Determinations of subnanomole elemental levels by NAA and their possible impact on human health related issues

Neutron activation analysis (NAA) is an appropriate tool for the determination of trace elements in biological systems. The virtually blank-free NAA procedures fittingly complement precautions employed in sampling and sample preparation of biological matrices. Results from instrumental NAA procedures used to establish baseline values and time trends for elements in human tissues demonstrate the advantages as well as the limits of these procedures for nanomole and, in a considerable number of instances, subnanomole elemental levels. In addition, subnanomole mass fractions have been determined with extremely low limits of detection by employing NAA with radiochemical separations isolating very low levels of radioactivity from the matrix background. The elements reviewed in this article include Cr, Se, Pt, and others that have been determined by NAA at subnanomole levels in human tissues and body fluids and in biological macromolecules.     

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.     

Applications of neutron activation analysis to the study of age-related neurological diseases

Although the etiology and pathogenesis of Alzheimer’s disease, Pick’s disease, and amyotrophic lateral sclerosis are still unknown, it has been suggested that perturbations in element metabolism may play a role. Even if not causative factors, these imbalances may prove to be markers that could aid in diagnosis. We have employed a sequential neutron activation analysis (NAA) procedure to determine elemental concentrations in brain, hair, fingernails, blood, and cerebrospinal fluid (CSF) of these patients and age-matched controls. Samples are first irradiated with accelerator-produced 14-MeV neutrons for determination of nitrogen and phosphorus, then with reactor thermal neutrons for the instrumental determination of 16–18 minor and trace elements, and, finally, reactor-irradiated again, followed by a rapid radiochemical separation procedure (RNAA) to determine four additional elements. Major advantages of NAA are: (1) its simultaneous multielement capability; (2) the relative freedom from reagent and laboratory contamination; (3) the absence of major matrix effects; and (4) an adequate sensitivity for most elements of interest. Ranges of concentrations by INAA and RNAA in selected control tissues and interelement correlations in control brain are presented to illustrate results obtained by the procedure. Longitudinal studies of tissues from Alzheimer’s disease (AD) and amyotrophic lateral sclerosis (ALS) patients are still in progress.     

Effect of calcium,copper, and zinc levels in a rapeseed meal diet on mineral and trace element utilization in the rat

Mineral and trace element interactions were studied in a balance trial with rats. Calcium, copper, and zinc were supplied to a rapeseed meal diet in a factorial design. Animals were fedad libitum, and absorption, excretion, and retention of the elements were evaluated either as fractions of total intake or in relation to nitrogen retention to account for differences in food intake and lean body mass increment. The intrinsic content of minerals and trace elements was sufficient to support growth at a rate that could be expected from the rapeseed protein quality. However, when calcium was included in the diet, the intrinsic dietary level of zinc appeared to be limiting, despite the fact that the zinc level was twice the recommended level. Additional zinc supply reversed growth impairment. This calcium-zinc interaction is believed to be owing to the formation of phytate complexes. Calcium addition influenced the calcium, phosphorus, magnesium, zinc, and iron—but not the copper—balances. The addition of calcium reduced the availability of the intrinsic zinc, whereas no effect was seen in the zinc-fortified groups. The availability of intrinsic copper was in a similar way significantly impaired by addition of dietary zinc, where-as copper-supplied groups were unaffected by zinc addition. Intrinsic iron availability was also dependent upon zinc addition, although in a more ambigouus way. Thus, addition of extrinsic minerals to a diet high in phytate can result in significant impairments of growth and mineral utilization.     

Two-year-old children copy more reliably and more often than nonhuman great apes in multiple observational learning tasks

Individuals observing a proficient model can potentially benefit by copying at least one of the following three elements: motor movements (i.e., actions), goals, and results. Although several studies have investigated this issue in human infants, there are still very few studies that have systematically examined great apes’ ability to spontaneously copy each of these three elements (particularly in comparison with human infants). We tested great apes and human children with eight two-target puzzle boxes—with varying levels of difficulty—to isolate the aspects that the various species may be more prone to copying. We found first trial evidence for observational learning of actions, goals, and results in children. Some copying was found for apes as well, but only if their performance was averaged across trials.     

Determination of main and trace element contents in human brain by NAA and ICP-AES methods

A study was undertaken to determine the average values for elements in normal human brain (11 individuals, age group 65–75). Twelve brain parts were selected from both hemispheres. Determinations were carried out by NAA and ICP-AES. The main elements (Na, K, Mg, Ca, Fe, P, S) and trace elements (Al, B, Co, Cr, Cu, Mn, Ni, Pb, Zn) were investigated. Quality control was ensured by using NBS Bovine Liver SRM. The results obtained with independent methods were compared, and the data show a good correlation. On the basis of these investigations, the regional distribution of elements can be given.     

