Comprehensive RNAA of cadmium,cobalt, nickel,and copper using109Cd,57Co,and reactor-produced67Cu as radioisotopic yield monitors

An existing radiochemical NAA procedure for Cd, Co, and Cu was improved to allow determination of individual radiochemical yields by the radioisotopic tracer technique, thus eliminating errors owing to variable recovery.¹⁰⁹Cd was used as tracer for Cd determination via¹¹⁵Cd/^115mIn,⁵⁷Co for Co via⁶⁰Co, and potentially for Ni via⁵⁸Co, whereas as a novelty⁶⁷Cu, produced by reactor irradiation of ZnO of natural isotopic composition (by the⁶⁷Zn [n,p]⁶⁷Cu reaction) was used for Cu via the indicator nuclide⁶⁴Cu. The simple production and purification of⁶⁷Cu by anion exchange is described. Results for biological RMs are given and discussed.     

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.     

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.     

Interlaboratory analysis of IRM NSC-21 Compost Vitahum

The preparation of internal reference material, NSC-21 Compost Vitahum, including its stabilization, homogeneity testing, and evaluation of an interlaboratory comparison in which 19 laboratories took part using several analytical methods is described. From the results of the intercomparison, consensus values were derived for the contents of Cd, Cu, Ni, Pb, and Zn, whereas for As, Co, Cr, Fe, Hg and Mn, information values were derived. Bimodal distribution of the As and Cr results was obtained, presumably because of incomplete dissolution of the elements from the matrix if insufficiently aggressive decomposition procedures were employed. Some problems encountered were elucidated by application of neutron activation analysis (NAA) in its nondestructive and destructive (radiochemical) modes.     

RNAA as compared to ICP-MS for the analysis of normal human serum

The merits of radiochemical neutron activation analysis (RNAA) and inductively coupled plasma mass spectrometry (ICP-MS) are critically discussed for the determination of trace and ultratrace elements in normal human serum. For RNAA, two semiautomated procedures, allowing the determination of up to 18 elements, are briefly described. ICP-MS has a series of interesting features for the determination of trace elements. Matrix and spectral interferences can mostly be avoided or corrected for. After a simple 5- or 10-fold dilution and addition of an internal standard, more than 20 elements can be measured precisely and accurately.     

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.

     

Metal Interrelationships in Plant Nutrition: I. EFFECTS OF SOME METAL TOXICITIES ON SUGAR BEET, TOMATO, OAT, POTATO, AND MARROWSTEM KALE GROWN IN SAND CULTURE

1.Sugar beet, tomato, potato, oat, and kale were grown in sandcultures with additions of several ‘heavy’ metalsincluding Cr, Mn, Co, Ni, Cu, Zn, Pb, Cd, V, Mo in equivalentconcentrations. 2.In sugar beet Cu++, Co++, Cd++ were usually highly activein causing chlorosis mainly suggestive of iron deficiency. Theeffect of Cr depended on valency and was greater as CrO₄––.Zn++, VO₃––, Cr+++, Mn++, and Pb++ were less activein order. 3.The visual responses to Co++ and Ni++ varied greatly withthe crop tested. Cu++, however, always induced typical irondeficiency. Crop susceptibility also varied greatly. For example,Cu++ readily caused chlorosis in beet and also in tomato, andpotato, but not in oat and kale. 4. Ni++ induced symptoms resembling manganese deficiency inpotato and tomato and unusual oblique white and green bandingleaves of oat. Zn++ induced apparent manganese deficiency insugar beet and Co++ toxicity in tomato initially resembled manganesedeficiency. Ni++ and Co++ were the most toxic of the metalstested.     

Trace Metals (Cd,Co, Cr,Cu, Hg,Ni, Pb,and Zn) in Food Supplements of Marine Origin

We determined the concentrations of Cd, Co, Cr, Cu, Hg, Ni, Pb, and Zn in dietary supplements of marine origin. Four supplement categories were studied; algae, coral, krill, and shark cartilage. A direct mercury analyzer was used for Hg determinations while acid digestions and ICP-AES were used for Cr analysis and ICP-MS for the other trace metals. Algae are the supplements showing the highest concentrations of Pb, Cr, and Ni with respective means of 1.6 mg Pb/kg dry weight (d.w.), 3.2 Cr mg/kg d.w., and 8.0 mg Ni/kg d.w. Krill supplements have the highest levels of Cd, Cu, and Zn with 0.65 mg Cd/kg d.w., 63 mg Cu/kg d.w., and 50 mg Zn/kg d.w., respectively. Shark cartilage supplements show the highest levels of Hg and Co with mean concentrations of 160 μg Hg/kg d.w. and 73 ± 51 μg Co/kg d.w., respectively. No samples in our study exceeded the provisional tolerable daily intakes set by Health Canada, the joint committee of the World Health Organization/Food and Agricultural Organization, or the U.S. Environmental Protection Agency. Nevertheless, Ni and Pb in algae and Hg in shark cartilage may end up contributing to a very significant portion of the allowable daily intake—leaving little room for normal intake through food consumption and other exposure pathways.     

