Multielement analysis of biological samples by inductively coupled plasma-mass spectrometry

Interest in the biological behavior of a growing number of elements, along with increasing recognition of the importance of interactions among them, demands a versatile and reliable technique for multielement analysis of biological samples. Significant improvements over the sensitivity achieved with conventional inductively coupled plasma (ICP) optical emission spectrometries have been realized with the introduction of quadrupole mass spectrometry (MS) for detection of ions in the plasma. The hybrid technique of ICP-MS promises to be a method of rapid multielement analysis, at detection limits that approach or surpass those of other technologies. However, the application of ICP-MS to analyses of biological interest is truly in its infancy. Here we report the use of ICP-MS for the determination of more than 30 elements of biological interest in a tissue and a biological fluid (rat liver and serum, respectively). Experimental values of the elements serve as a basis for discussion of analytical protocols, performance criteria, and certain problems peculiar to ICP-MS.     

Background Values for Essential and Toxic Elements in Children’s Nails and Correlation with Hair Levels

Human nails are an attractive matrix for assessing environmental exposures to toxic elements as well as the deficiency of essential elements since it is noninvasively collected and can be stored at room temperature. However, reference or baseline levels in nonexposed and healthy populations are not yet established. Then, the aims of this study were (a) to estimate background values for essential and toxic elements in nails from a healthy young population in southern Brazil and (b) to evaluate possible correlations between essential and toxic elements in nails. Furthermore, this report took part of a recent study of background values in the hair of a young population. Thus, correlations between chemical elements in nails and hair were also evaluated. Nails were collected from healthy children (n?=?126), and element concentrations were determined by inductively coupled plasma mass spectrometry. This study provides new and reliable reference concentrations for toxic and essential elements in children's nails. The results can be used as reference values for epidemiological or clinical investigations based on trace elements in nails. Additionally, we also showed weak to strong correlations between Cu, Mg, Mn, Se, and Zn levels in nails and hair.     

Methodological Aspects of In Vitro Assessment of Bio-accessible Risk Element Pool in Urban Particulate Matter

In vitro tests simulating the elements release from inhaled urban particulate matter (PM) with artificial lung fluids (Gamble’s and Hatch’s solutions) and simulated gastric and pancreatic solutions were applied for an estimation of hazardous element (As, Cd, Cr, Hg, Mn, Ni, Pb and Zn) bio-accessibility in this material. An inductively coupled plasma optical emission spectrometry (ICP-OES) and an inductively coupled plasma mass spectrometry (ICP-MS) were employed for the element determination in extracted solutions. The effect of the extraction agent used, extraction time, sample-to-extractant ratio, sample particle size and/or individual element properties was evaluated. Different patterns of individual elements were observed, comparing Hatch’s solution vs. simulated gastric and pancreatic solutions. For Hatch’s solution, a decreasing sample-to-extractant ratio in a PM size fraction of <0.063 mm resulted in increasing leached contents of all investigated elements. As already proved for other operationally defined extraction procedures, the extractable element portions are affected not only by their mobility in the particulate matter itself but also by the sample preparation procedure. Results of simulated in vitro tests can be applied for the reasonable estimation of bio-accessible element portions in the particulate matter as an alternative method, which, consequently, initiates further examinations including potential in vivo assessments.     

Elemental characterisation of the medical plant Alchemilla velebitica

Alchemilla, commonly called “lady's mantle”, is a genus of herbaceous perennial plants belonging to the family Rosaceae. The species Alchemilla velebitica is found only in Southern Europe, like in the Croatian National Park Northern Velebit. Its benefits, such as a astringent and emmenagogue activity as well as wound healing are correlated to the organic compounds found in the plant, but also certain trace elements are known to reduce skin lesions, such as zinc, selenium, copper, manganese, silicon and lithium.Thus the objective of the present study was the elemental characterization of leaves, blossoms and roots of A. velebitica. After acidic microwave assisted digestion the concentrations of selected essential and trace elements were determined by inductively coupled plasma – atomic emission spectrometry and inductively coupled plasma – mass spectrometry. Other minor elements, such as Al, B, Cu, Fe, Mn, Sr and Zn are also found in leaves, blossoms and roots with contents in μg/kg range. The preparation of decoctions and the extraction yields of the elements of interest are calculated.     

