Correlations of trace element levels within and between different normal autopsy tissues analyzed by inductively coupled plasma atomic emission spectrometry (ICP-AES)

Imbalance in trace metal metabolism may lead to metal interactions that may be of patho-physiological importance. Knowledge of the relation between trace metals in normal tissues is needed to assess abnormal deviations associated with disease. In this study correlations between Cu, Co, Cr, Fe, Mn, Ni, Se, Zn, Al, Ba, Cd, Pb and Sr within the same and between 6 different, normal autopsy tissues were determined using Spearman rank correlation analysis based on analytical data obtained by inductively coupled plasma atomic emission spectrometry (ICP-AES). Fe-Co were correlated in most tissues. Cu-Mn, Zn-Cu, Zn-Mn and Zn-Cd were highly correlated in the kidney medulla. Ni-Ni, Sr-Sr and Cd-Cd were correlated between several tissues, while Fe-Fe, Zn-Zn and Cu-Cu were correlated between kidney cortex and medulla. Mn-Mn was highly correlated between the liver and brain front lobe, cerebellum and heart. High correlations were found for Ni-Co and for Se-Mn between the kidney cortex and brain front lobe and pancreas respectively. Inverse correlations were found for Se-Cd between kidney cortex and cerebellum, for Se-Cd and Cd-Zn between kidney medulla and heart, for Co-Sr and Fe-Sr between the liver and kidney cortex and heart respectively, and for Sr-Mn between kidney medulla and pancreas. A large number of trace elements are statistically correlated within and between different, normal tissues. Knowledge of these correlations may contribute to increase the understanding of kinetic interactions of trace metals in the body and the role of such interactions in normal and disturbed trace metal metabolism.     

Multielemental analysis of human fetal tissues using inductively coupled plasma-mass spectrometry

Inductively coupled plasma-mass spectrometry (ICP-MS) was used to study the distribution of 26 major and trace elements in six tissues from 21 human fetuses aged 16–22 wk. Brain, lung, spleen, kidney, heart, and liver were analyzed following a microwave oven digestion step carried out according to clean techniques designed for ultratrace metal analyses. Precision and accuracy controls were conducted using standard reference material #1577b Bovine Liver. Significant differences among tissues were found for most of the elements. Essential trace elements seem to be increasingly retained as fetal tissues mature and become physiologically functional. The ranges of concentrations measured in fetal tissues at this stage of development are generally lower and much narrower than in adult tissues. The age of the fetus, which is not given in most studies, as well as the different techniques and levels of quality assurance could be responsible for the discrepancies in the trace metal concentrations reported here and in the literature. Intratissue homogeneity was also assessed in five human fetal brains. Frontal, occipital, parietal and temporal lobes, striatum, hippocampus, and thalamus were isolated and analyzed separately. No significant differences were found in the distribution of any of the elements at this stage of development. Because of the relatively narrow ranges of concentrations found for most elements, we believe that the results presented in this study represent the inorganic fingerprint of the main tissues of normal fetuses at midpregnancy for the Greater Montreal area.     

Multielement determination in small samples of human milk by inductively coupled plasma atomic emission spectrometry

Inductively coupled plasma atomic emission spectroscopy (ICP-AES) was used for routine analysis of small samples of human milk. The concentrations of calcium (Ca), copper (Cu), iron (Fe), magnesium (Mg), manganese (Mn), phosphorus (P), and zinc (Zn) were determined in 203 milk samples from postpartum women at different stages of lactation after stepwise digestion in HNO₃, HCIO₄, and H₂O₂ under heat. Validation of the procedure was achieved using certified reference material of bovine liver (NBS 1577) with mean recoveries of 103.5%. The concentrations of the above elements in milk matrix were comparable with previously reported values. The analytical results from breast milk will provide reference information for mineral studies of Brazilian mothers and breast-fed infants.     