Selenium in platelets

Blood and its main components are commonly used to detect states of selenium deficiency. In order to examine whether human platelets are able to provide better or additional information, improvements analytical method resulted in surprisingly narrow normal ranges for selenium and other mineral elements using neutron activation analysis (NAA) and atomic absorption spectrophotometry (AAS), and controlling thermal neutron flux, (n,γ)-cross sections, mean platelet wet wt, and water fraction of the platelets. Previously reported selenium concentrations in platelets on wet wt basis in the order of 500 ng/g—half of which had been found to derive from early bone marrow precursors using⁷⁴Se-selenite—were reproduced by NAA and AAS. However, with the new analytical method the selenium concentrations showed a narrower normal range than that of plasma. Moreover, platelet selenium did not in all cases correlate with plasma selenium. Cellular tissues such as platelets should, therefore, help to detect latent states of selenium deficiency.     

Preliminary study of the distribution of the toxic elements As,Cd, and Hg in human hair and tissues by RNAA

In order to study the relationships between trace element concentrations of hair and internal body burdens, a radiochemical NAA technique has been used for determination of the elements As, Cd, and Hg in autopsy samples of liver, kidney-cortex, lung, and hair from 24 male persons who died by accident. High significant positive correlations were observed between the As concentration in hair and in kidney-cortex, and between Cd and Zn concentrations in kidney-cortex. The contents of Cd, both for lung and kidney-cortex, were related to the smoking habits of the subjects.

     

Impacts of land use and water quality on macroinvertebrate communities in the Pearl River drainage basin,China

The East River (Dong Jiang), a major tributary of the Pearl River (Zhu Jiang, the second largest river in China by discharge), is situated in southern China, which has the highest rates of urbanization and development on Earth. The East River also provides 80% of Hong Kong’s water supply. However, there have been no ecological studies to examine the combined impacts of changes in land use and water quality degradation on this river ecosystem. We tested the hypothesis that land-use disturbance and water quality degradation would significantly reduce benthic biodiversity in the East River by investigating macroinvertebrate community composition and relating it to data on water quality and catchment condition. The percentage of total impervious area within each catchment (%TIA—an indicator of land-use disturbance) was negatively related to a composite water quality index—the ERWQI—we developed for the East River. Modeling by partial least squares projection to latent structures (PLS) showed that family richness and relative abundance index (RAI) of macroinvertebrates were strongly influenced by both %TIA and ERWQI. Multi-response permutation procedure (MRPP) tests showed highly significant differences in family richness composition and RAI of macroinvertebrates among sites in the upper, middle, and lower course of the East River. MRPP also revealed differences in the family richness composition of nighttime drift samples between upper and middle site groups. Abundance (individuals m⁻³) and total family richness of drifting macroinvertebrates at each site were positively related to %TIA (range: 1.0–8.5%), while drift biomass was negatively related to dissolved oxygen and positively related to total suspended solids. Thus, human disturbances associated with land-use changes (increasing %TIA) and nutrient inputs severely degraded ecosystem integrity and the water quality of the East River and thereby reduced aquatic biodiversity.     

Correction factors used for estimating prey biomass in the diet of American minkMustela vison

Feeding experiment on nine feral minkMustela vison Schreber, 1777 was carried out to find differences in digestibility of particular prey types. The values of correction factors (CF), which show the ratio between consumed prey biomass and undigested remains, were calculated for seven food types. The experiment revealed that results obtained by commonly used percentage of occurrence methods differed from the real intake of food. Food types which were intensively digested were underestimated by percentage of occurrence methods and prey which had hardly digestive elements of their body were overestimated. The calculated values of CF are as follows: crayfish — 14.8, fish — 30.8, frog — 61.3, small passerine bird — 17.2, chicken — 41.3, rodent — 17.3, egg — 687.5. The variability in CF values did not depend on mink individuals but could be explained by the mean weight of prey items eaten by mink. The positive correlation between the prey size and its digestibility was recorded for crayfish, fish and chicken. The biomass of frog, passerine and rodent remains was not related to the body mass of eaten prey. The use of evaluated correction factors enables more accurate estimates of the food composition of wild living mustelids.     

Cadmium and cardiovascular diseases: cell biology,pathophysiology, and epidemiological relevance

Today cardiovascular diseases (CVDs) are the killer number one world wide. In 2004 an estimated 17.1 million people died due to CVDs and this number will further increase to an estimated 23.6 million by 2030. Importantly, currently known risk factors, like hypertension, and hypercholesterolemia, can only be made responsible for about 50–75% of all CVDs, highlighting the urgent need to search for and define new CVD risk factors. Cadmium (Cd) was shown to have the potential to serve as one such novel risk factor, as it was demonstrated—in vitro, in animal studies, and in human studies—that Cd causes atherosclerosis (the basis of most CVDs). Herein, we discuss the molecular and cellular biological effects of Cd in the cardiovascular system; we present concepts on the pathophysiology of Cd-caused atherosclerosis, and provide data that indicate an epidemiological relevance of Cd as a risk factor for CVDs.     

