Nuclear and atomic analytical techniques in environmental studies in South America

The use of nuclear analytical techniques for environmental studies in South America is selectively reviewed since the time of earlier works of Lattes with cosmic rays until the recent applications of the PIXE (particle-induced X-ray emission) technique to study air pollution problems in large cities, such as São Paulo and Rio de Janeiro. The studies on natural radioactivity and fallout from nuclear weapons in South America are briefly examined.

     

Intercomparison of techniques available at INETI in the analysis of two IAEA candidate research materials

Under contract with the IAEA, the epiphytic lichenEvernia prunastri was collected to prepare a multielement lichen reference material for quality assurance of environmental studies. An intercomparison run on trace and minor elements in this candidate research material (IAEA-336) was organized in which six analytical groups of the National Institute of Engineering and Industrial Technology (INETI) took part. INAA, PIXE, XRF, AAS, and ICP-ES were applied. The results obtained by different methods are compared, and their complementarity is discussed. As a quality control, the IAEA cabbage research material (IAEA-359) was analyzed. The results agree quite well with the estimated values given by the IAEA.     

Charged-particle activation analysis of biological material

Charged-particle activation analysis offers a number of interesting possibilities for the determination of trace elements in biological material. It allows the determination of those elements that are difficult or impossible to determine by neutron activation, such as Li, B, Al, Si, V, Cr, Ni, Cd, Sn, Tl, and Pb. Up to now, protons have been successfully applied to samples of both vegetale and human origin. A number of difficulties have to be overcome, one of which is excessive heating of the samples owing to the limited range of the charged particles, thus giving rise to a high energy deposition in a small volume. Moreover, the sample composition has to be known to allow the calculation of the range of the particles. an interesting alternative has been proposed using an internal standard together with a standard additions procedure. Proton activation analysis was tested on a wide variety of reference materials, giving evidence that accurate results can be obtained for many trace elements, even when applying a purely instrumental method. Thus, the method can also be applied in the certification of reference materials, since nuclear methods are independent of chemical properties of the sample.     

Levels of some trace elements in selected autopsy organs,and in hair and blood samples from adult subjects of the Italian population

This study, which is part of a research program for the determination of trace element reference levels in various human tissues for the Italian population, presents the concentrations of Se, Hg, Cr, Cs, Sc, Rb, Zn, Fe, Co, and Sb in lung, liver, spleen, and kidney autopsy samples taken from 14 adult subjects of the Italian population who died from accidental causes. Concentrations of the same trace elements are given also for blood and hair samples taken from subjects of the general Italian population and of a population group living in a small coastal town that has an average annual fish consumption well above the national average. The analytical method used was Instrumental Neutron Activation Analysis. The levels and distribution of the trace elements in the various human organs examined are analyzed and discussed.     

Multielement determination in rice,wheat, and barley by instrumental neutron activation analysis

INAA has been used for the determination of Na, Mg, Al, Cl, K, Sc, Cr, Mn, Fe, Co, Cu, Zn, As, Se, Br, Rb, Sr, Mo, and W in grains of rice, wheat, and barley, which were collected from different plant fields in Iraq. Samples and standards were irradiated in the IRT-5000 reactor, at neutron fluxes of 2 × 10¹³ cm⁻²·s⁻¹ and 3.2 × 10¹¹ cm⁻²·s⁻¹. Interferences of photopeaks with each other were considered, and reaction interferences were calculated and determined experimentally. Accuracy of our method was assessed by the analysis of IAEA standards Wheat Flour and Bovine liver. A good agreement has been achieved between the present results and recommended values. The precision and detection limit were determined for all elements in all types of grain.     

Determination of selenium in duplicate diets of residents of Pinhel,Portugal, by neutron activation

A rapid cyclic instrumental neutron activation analysis (CINAA) method has been used to determine the selenium content of 27 duplicate diet samples from each of the 27 districts surrounding Pinhel, Portugal. The accuracy and precision of the CINAA method have been evaluated by analyzing certified reference materials and observed to be within ±5–10% for samples containing at least 40 ppb of selenium. The detection limit has been found to vary between 26–42 ppb selenium depending on the sample composition. The average daily dietary intake has been calculated as 37 μg of selenium per day.     

Metabolic deposition of selenium and cadmium into the hair and other tissues of the guinea pig

To better understand the significance of hair trace-element measurements and their relationships with the trace-element levels in body organs and fluids, a series of controlled animal experiments were conducted in which several trace elements were periodically measured during a 90-day chronic exposure to selenium and cadmium. Chronic selenium exposure appeared to be reflected by elevated selenium levels in the hair, kidneys, and liver. Chronic cadmium exposure, although reflected by kidney and liver elevation, appeared not to be reflected by corresponding increases in its concentration in the hair.     

Study of correlation of se content in human hair and internal organs by INAA

The correlations of essential element Se between human hair and kidney-cortex, liver, and lung from the same subjects were investigated by instrumental neutron activation analysis, using the reaction⁷⁶Se (n, γ)^77mSe, for 24 Chinese autopsies. The concentration of Se is higher in kidney-cortex (2.04–5.36 mg/kg) than in liver (0.73–2.29), lung (0.50–1.85), and hair (0.37–1.43). It is important to know that there are significant relationships of Se concentration between hair and the other three internal organs. The correlation coefficient by linear regression analysis are 0.639, 0.570, and 0.635 for liver, lung, and kidney-cortex, respectively; and theP values are all less than 0.01 for the three tissues.     

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.     