Nutritional and toxic elemental analysis of dry fruits using laser induced breakdown spectroscopy (LIBS) and inductively coupled plasma atomic emission spectrometry (ICP-AES)

Quantitative investigation of essential and trace heavy elements present in health-beneficial dry fruits (Pistachio, Almonds, Black walnut, White walnut, and Cashew) was investigated using Laser Induced Breakdown Spectroscopy. For an accurate elemental exposure using LIBS technique, the local thermo-dynamical equilibrium of the laser induced plasma was established and verified using McWhirter criterion based on the electron number density in the plasma. Earlier to engage, our LIBS detector was optimized. For quantification of elements, standard calibration curves (CC)-LIBS method was applied. Using our LIBS system, the nutritional elements such as Al, Mg, Ca, Fe, K, Zn, and Na and toxins like Pb, Cr, and Cu were detected in dry fruits. The elemental quantification of dry fruit contents were validated using standard (ICP-AES) method and the relative accuracy of our experimental setup in comparison to ICP approach was in the ranging from 0.1 to 0.3 at 2.5-% error confidence.     

Determination of the concentration of complex boronated compounds in biological tissues by inductively coupled plasma atomic emission spectrometry

The application of inductively coupled plasma atomic emission spectrometry (ICP-AES) to the determination of the concentration of complex boron-containing compounds in biological tissue samples is described. Tissue digestion is achieved with perchloric acid and hydrogen peroxide in 1 hr at 75 degrees C. The ICP-AES method gave a linear response for elemental boron concentration in the range 0.05 to 100 ppm and does not require the reduction of the boron to a simple species, such as boric acid. Complete recovery of boron in complex boron cluster compounds was obtained. The procedure has been applied to the determination of the boron content in compounds synthesised for neutron capture therapy and is suitable for use in biodistribution studies of such compounds.     

Assessment of trace elements in human brain using inductively coupled plasma mass spectrometry

Recent brain research reveals a major role of trace elements in various diseases such as multiple sclerosis, Alzheimer's and Wilson's disease. The majority of published tissue concentrations dates back decades, and was assessed with various methods. Little is known about hemispherical differences, the correlation of trace elements or age-dependent changes in the human brain. Thus, the aim of this study was to examine trace element concentrations in different human brain regions after whole brain formalin fixation.549 samples of 13 brain regions were investigated in 11 deceased subjects without known history of brain pathology. Regional wet-to-dry mass ratios and concentrations of iron, copper, magnesium, manganese, calcium and zinc were determined using inductively coupled plasma mass spectrometry.Cortical gray matter revealed higher water content (wet-to-dry mass ratios 5.84–6.40) than white matter regions (wet-to-dry mass ratios 2.95–3.05). Element concentrations displayed specific regional differences. Good linear correlation of concentrations between elements was found for iron/copper as well as for manganese/magnesium (Spearman's rank correlation coefficient 0.74 and 0.65, respectively). Significant inter-hemispherical differences were found for copper in occipital white matter, for magnesium and calcium in putamen and for iron and copper in temporal white matter. An age dependent increase was seen in cortical gray matter for calcium, for magnesium in all regions except in cortical gray matter, for copper in substantia nigra and for zinc in occipital cortex.The presented trace element concentrations can serve as a fundamental basis for further brain research. Wet-to-dry mass ratios allow a comparison with reference data from other studies.     

Determination of trace elements in human serum by inductively coupled plasma-mass spectrometry

The determination of trace and ultratrace elements in human serum by ICP-MS is described. The accuracy of the method is tested using a “second generation” human serum reference material. Elements determined include Fe, Co, Cu, Zn, Br, Rb, Sr, Mo, and Cs. The method is compared to nuclear analytical methods (NAA, PIXE). Perspectives for the future are also discussed.     

Microwave-assisted acid extraction methodology for trace elements determination in mastic gum of Pistacia lentiscus using inductively coupled plasma atomic emission spectrometry