An evaluation of thermal and epithermal neutron activation analysis compton suppression methods for biological reference materials

For neutron activation analysis (NAA), the usual matrix problems of sodium, chlorine, and bromine are well known to give rise to high backgrounds that inhibit the determination of several trace elements for short-lived or medium-lived NAA. For long counting times in long-lived NAA, very low backgrounds are required to achieve good sensitivities. We have investigated the use of thermal and epithermal NAA in conjunction with Compton suppression to determine several elements such as arsenic, antimony, cadmium, and mercury, at the level of a few nanograms. The values of these techniques are discussed in contrast to the standard radiochemical methods.     

Generalization of the variance-covariance method for microdosimetric measurements

The variance method of microdosimetric measurements and its extension, the variance-covariance method, permit the determination of an essential parameter of radiation quality, the dose mean event size,y _d. The methods have — among other advantages — the feature that they permit measurements for smaller simulated sites than the conventional single-event technique. It is, therefore, desirable to employ them also for the determination of further moments of the distribution ofy. The formulae for the first three moments are here derived both for the case of constant dose rate and of fluctuating dose rates. A second article will use the same mathematical approach to deduce formulae that remain valid even if there are slow changes of the ratio of dose rates in the two detectors for the variance-covariance method. A third article will explore — in terms of microdosimetric data — the applicability of the formulae.     

Serum Copper,Zinc, and Magnesium Levels in Patients with Chronic Fluorosis

Although there are many studies on effect of fluoride on trace elements in experimental animals, few studies exist on serum trace elements levels in patients with endemic fluorosis. We aimed to determine the serum levels of trace elements including serum copper (Cu), zinc (Zn), and serum levels of minerals including calcium (Ca), phosphorus (P), magnesium (Mg), sodium (Na), potassium (K) in patients with endemic fluorosis. The study group consisted of 30 patients with endemic fluorosis (17 females, 13 males, mean age 33.53 ± 9.85 years). An age, gender, and body mass index matched 30 healthy volunteers comprised control group (21 females, ten males with a mean age 33.93 ± 7.39 years). Urine fluoride levels of chronic fluorosis patients were significantly higher than that of control subjects as expected (1.92 ± 0.10 mg/l vs. 0.41 ± 0.09 mg/l, respectively; P < 0.001). Serum Cu levels (89.14 ± 16.77 μg/dL vs. 102.69 ± 25.04 μg/dL, respectively, P = 0.017), serum Zn levels (77.98 ± 20.58 μg/dL vs. 94.57 ± 35.87μg/dL, respectively, P = 0.032), and serum Mg levels (1.92 ± 0.18 mg/dL vs. 2.07 ± 0.31 mg/dL, respectively, p = 0.022) was significantly lower in chronic fluorosis patients than in controls. There were no statistically significant differences between the fluorosis group and control group with respect to serum levels of Na, K, Ca, and P. We concluded that chronic fluorosis is associated with reduced serum levels of Cu, Zn, and Mg.     

Reference values for the concentrations of As,Cd, Co,Cr, Cu,Fe, I,Hg, Mn,Mo, Ni,Pb, Se,and Zn in selected human tissues and body fluids

This report attempts to formulate reference ranges of elemental concentrations for 15 trace elements in selected human tissues and body fluids. A set of samples consisting of whole blood, blood serum, urine, milk, liver, and hair were chosen and considered for 15 elements of biological significance: As, Cd, Co, Cr, Cu, F, Fe, I, Hg, Mn, Mo, Ni, Pb, Se, and Zn. The results represent wholly or partially data received from 40 countries of the global regions of Africa, Asia, Europe, North, South, and Central America, Australia, and New Zealand. This survey, even if qualitative, has been useful in demonstrating certain trends of trace-element scenarios around the world. It is of course recognized that both diet and environment exert a strong influence on the distribution pattern of several elements, such as As, Cd, Mn, Pb, Se, and Zn. A limited comparison of the available information on soil status of different countries reflected some interesting associations for elements, such as Mn and Zn. Importantly, this study revealed that only a few countries were in a position to identify a reasonable amount of data on samples requested for this project. Regretably, for a number of countries, any dependable data for even such essential elements as Cu, Fe, and Zn were not available. In view of the nutritional importance of many elements, the time is ripe for concerted efforts by intergovernmental agencies to initiate investigations or commission task forces/projects to generate reliable reference data for selected global regions, which sadly lack data of any kind at present.     

