Environmental and biochemical trace-metal speciation studies by radiotracers and neutron activation analysis

Although knowledge of the total concentrations of trace metals in the environment and living organisms is still the essential starting point for any toxicological evaluation, it is, however, not sufficient to explain the mechanisms responsible for retention and toxic effect of trace metals. Differentiation between their chemical and biochemical forms is necessary. The need to resolve the total concentration of trace metals into single chemical species poses great experimental difficulties and imposes the use of very sensitive analytical techniques for trace metal determinations after specific preseparation procedures of the different chemical species. Thus, once the chemical or biochemical metal species have been selectively isolated, the speciation becomes merely an analytical problem, which requires high sensitivity and accuracy, as well as the evaluation of matrix effects, blanks, contamination, loss, and sampling. This paper describes the use of nuclear and radiochemical techniques related to chemical and biochemical speciation problems at the Joint Research Centre, Ispra, with carrier-free radiotracers and radiochemical neutron activation analysis.     

Determination of selenium in canadian food items by cyclic instrumental neutron activation analysis

Instrumental neutron activation analysis (INAA) and pseudocyclic INAA (PCINAA) have been used to determine the selenium content of a variety of Canadian food items. Use of the 162-keV gamma ray of short-lived^77mSe in INAA allowed relatively simple and rapid determinations and was suitable for many of the foods. PCINAA was found to give lower detection limits and was used for the low-selenium food samples. Both internal and external quality assessments were used to evaluate and assure the accuracy and precision of the methods developed.     

Vanadium determination at the ultra-trace level in biological reference materials and serum by radiochemical neutron activation analysis

In order to help resolve present inconsistencies of two orders of magnitude or more in reported levels of vanadium in human serum and blood, a totally postirradiation radiochemical neutron activation analysis (NAA) method was further developed and applied to some pertinent nanogram and subnanogram reference materials. In particular, the second generation human serum reference material of Versieck was found to contain a value of 0.67±0.05 ng/g dry wt., corresponding to 0.061±0.005/4/ (see Table 1) ng/mL original fresh serum. Results are also reported for some other appropriate CRMs. Additionally, a small-scale study in 10 normal subjects (5 m, 5 f) revealed levels similar to those in the serum reference material and in agreement with the lowest data reported in the literature. Discussion of pitfalls of vanadium determination and the use of reference materials is included.     

Comparison of SR-excited X-ray fluorescence analysis with neutron activation analysis for hair and fiber

Human scalp hair and some kinds of vegetable and animal fibers were analyzed by means of the SR excited X-ray fluorescence method (SRXFA) and the neutron activation method (NAA). Human hair samples collected from five males and five females were washed by the IAEA method prior to analysis. In the SRXFA analysis, samples were excited by monochromated X-rays. Fluorescence X-rays were measured by an Si(Li) detector. The elements detected in all hair samples were S, Ca, Cu, Fe, Zn, Br, and Sr. The elements K, Ti, Cr, Mn, Ni, Se, Hg, and Pb were also detected in several samples. After SRXFA analysis these same samples were analyzed by the NAA method. Elements such as Cu, Zn, and Br were detected by both methods, and their relative concentrations show a good agreement of variation between individuals. However, Pb was only detected by SRXFA, and Na, Au, and Sb were only detected by NAA. Therefore, these two methods are complementary to each other for trace element analysis.     

Investigation of selenium distribution in subcellular fractions of human liver by neutron activation analysis

Selenium is an important and essential trace element to living systems. In the article, two methods of instrumental neutron activation analysis and hydride generation-atomic fluorescence spectrometry were applied to determine Se in biological samples and the accuracy was evaluated by several reference materials. The subcellular distribution of selenium in human liver samples, which were obtained from normal subjects who had an accidental death, was investigated by differential centrifugation combined with INAA. Selenium was mainly enriched in mitochondria, nuclei, and cytosol. Almost half of the total Se content existed in nuclei as a result of the large amount in liver and the high Se concentration. Generally, the highest Se concentration in the mitochondrial fractions of each liver sample suggested that Se had important functions in this liver component.     

Study of physiopathological phenomena in dental enamel by neutron activation analysis

An epithermal neutron activation method is used to determine the concentration of mineral elements in human dental enamel. A large number (252) of samples from ancient and modern origins are analyzed. The analytical results are mathematically processed using a statistical multivariant method. This allows to differentiate deciduous from permanent teeth and decayed from sound enamel. It is also possible to distinguish the teeth coming from two different necropoles. The origin and the localization of determined elements in the mineralized part, or in the aqueous-organic part, of enamel is suggested. Their role, as witnessed in the physiopathological phenomena of dental enamel, is discussed.     