Introduction – To ensure food safety, accurate knowledge of the levels of several trace elements is necessary. This is also true for natural products of plants and resins used for human consumption or therapeutic treatment, like the mastic gum of Pistacia lentiscus. The rapid analysis of gum and resin matrices is a challenge because there are problems with the decomposition of such complicated matrices. Objective – To develop an efficient multielemental analytical method for the determination of trace elements and to compare different procedures for analyte extraction when microwave‐assisted digestion is applied. Methodology – The inductively coupled plasma atomic emission spectrometric (ICP‐AES) technique was applied and the optimum ICP conditions like radiofrequency power, argon flow rate and nebuliser sample uptake flowrate were found. The microwave‐assisted procedure was compared with that with conventional heating. Since mastic and resinous materials are difficult for dissolution and extraction of trace element, influential acid mixtures containing hydrofluoric acid proved to be capable of quantitative extraction of the analytes. Results – The digestion of mastic resin or similar matrices is significantly facilitated by using microwave radiation instead of conventional heating since the obtained recovery for several analytes is much higher. It was proved that the acid mixture of HCl–HNO₃–HF was the most efficient for complete sample digestion and recovery of the analytes. Conclusions The performance characteristics of the developed method were evaluated against certified reference material and the method was proved reliable and applicable to the analysis of mastic gum and possibly to similar resinous matrices. Copyright © 2010 John Wiley & Sons, Ltd.     

Determination of nonheme iron using inductively coupled plasma-atomic emission spectrometry

A technique for the rapid and accurate estimation of nonheme iron using inductively coupled plasma-atomic emission spectrometry is described. Yttrium was used as an internal standard. An external calibration method was used. The standards were prepared in a matrix composed of 2.5N HCl in 10% (w/v) trichloroacetic acid. The supernatant and coagulum fractions of liver nonheme iron were separated by the method of Drysdale and Ramsay with minor modification. The data determined by this procedure was compared and found to be agreement with data determined by the method of Hallgren. To evaluate the iron status of rats, hemoglobin and liver nonheme iron were determined. Hemoglobin and all of the nonheme iron fractions of the rats fed an iron-deficient diet were significantly lower than those of the rats fed an iron-sufficient diet. The blood content in the liver was estimated to be 80 microL/g from the blood iron concentration, and the difference between total and nonheme iron concentration in liver.     

Determination of trace elements in porcine brain by inductively coupled plasma-mass spectrometry,electrothermal atomic absorption spectrometry,and instrumental neutron activation analysis

Methods have been developed for the analyses of trace metals in various areas of porcine brains, (temporal, parietal, frontal cortex, both right and left hemispheres). Determinations were carried out using inductively coupled plasma-mass spectrometry (ICP-MS) and electrothermal atomic absorption spectrometry (ETAAS). The elements investigated were Li, Mn, Cu, Zn, Cd, Hg, and Pb by ICP-MS and Cu, Cd, and Mn by ETAAS. For determination by ICP-MS, a method of standard additions calibration coupled with internal standards was used, and for ETAAS, standard additions calibrations were prepared. The accuracy of all methods was determined using NIST and IAEA certified reference material. A small number of pig brains were analyzed by instrumental neutron activation analysis for Cr, Co, Cs, Fe, Rb, Se, Sc, Sb, and Zn using the comparator method of analysis. Four separate NIST standard reference materials have been used to examine the validity of the comparator method.     

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.

     

Examination of granuloma of revised cemented or cementless total hip arthroplasties using inductively coupled plasma atomic emission spectrometry (ICP-OES)]

INTRODUCTION: Aseptic loosening is the most common problem in total hip arthroplasty (THA). One main aspect is inflammatory reaction against wear particles of the prosthesis materials. Analysing failure mechanisms in THA analysis of the particles and their element distribution of revised granulomatous tissue is essential to improve materials used in THA. MATERIALS AND METHODS: 23 granulomas of revised THA due to aseptic loosening, 13 of which with metal on metal bearing (M/M), were analysed using inductively coupled plasma atomic emission spectrometry (ICP-OES). RESULTS: Elements Cr, Mn, Ni, Al, Cu, Zn, Cd, Ti, V, Zr, Nb and Fe could be detected. The maximum value of Cr was 23.88 ppb (parts per billion), Al 191.02 ppb, Ni 64.95 ppb and Zr 9.96 ppb. The highest value of Al could be found in cementless implants. The maximum value of the elements Cr and Ni could be detected in M/M. In cemented implants the highest value of Zr was found. DISCUSSION: The origin of Zr was the used bone cement in cemented THA. The elements Cr and Ni were significantly higher in M/M bearings. The highest value of Al was detected in granulomas of revised corund rough blasted cementless implants. The histopathologic findings of the revised M/M bearings have been published recently. Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-OES) could not show any differences of the alloying constituents in cases with or without allergic reactions. ICP-OES analysis seems to be not useful examination of histologic sections using SEM with cryotransfer unit.     