Identifying sources of groundwater pollution using trace element signatures

A simple receptor modeling approach has been applied to groundwater pollution studies and has shown that maker trace elements can be used effectively in source identification and apportionment. Groundwater and source materials from one coal-fired and five oil-fired power plants, and one coal-tar deposit site have been analyzed by instrumental neutron activation analysis for more than 20 minor and trace elements. In one of the oil-fired power plants, trace element patterns indicated a leak from the hazardous waste surface impoundments owing to the failure of a hypolon liner. Also, the extent and spatial distribution of groundwater contamination have been determined in a coal-tar deposit site.     

Effects of etretinate on the distribution of elements in rats

We studied in the rat the effects of the drug etretinate (Tigason), given at three doses 3, 10, and 30 mg/kg body wt for 1 mo, on the concentrations of Na, K, Ca, Mg, Fe, S, P, Cu, and Zn in the plasma, brain, thymus, heart, liver, lung, kidney, testicle, muscle, and bone. The elements were simultaneously determined in tissues after nitric acid dissolution by inductively coupled plasma emission spectrometry using a JY 48 instrument. At the dose of 3 mg/kg, etretinate did not induce any statistically significant modifications of the element distribution. At the dose of 10 mg/kg, the main observed modifications were in plasma an increase of copper (+38%) and a decrease of zinc (-25%). At the highest dose of 30 mg/kg, some variations of the concentrations of elements in tissues were observed. But, on no account did retinoids induce an alteration of the mineral composition of bone, despite obvious macroscopic bone alterations.     

Trace element content in breasts with fibrocystic disease

The trace elements antimony, bromine, cesium, cobalt, iron, rubidium, scandium, strontium and zinc were determined by instrumental neutron activation analysis in breast tissue samples with fibrocystic disease and in samples with fibroadenoma tumors. The histological lesions of each breast sample with fibrocystic disease were recorded, and a statistical analysis of the lesions in combination with the determined trace elements was carried out. The results showed that the element mean values in fibroadenoma tumors are higher than those of fibrocystic disease. Some other remarkable results of statistical examination are also presented.     

A comparative study of elemental composition of human breast milk and infant milk substitutes

Instrumental neutron activation analysis (INAA) and protoninduced X-ray emission (PIXE) analysis have been employed to determine the concentration of 13 elements in human breast milk, various infant formulas, and locally produced cereals from Nigeria, as well as from various infant formulas and natural cow and goat milk available in the UK. The study shows that if the locally produced cereal is to be used on a regular basis for babies in Nigeria, then their diet must be supplemented with essential trace elements. Furthermore, parents should be discouraged from giving their infants cow and goat milk because of the high concentration of major elements compared to human breast milk.     

Enhancement of the kidney Cd burden by SH-containing chelating agents

The accumulation of Cd in the kidneys is enhanced markedly if chelating agents that contain SH-groups like 2,3 dimercaptopropanol (BAL) are injected immediately after the metal. This is not a transient effect but persists for more than 3 d. It is less pronounced at higher chelate doses or when the pH of urine is increased. Our experiments indicate that chelating agents, which form unstable complexes at acid pH and are able to pass through the cell membrane, will cause metal accumulation in the kidneys.     

An application of INAA and PIXE on the analysis of nutritional and toxicological elements in samples of drinkable water

Multielemental detection using Instrumental Neutron Activation Analysis (INAA) and Proton-Induced X-Ray Emission (PIXE) of drinkable water of Florence (Italy) is described. The concentrations of 52 elements were measured. No chemical treatment was performed on the samples, before or after irradiation. On the basis of an appropriate combination of the two analytical techniques, a procedure for aluminum determination was developed. Results are briefly discussed from a methodological point of view.     

Study of trace elements in blood of cancer patients by proton-induced X-ray emission (PIXE) analysis

Proton-induced X-ray emission (PIXE) analysis was employed to determine the concentrations of six elements in the plasma and erythrocytes of 18 cancer subjects (15 males and 3 females) with neoplastic disorders and in 70 controls (35 males and 35 females). It was found that the concentrations of Br, K, and Zn were significantly elevated in the erythrocytes of the cancer subjects compared to the controls, whereas the concentration of Fe was significantly depressed, but with no difference observed in the concentration of Ca. In the plasma, the concentrations of Br, Cu, Ca, and K were significantly elevated, whereas the concentrations of Fe and Zn were found to be significantly depressed compared to the controls.     

Changes of concentrations of the elements Co,Cr, Sb,and Sc in tissues of persons with joint implants

Elevated levels of Co and Cr were found in several organs of deceased implant bearers (CoCr-alloy/polyethylene joint prostheses) by means of instrumental and radiochemical neutron activation analysis as compared to normal persons. For comparative purposes, concentrations of the elements Co, Cr, Sb, and Sc were measured in heart, kidney, liver, and spleen of the patients and normal persons. For Cr determination, a new radiochemical separation technique with sufficiently low determination limit was employed. The importance of such investigations for studying possible carcinogenic effects of corrosion products and wear particles of metallic prostheses is mentioned.     

Toxic heavy metals and other trace elements in foodstuffs from 12 different countries

A research program related to the assessment of toxic heavy metals and essential trace elements in foodstuffs has been carried out in 12 countries under the auspices of the IAEA. The main purpose of this program was to obtain data on the elemental concentrations of potentially toxic elements in foodstuffs in various countries, and to compare them with the maximum permissible levels specified in national legislation and international guidelines. High-priority elements for this study were As, Cd, Cr, Pb, Hg, and Se. Also of interest, but of lower priority, were Sb Cu, and Zn/ Emphasis was placed on the use of nuclear and nuclear-related analytical techniques, complemented by conventional methods, and on quality assurance.     

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.