Minor and trace elemental contents of cancerous breast tissue measured by instrumental and radiochemical neutron activation analysis

Many minor and trace elements influence the permeability of cell membranes by competing for binding sites, and exert direct or indirect action on the carcinogenic process. Instrumental and radiochemical neutron activation analysis has been employed for the determination of more than 20 elements in normal and cancerous breast tissues of 6 patients. Most trace elements, viz., Zn, Cu, Mn, Co, Se, Br, As, Sb and Cd, are elevated in cancerous tissue, whereas lower levels are observed for Fe, Cs, I, and Sr. Similarly, concentrations of minor constituents, such as Na, K, P, Cl, and Mg, are enhanced compared to normal tissue. Several elements incorporate into the normal cell, change its enzymatic activity, and accelerate the growth of tumor.

     

Role of direct reactivity with metals in chemoprotection by N-acetylcysteine against chromium(VI), cadmium(II), and cobalt(II)

The antioxidant N-acetylcysteine (NAC) is widely used for the assessment of the role of reactive oxygen species (ROS) in various biological processes and adverse drug reactions. NAC has been found to effectively inhibit the toxicity of carcinogenic metals, which was attributed to its potent ROS-suppressive properties. However, the absence of redox activity among some metals and findings from genetic models suggested a more diverse, smaller role of oxidative stress in metal toxicity. Here, we examined mechanisms of chemoprotection by NAC against Cd(II), Co(II), and Cr(VI) in human cells. We found that NAC displayed a broad-spectrum chemoprotective activity against all three metals, including suppression of cytotoxicity, apoptosis, p53 activation, and HSP72 and HIF-1α upregulation. Cytoprotection by NAC was independent of cellular glutathione. NAC strongly inhibited the uptake of all three metals in histologically different types of human cells, explaining its high chemoprotective potential. A loss of Cr(VI) accumulation by cells was caused by NAC-mediated extracellular reduction of chromate to membrane-impermeative Cr(III). Suppression of Co(II) uptake resulted from a rapid formation of Co(II)–NAC conjugates that were unable to enter cells. Our results demonstrate that NAC acts through more than one mechanism in preventing metal toxicity and its chemoprotective activity can be completely ROS-independent. Good clinical safety and effectiveness in Co(II) sequestration suggest that NAC could be useful in the prevention of tissue accumulation and toxic effects of Co ions released by cobalt–chromium hip prostheses.     

Quantification of 26 metals in human urine samples using ICP-MSMS in a random sample collective of an occupational and environmental health care center in Aachen,Germany

Despite several studies on metal exposure in the general population, the knowledge on the background burden of distinct metals is still sparse (e.g. Cu, In, Mn, Pb, Sn, Sr, Ta, Te). While up to date reference values exist for 16 distinct metals as Biological Reference Value (BAR) or the 95th percentile for Al, As, Ba, Be, Cd, Co, Cr, Hg, Li, Mo, Ni, Pt, Sb, Se, Tl and U respectively, the background burden of the general population for the remaining elements is unknown or yet no matter of scientific counselling. We established and validated an inductively coupled plasma triple quadrupole mass spectrometry (ICP-MSMS) human biomonitoring method (HBM), that enabled us to determine 26 metals in urine. Al, As, Ba, Be, Cd, Co, Cu, Ga, Gd, Hg, In, Li, Mo, Ni, Pb, Sb, Se, Sn, Sr, Ta, Te, Tl, V and Zn were analyzed. The method was applied to 88 urine samples collected in the ambulance of the Institute for Occupational, Social and Environmental Medicine (IASU) Aachen, Germany. Patients from two major metal processing companies (steel and copper) and a more heterogenous group of occupational exposed and non-exposed persons were defined and distinguished. HBM data from about 88, in general occupationally unexposed persons against certain metals served as a collective representing the general population in first approximation. For these the 95th percentiles are reported. Significant differences of urinary metal concentrations of the employees of the two metal processing companies compared to the third group were observed among others for Cu, Cr, Ni, Mn and are discussed, thus demonstrating the usefulness of the method for both environmental and occupational purposes.     

Correlation between serum cholesterols and trace element uptake in liver,kidney, and blood of hypercholesterolemic mice

The radioactive multitracer technique was applied to the simultaneous determination of the uptake of 17 trace elements (Be, Na, Sc, V, Cr, Mn, Fe, Co, Zn, As, Se, Rb, Sr, Y, Zr, Nb, and Ru) in the liver, kidney, and blood of hypercholesterolemic model mice. The uptakes of Be, Sc, V, Cr, Fe, As, Rb, Y, Zr, Nb, and Ru in liver increased with an increasing feeding period of a cholesterol-rich diet, whereas the uptakes of Zn and Se decreased. Feeding of the diet resulted in a marked increase in serum total cholesterol, triglycerides, and low-density lipoprotein cholesterol. The metabolism of trace elements between cholesterolemic and normal mice was compared with respect to their serum cholesterol levels. A significant positive correlation was found between the concentration of serum triglycerides and liver uptakes of Cr, Fe, and As and a negative correlation for the uptake of Zn. A significant positive correlation was found between the concentrations of serum high- and low-density lipoprotein cholesterols and kidney uptakes of Cr and Rb. A negative correlation was found between the uptake of Be in the blood and the concentration of serum triglycerides. These results suggest that cholesterolemia have some specific effects on the metabolism of some elements.     