Determination of major and trace elements in the liver of Wistar rats by inductively coupled plasma-atomic emission spectrometry and mass spectrometry

Inductively coupled plasma-mass spectrometry (ICP-MS) and inductively coupled plasma-atomic emission spectrometry (ICP-AES) were used to determine age-related changes in the concentrations of constituent elements in the livers of Wistar rats of 1 week to 12 months old. At first, sample preparation and analytical conditions were investigated in order to set up a simple routine procedure for measuring multiple elements simultaneously. Seventeen elements in the standard reference samples of bovine and pork livers as well as rat liver samples could be determined with a reasonable precision and reproducibility. They were P, K, Na, Fe, Mg, Ca, Zn, Rb, Cu, Mn, Mo, Al, Co, Sr, Cs, Pb, and Cd in order of the levels of concentration in the adult rat livers. Of these elements, the five major elements (P, K, Na, Fe, Mg, Ca) were determined with ICP-AES and the others with ICP-MS. Although the number of animals was too small to draw a statistically definite conclusion, it seems that age-related changes in the concentrations of these elements could be categorized into three general patterns: (1) remaining essentially constant throughout the animal ages, as observed for P, K, Na, Mg, Ca, Rb, Sr, Cs, and Pb, (2) increasing with age, as observed for Fe, Mn, Mo, Co, and Cd, and (3) decreasing with age, especially in the early stages of growth, as observed for Cu and Zn.     

Speciation of trace elements in human serum by micro anion exchange chromatography coupled with inductively coupled plasma mass spectrometry

Speciation analysis of essential trace elements in human serum provides important information on nutritional status and homeostatic mechanisms regulating transport processes, acute phase reactions, and protection against oxidative damage. Anion exchange high-performance liquid chromatography (HPLC) combined with inductively coupled plasma mass spectrometry (ICP-MS) has proved to be a useful tool in speciation. Here we describe a fast method that can be applied to carry out the speciation of Fe, Cu, Zn, and Se in as little as 1 microl [corrected] of serum. The method employs monolithic anion exchange micro columns installed on a tandem HPLC system coupled on-line with an ICP-MS detector. The chromatographic separation is similar to those reported previously but with considerable gain in terms of time and sample requirement. Reproducibility is acceptable for most species. Using our method, we were able to find species-specific differences between different commercially available trace element reference materials. Because the method chosen to collect blood might interfere with speciation, the proposed methodology was used to compare heparinized plasma, ethylenediaminetetraacetic acid (EDTA) plasma, and serum from adult healthy volunteers. As expected, EDTA strongly affects speciation analysis (especially for Fe and Zn), whereas changes due to the use of lithium-heparin (Li-He) as anticoagulant appear to be minimized.     

Respective contributions of atomic emission spectrometry (AES) and secondary ion mass spectrometry (SIMS) to trace element quantification

By means of Secondary Ion Mass Spectrometry (SIMS) it is possible to measure in situ the relative concentration of a given element in a volume of 1 micron 3. Atomic Emission Spectrometry (AES) allows absolute quantitation of tissue homogenates. The use of both techniques lead to correlate relative and absolute elemental concentrations. These methods have been applied to lithium and manganese quantitation after treatments at a therapeutic dose. The results assess the sensibility of SIMS analysis, around 0.1 ppm in biological specimens, and confirm the adequacy of the instrument to trace elements study.     