Trace-element analysis by charged-particle-induced reactions as a tool for physicians and chemists

The object of this article is to apprise physicians and chemists of nuclear analytical techniques and, in particular, of ion beam analysis (PIXE and PIGE) for the purpose of application to the clinical diagnostic method. The feasibility of the technique, sampling, and sample preparation for trace element analysis in biological and biomedical samples has been described previously (1–3). Analysis data from normal human blood samples and biomedical samples by ion beam reactions have been compared at the end. Emphasis will be placed on the use of the analytical technique on determination of the range of trace and toxic elements in human blood samples.     

Rapid and direct determination of selenium, copper, and zinc in blood plasma by flow injection-inductively coupled plasma-mass spectrometry

A flow injection-inductively coupled plasma-mass spectrometry (FI-ICP-MS) with a simple sample preparation procedure was developed for the determination of selenium, copper, and zinc in blood serum/plasma. A serum/plasma sample was filtered through a 0.45-μm membrane filter and diluted with a mixture of trace elements in a standard solution (9∶1, v/v). Measurement of the reference serum sample confirmed the accuracy of our method for selenium, copper, and zinc concentration. In the case of blood plasma samples obtained from six healthy adult males, the selenium, copper, and zinc concentrations were similar to those of a typical healthy male in Japan. These results suggest that the sample prepartive procedure coupled with FI-ICP-MS can be used for the routine determination of selenium, copper, and zinc in human blood serum/plasma.     

Rapid and simple determination of selenium and other trace elements in very small blood samples by XRF

Selenium and other trace elements (Cu, Zn, Br, and Rb) were determined in very small (0.75 μL) human serum and mice whole blood samples, by an XRF method. Accurate results of elemental concentration were obtained without the need of exact volume measurement, because of the backscatter correction used. The XRF method is highly sensitive (M.D.L.=0.06, 0.13, 0.09, 0.07, and 0.05 ppm for Se, Cu, Zn, Br, and Rb, respectively), rapid (counting time—100 s/sample), easy to perform and therefore suitable for routine trace element analyses. The results obtained are in good agreement with the values reported in the literature.     

The effects of diet on plasma and yolk steroids in lizards (Anolis carolinensis)

Steroids present in egg yolk have been shown to vary as a resultof numerous social and environmental influences and to produceboth positive and negative phenotypic outcomes in offspring.In the present study, we examined how quality of the diet affectsplasma and yolk steroids in the green anole (Anolis carolinensis),a lizard species with genotypic sex determination. We documentedthe effects of body condition on plasma testosterone (T) andcorticosterone (CORT)—steroids with frequently opposingeffects—in breeding females and on the T and CORT contentof their eggs. We chose to manipulate body condition via dietbecause resource availability is a relevant, fluctuating variablein the environment to which females can be expected to respond.Field-collected females were housed in the laboratory and kepton either a reduced, standard, or enhanced diet (differing innutritional quality and/or quantity) for ten weeks. Althoughfemales did not differ in body condition at the beginning ofthe study, we found these diet regimes effective in producingfemales that differed in condition by the end of the study.Females on diets of enhanced quality were in better condition,produced more, but not heavier, eggs, and had higher plasmaT concentrations than did females on a standard diet or oneof reduced quality. There was also a significant positive relationshipbetween laying sequence of eggs and yolk T for females on dietsof enhanced quality, but not for the females on diets of standardor reduced quality. There were no effects of quality of dieton CORT in plasma or yolk, but yolk T and yolk CORT exhibiteda strong positive correlation irrespective of treatment. Femaleson diets of reduced quality did not differ from females on standarddiets either with respect to reproductive output or to endocrineprofiles, in spite of being in worse body condition. These resultsdemonstrate that females’ body condition, physiology,and reproductive output can be manipulated by quality of diet,and that changes in deposition of yolk steroids in responseto diet may be minimal.     

Apes and Tricksters: The Evolution and Diversification of Humans’ Closest Relatives

The evolutionary history of humans comprises an important but small branch on the larger tree of ape evolution. Today’s hominoids—gibbons, orangutans, gorillas, chimpanzees, and humans—are a meager representation of the ape diversity that characterized the Old World from 23–5 million years ago. In this paper, I briefly review this evolutionary history focusing on features important for understanding modern ape and human origins. As the full complexity of ape evolution is beyond this review, I characterize major geographic, temporal, and phylogenetic groups using a few flagship taxa. Improving our knowledge of hominoid evolution both complicates and clarifies studies of human origins. On one hand, features thought to be unique to the human lineage find parallels in some fossil ape species, reducing their usefulness for identifying fossil humans. On the other hand, the Miocene record of fossil apes provides an important source for generating hypotheses about the ancestral human condition; this is particularly true given the dearth of fossils representing our closest living relatives: chimpanzees and gorillas.