Heavy metals in water,sediments, fish and plants of river Hindon,U.P., India

We analysed the concentrations of Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn in the water, sediments, fish and plants of the River Hindon, U.P., India, at seven sampling stations, in the year 1982. Considerable variation in concentration between water, sediments, fish and plants were noted. The concentration in the water was in the order Fe > Zn > Cr > Mn > Cu > Pb > Ni > Co > Cd, in the sediments, Fe > Mn > Zn > Ni > Cr > - Co > Cu > Pb > Cd; in a fish (Heteropnuestes fossilis) Fe > Zn > Mn > Pb > Ni > Co > Cu > Cd > Cr, and in a plant (Eicchornia crassipes) Fe > Mn > Zn > Ni > Cu > Cr > Pb > Co > Cd.     

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.     

Growth and bioaccumulation characteristics of watercress (Nasturtium officinale R. BR.) exposed to cadmium,cobalt and chromium

Abstract

The aim of this study is to determine the effects of Cd, Co and Cr on the growth of watercress (Nasturtium officinale) and to determine the bioaccumulation properties of these heavy metals by the plant. N. officinale individuals were exposed to different concentrations of Cd, Co and Cr for 72 h. Relative growth rates (RGR) and bioconcentration factor (BCF) ratios were calculated for each metal concentration. RGR values of plants exposed to Co slightly increased in lower concentrations, but then decreased again. In contrast, RGR values of plants exposed to Cd and Cr decreased linearly. Significant positive relationships were observed among the concentrations of Cd, Co and Cr in N. officinale and in the culture solution. BCF ratios were highest for plants exposed to Co, and lowest for plants exposed to Cr. The most efficient uptake of Cd, Co and Cr occurred at the external solution concentrations at 0.5, 0.5 and 10 mM, respectively.     

Chromium Exposure in the Adult Population,Consuming Different Types of Smokeless Tobacco Products in Pakistan

The pervasive smokeless tobacco (SLT) consumption and diseases related to its use is a hot topic for the public discussion. In this study, concentrations of chromium (Cr) were measured in different SLT products [snuff (dry and moist), mainpuri, and gutkha] offered and used in Pakistan. The current study was also designed to assess the Cr levels in the biological (scalp hair and blood) samples of male and female subjects, age ranged from 25 to 60 years, chewing different SLT products. For comparative purpose, the healthy persons of the same age group, who did not consume any SLT products, were selected as referents. The concentrations of Cr in SLT products and biological samples were measured by electrothermal atomic absorption spectrophotometer after microwave-assisted acid digestion. The validity and accuracy of the methodology were checked by certified reference materials (CRMs). The resulted data indicated that the adult persons, who consumed different SLT products, have 2–3 fold higher levels of Cr in biological samples as compared to referent subjects (p < 0.01). The persons, who chew/sniff different SLT products, have 50–80 and 42–82 % higher levels of Cr in their scalp hair and blood samples as related to referents. The daily intake of Cr is lower as compared to the recommended value of 50–200 μg/day. It was expected that 10 g consumption of various kinds of SLT products (snuff, mainpuri, and gutkha) may subsidize 21.2–220, 17.7–122, and 18.4–273 % of the recommended daily intake of Cr, respectively.     

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.     

INAA of trace elements in colorectal cancer patients

The concentration of trace elements in samples of both colorectal cancer tumors and normal tissues of a Mexican population were irradiated for 30 s and 4 h and their elemental content were measured by instrumental neutron activation analysis. Ca, Cu, Co, I, Mg, Se, Fe, Zn, Hg, Ba, and Cr were analyzed. Alterations in Co, Fe, I, and Ba were found in tumors with respect to normal tissues.     

Artificial radionuclides in aquatic plants of the Yenisei River in the area affected by effluents of a Russian plutonium complex

The Yenisei River, one of the largest rivers in the world, is contaminated with artificial radionuclides released by one of the Russian nuclear plants, which produces weapons-grade plutonium and has been in operation for many years. The aim of the study that was conducted between 1997 and 2002 was to investigate accumulation of artificial radionuclides by aquatic plants of the Yenisei River. The aquatic plants sampled were: Potamogeton lucens (shining weed) and Fontinalis antipyretica (water moss). The -spectrometric analysis of the samples of aquatic plants for artificial radionuclides has revealed a wide spectrum of long-lived and short-lived radionuclides. Artificial radionuclides such as ⁵¹Cr, ⁵⁴Mn, ⁵⁸Co, ⁶⁰Co, ⁶⁵Zn, ¹³⁷Cs, and ¹⁵²Eu were found in aquatic plants collected both near the plutonium complex and 194 km downstream in the river. The radiochemical analysis of aquatic plants revealed strontium and isotopes of plutonium. Fontinalis antipyretica had very high concentration factors of the principal radionuclides: 14220, 3110 and 500 of ⁵¹Cr, ⁴⁶Sc and ²³⁹Np, respectively.