Determination of isotope ratios in human tissues enriched with zinc stable isotope tracers using inductively coupled plasma-mass spectrometry (ICP-MS)

Enriched fecal and urine samples were prepared using ion-exchange column chromatography for analysis by Inductively Coupled and Fast Atom Bombardment Mass spectrometry (ICP-MS, FAB-MS) to compare precision between methods. Unenriched samples of human milk, feces, and whole blood were prepared similarly to monitor instrumental precision and analytical error. A least squares fit of the ICP-MS results vs the FAB-MS for⁷⁰Zn/⁶⁴Zn gave a slope of 0.98, with a relative standard deviation (RSD) of only 0.7%. The results for⁶⁸Zn/⁶⁴Zn gave a slope of 0.82, with a RSD of 14%. For unenriched tissues, all potential interferences were removed by the preparation procedure with no significant differences between preparation for isotope ratios of⁷⁰Zn/⁶⁴Zn,⁶⁸Zn/⁶⁴Zn,⁶⁷Zn/⁶⁴Zn, and⁶⁶Zn/⁶⁴Zn. Poisson counting statistics are a major contribution to the total analytical error indicating the usefulness of this procedure for enrichment studies.     

Matrix interferences in the analysis of digested biological tissues with inductively coupled plasma-mass spectrometry

To investigate the physiological roles or toxicity of trace or toxic elements, multielement analysis of limited quantities of samples in the biological tissues is required. Inductively coupled plasma mass spectrometry (ICP-MS) suits this requirement, but spectral and nonspectral interferences are inevitable. We examined correction methods for the nonspectral interferences by analyzing signals of 21 elements in various concentrations of HNO₃ as well as five major elements (Na, K, P, Ca, and Cl). Using internal standards, the interferences caused by the major elements were corrected, but the interferences caused by HNO₃ were impossible to correct for elements with high ionization potentials. The analytical results using the standard addition method on 14 elements in standard reference materials and fresh brain tissues confirmed the accuracy of this method. Thus, we concluded that the standard addition method is useful to correct for the nonspectral interferences.     

Composition of the major elements and trace elements of 10 methanogenic bacteria determined by inductively coupled plasma emission spectrometry

The elemental composition of 10 methanogenic species was determined by inductively coupled plasma emission spectrometry and by a C-H-N-analyzer. The 10 species were representative of all three orders of the methanogens and were cultivated under defined conditions. Special emphasis was given toMethanosarcina barkeri, represented by 5 strains and cultivated on various substrates. The following elements with the lowest and highest values in parentheses were determined: C (37–44%, w/w), H (5.5–6.5%), N (9.5–12,8%); Na (0.3–4.0%), K (0.13–5.0%), S (0.56–1.2%), P (0.5–2.8%), Ca (order I: 85–550 ppm; order II: 1000–4500 ppm), Mg (0.09–0.53%), Fe (0.07–0.28%), Ni (65–180 ppm), Co (10–120 ppm). Mo (10–70 ppm), Zn (50–630 ppm), Cu (<10–160 ppm), Mn (<5–25 ppm). The biggest variations were found with respect to N and K, which both seem to have important physiological functions. Although it is unknown whether zinc and copper are essential trace elements for methanogens, all investigated species contained remarkably high zinc contents, whereas copper seemed to be present only in some species.     

Multianalysis of trace elements in mosses with inductively coupled plasma-mass spectrometry

As a part of an air-pollution biomonitoring survey, a procedure using inductively coupled plasma-mass spectrometry (ICP-MS) and microwave digestion was developed to achieve a high sample throughput and guarantee the accuracy of the results. This article presents an analytical method to measure 22 trace elements. As, Ba, Cd, Ce, Co, Cr, Cs, Cu, Fe, Hg, La, Mo, Ni, Pb, Rb, Sb, Sr, Th, Tl, U, V, W were analyzed in 563 mosses collected in France. The digestion was performed in polytetrafluoroethylene (PTFE) vessel using the mixture HNO₃-H₂O₂-HF. The data were reprocessed taking into account the drift curve calculated for each element. The detection limits (DL) calculation was based on the standard deviations of the reagent blanks concentrations. The DL varied from one batch to another, because of the heterogeneity of the mosses’ elemental contents. The DL ranged between 0.001 μg/g (Cs, Tl) and 70 μg/g (Fe) and were mainly around 0.01 μg/g (As, Cd, Ce, Co, Hg, La, Mo, Sb, Sr, U, V, W). The detection limits obtained were in agreement with the concentrations observed in the samples, except for Hg and Ni. The reproducibility between duplicates and the analytical precision were near 10%. The procedure was tested with the mosses’ reference materials.     

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.