A survey of trace elements in fresh-water fish and rice along the Han River by neutron activation analysis

For a case study of environmental pollution, radiochemical neutron activation analysis (RNAA) was applied to the crucian and rice collected along the Han River. The crucian was analyzed for three times in 1973, 1987, and 1990. Sixteen trace elements (Hg, Cd, As, Br, Cu, Na, K, Se, Cr, Hf, Rb, Fe, Zn, Co, La, and Cs) were determined by RNAA using distillation and diethyldithiocarbamate extraction methods. Contents of Na, K, Se, Hf, Fe, Zn, and Co were almost constant regardless of the sampling place and year. The contents of the other elements showed increasing trends down river, especially in the first investigation. At the lower part of the river, the contents showed decreasing trends with the time of sampling, especially during the first two investigations. These trends were typical for Hg and Cd. Rice was analyzed by the same method for 12 elements, and the results showed no regional trends, but have decreased after 1973.     

A new microcomputer-controlled neutron activation and analysis system

A microcomputer-controlled irradiation and measurement system and a microprocessor-controlled sample changer have been installed at the SLOWPOKE-2 Facility at the Royal Military College of Canada (RMC). These systems can provide the gamut of instrumental neutron activation analysis (INAA) techniques for the analyst. Custom software has been created for system control, data acquisition, and off-line spectral analysis using programs that incorporate Gaussian peak-fitting methods of analysis. The design and use of the equipment is discussed, and the performance is illustrated with results obtained from the analysis of marine sediment and biological reference materials.     

Determination of trace elements in tissue of human uterine cancer by instrumental neutron activation analysis

In this article, the low-temperature freeze-drying pretreated technique and instrumental neutron activation analysis were used to determine 29 trace elements in samples of human uterine cancer tissue. The content of these trace elements in uterine cancer tissue was compared with that in cervicitis tissue and in healthy tissue, respectively. Preliminary results indicated that significant differences in contents of Au, I, and Se were observed in these tissues.     

Multielement compositions of marine phytoplankton samples from coastal areas of japan by instrumental neutron activation analysis

Phytoplankton samples were collected during spring bloom of diatoms from three coastal areas of Japan using a NORPAC P-25 net (25-Μm opening) with a NGG52 prenet (335-Μm opening), and 25 major and trace elements have been analyzed by INAA. Concentration ranges of analyzed phytoplankton samples are much wider than the concentration ranges compiled by Bowen (1979) except for As, and data of marine phytoplankton samples for Br, Sb, Hf, Sc, La, Ce, Sm, and Eu were not included in the compilation. The 25 analyzed elements have been categorized into three groups: elements showing positive correlation with Br, positive correlation with Al, and no positive correlation with Br or Al. The marine phytoplankton samples have been plotted on a Masuzawa-Koyama-Terazaki (MKT) plot and it proved that the MKT plot is applicable to marine phytoplankton samples.     

An elemental correlation study in cancerous and normal breast tissue with successive clinical stages by neutron activation analysis

Influence of trace elements in body metabolism and their physiological importance in various diseases have motivated their accurate and quantitative determination in biological tissues and fluids. Instrumental Neutron Activation Analysis (INAA) using short and long term irradiation has been employed to determine five minor elements (Cl, K, Na, Mg, P) and 15 trace elements (As, Br, Co, Cr, Cs, Cu, Fe, Hg, Mn, Rb, Sb, Se, Sc, Sr, and Zn) in cancerous and normal breast tissue from 30 patients of four clinical stages. Several elements show enhancement in cancerous breast tissue. Selenium shows maximum enhancement of 94.7% followed by K (81.6%), Sc (66.7%), Cu (58.2%), Na (48.5%), P (44.4%), and Zn (39.2%). Some element, such as Fe, Cr, and Mn, are depressed by 30.8, 30.1, and 12.8%, respectively. These elements compete for binding sites in the cell, change its enzymatic activity and exert direct or indirect action on the carcinogenic process accelerating the growth of tumors. This is further evidenced by histopathological examination of cancerous cells showing poor cytological differentiation. An attempt has been made to correlate trace element concentrations of Se, Cu, Zn, Rb, Br, Hg, As, Co, Fe, Cr, and Mn and the ratios of Se/Zn, K/P, Cu/Zn, Na/K, and Se/Fe with the clinical stages of cancer. Inhibition of enzymatic activity caused by variation in trace element concentrations results in immunological breakdown of the body system.     