Toxic Element Profiles in Selected Medicinal Plants Growing on Serpentines in Bulgaria

Populations of medicinal plants growing on serpentines and their respective soils were analyzed for Fe, Ni, Mn, Cr, Co, Cd, Cu, Zn, and Pb using inductively coupled plasma atomic emission spectrometry. Aqua regia extraction and 0.43 M acetic acid extraction were used for the quantification of pseudototal and bioavailable fractions, respectively, of elements in soil and nitric acid digestion for determination of total element content in plants. Screening was performed to (1) document levels of toxic metals in herbs extensively used in preparation of products and standardized extracts, (2) compare accumulation abilities of ferns and seed plants, and (3) estimate correlations between metal content in plants and their soils. The toxic element content of plants varied from site to site on a large scale. The concentrations of Fe and Ni were elevated while those of Cu, Zn, and Pb were close to average values usually found in plants. The highest concentrations for almost all elements were measured in both Teucrium species. Specific differences in metal accumulation between ferns and seed plants were not recorded. The investigated species are not hyperaccumulators but can accumulate toxic elements, in some cases exceeding permissible levels proposed by the World Health Organization and European Pharmacopoeia. The harvesting of medicinal plants from serpentines could be hazardous to humans.     

An elemental analysis of archaeological bone from Sicily as a test of predictability of diagenetic change

Cortical human bone samples from three tightly dated components of a single Sicilian site were chemically analyzed employing the highly sensitive technique of inductively coupled plasma emission spectroscopy. Although the skeletons appeared to be excellently preserved, significant diagenesis was detected. Moreover, a majority of the elements tested showed no constant or linear variation over time, implying that diagenetic change tends not to be a predictable function of duration of interment. Variation among major long bones of a single skeleton was quite high, as was variation across the cortex. The latter may reflect chemical inhomogeneity in bone tissue or may be an artifact of postmortem change. The results demonstrate the hazards of unsuspected and unpredictable diagenesis, which must be controlled before reliable dietary inferences can be drawn.     

基于电感耦合等离子体质谱的蛋白质定量技术研究进展

综述了ICP-MS法应用于蛋白质定量技术方面的研究进展.蛋白质定量研究已成为蛋白质组学研究领域的热点,它是解析生物体蛋白质功能的重要途径.基于同位素标记和生物质谱分析技术是蛋白质定量最常用的方法之一,近年来,随着质谱技术的发展,电感耦合等离子体质谱(ICP-MS)技术成为元素测量的重要手段,这使其在蛋白质定量中具一定的应用前景.     

Chemical Elements in Organic and Conventional Sweet Oranges

This work focuses on the determination of chemical elements in sweet oranges of variety Valencia produced under organic and conventional systems using instrumental neutron activation analysis and inductively coupled plasma mass spectrometry. The distribution of chemical elements was variable among the fruit parts with usually higher concentrations of Br, Ca, Ce, K, La, Na, Rb, and Sc in the peel. However, K, Na, and Rb also presented high values in the juice samples, while Fe and Zn were higher in the seeds. Differences between organic and conventional oranges were found for Br and Cu.     

Survey of atmospheric heavy metal deposition in Suqian using moss contamination

Abstract

Heavy metal pollution in the atmosphere is a major environmental problem, which has important impacts on ecosystems and human health. In this study, the atmospheric deposition of cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni), lead (Pb), vanadium (V), and zinc (Zn) in Suqian, China, was investigated by using the moss Haplocladium microphyllum as a bioindicator. The survey was carried out during the summer of 2017 at 40 homogenously distributed sampling sites. Cr, Cu, Ni, Pb, V, and Zn were analyzed by inductively coupled plasma atomic emission spectrometry, and Cd was analyzed by inductively coupled plasma mass spectrometry. Wide variations in heavy metals (Cd, Pb, and Zn) indicated that the concentrations of elements are influenced by local emission sources. Spatial distribution maps of the elements were constructed using geographic information system technology. The pollution load index showed that the study area was moderately polluted to unpolluted. Significant positive correlations (p?<?.01) and weak positive correlations (p?<?.05) were identified among some of the elements, indicating that they originated from common sources. A principal component analysis classified the heavy metals into natural and anthropogenic sources, and identified four primary sources: nature soil dust, industry activities, traffic emission, and agricultural activities.     

Plasma Copper and Bone Mineral Density in Osteopenia: An Indicator of Bone Mineral Density in Osteopenic Females

Copper concentrations in blood plasma have been determined in 25 osteopenic females using inductively coupled plasma–mass spectrometry. A high degree of correlations has been demonstrated between the copper concentrations in plasma and the bone mineral density of the lumbar spine as measured using dual energy X-ray absorptiometry and quantitative computerized tomography. Results clearly indicate the involvement of copper in bone health and osteopenia. It is further suggested that plasma copper might be useful as a cheap and simple method indicative of bone mineral density in osteopenic postmenopausal females.