Determination of aluminum by neutron activation analysis in human lung tissue and in chemicals for dialysis of uremic patients

Aluminum (Al) determination in human lung tissue, in chemicals for dialysis fluids, and in commercially available dialysis solutions is carried out using both Instrumental and Radiochemical Neutron Activation Analysis (INAA and RNAA). For some matrices, pre-and post-irradiation Al separations are tested. Chelex 100 resin and HDEHP, this latter adsorbed both on teflon and polyurethane foam, are employed for the pre-irradiation Al separations. The postirradiation procedures are performed using roughly the same schemes; the conventional Al precipitation as hydroxide is also carried out. Al values found in lungs of workers exposed to Al containing dust appear to be much higher than those found for unexposed people. Chemicals analyzed seem pure enough to give suitable dialysis solutions; for commercially available dialysis fluids, a 10-fold reduction of Al content should be convenient.     

Content of trace elements in the respirable fractions of the air particulate of urban and rural areas monitored by neutron activation analysis

The concentrations (ng/m³) of more than 30 trace elements have been determined in the total air particulate matter and in the sizesegregated fractions collected in urban, industrialized, and rural residential areas in northern Italy by means of a multistage inertial impactor with the PM10 inlet. All measurements have been carried out by instrumental neutron activation analysis, except for Pb and Cd, which have been determined by electrothermal atomic absorption spectroscopy. Analytical quality assurance procedures have been developed with special regard to blanks, reagents, and sampling. Total concentrations and the granulometric distribution found in the different locations are reported and compared.     

An environmental research on trace elements in freshwater fish by neutron activation analysis

For a case study of environmental contamination, radiochemical activation analysis has been applied to the crucians collected in the Han River. Sixteen trace elements (Hg, Cd, As, Br, Cu, Na, K, Se, Cr, Hf, Rb, Fe, Zn, Co, La, and Cs) were separated into three groups using distillation and diethyldithiocarbamate extraction methods, and their contents were determined by a single comparator method. Compared with the values 15 years ago, the values for mercury and cadmium have been drastically decreased at the middle and lower part of the river, but no typical change is found in other elements.     

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.     

Simultaneous determination of 76As, 122Sb and 153Sm in Chinese medicinal herbs by epithermal neutron activation analysis

Optimal conditions for the simultaneous determination of As, Sb and Sm in Chinese medicinal herbs using epithermal neutron activation analysis were investigated. The minimum detectable concentrations of 76As, 122Sb and 153Sm in lichen and medicinal herbs depended on the weight of the irradiated sample, and irradiation and decay durations. Optimal conditions were obtained by wrapping the irradiated target with 3.2 mm borated polyethylene neutron filters, which were adopted to screen the original reactor fission neutrons and to reduce the background activities of 38Cl, 24Na and 42K. Twelve medicinal herbs, commonly consumed by Taiwanese children as a diuretic treatment, were analysed since trace elements, such as As and Sb, in these herbs may be toxic when consumed in sufficiently large quantities over a long period. Various amounts of medicinal herbs, standardised powder, lichen and tomato leaves were weighed, packed into polyethylene bags, irradiated and counted under different conditions. The results indicated that about 350 mg of lichen irradiated for 24 h and counted for 20 min following a 30-60 h decay period was optimal for irradiation in a 10(11)n/cm s epithermal neutron flux. The implications of the content of the studied elements in Chinese medicinal herbs are discussed.     

Determination of antimony in natural waters by preconcentration on a chelating sorbent followed by instrumental neutron activation analysis

Antimony was preconcentrated from natural waters on thionalide-loaded acrylic polymer (Bio-Beads SM-7) from 0.5 m HCl solution. Prior to the preconcentration, Sb(V) was reduced to Sb(III) with potassium iodide. The antimony retained on the resin was determined by neutron activation and γ-spectrometric measurement of¹²²Sb (564 keV). The lower limit of detection was 0.023 μg/L for a 100-mL sample.     

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.     

Neutron activation analysis of biological samples with a preirradiation chemical separation

A preirradiation separation procedure has been developed to separate Al, Cu, Mn, and V from biological materials. Chelex-100 resin is used as the separation medium, and the resin is irradiated directly. Three NIST biological Standard Reference Materials and five samples of human blood serum, obtained under carefully controlled conditions, have been analyzed by NAA following this separation.     

Determination of mercury in human serum and packed blood cells by neutron activation analysis

A method is described for the determination of mercury in human blood serum and packed blood cells employing neutron activation analysis. Great attention was devoted to the collection and manipulation of the samples. The accuracy and precision of the method were tested by analyzing biological reference materials and by comparing the concentrations measured in a number of serum samples to those obtained by another, independent technique (cold vapor atomic absorption spectrometry) in the same samples. The article reports the levels measured in blood serum and packed blood cells samples from 15 adult volunteers, as well as the figures determined in a “second-generation” biological reference material (freeze-dried human serum), prepared and conditioned at the University of Ghent.