Dag Brune

Distribution of 23 elements in the kidney, liver and lungs of workers from a smeltery and refinery in north Sweden exposed to a number of elements and of a control group

The levels of antimony, arsenic, cadmium, caesium, chromium, cobalt, copper, gold, iron, lanthanum, lead, manganese, mercury, molybdenum, phosphorus, rubidium, scandium, selenium, silver, tellurium, tin, tungsten and zinc in the kidney, liver and lungs of autopsy specimens from exposed workers in North Sweden, as well as from a control group, have been assayed quantitatively. The workers had been exposed to several elements and their compounds, e.g. lead, mercury, arsenic and cadmium, for long periods in arsenic, lead or selenium plants and in a lead or copper smelter. The chemical analysis was by neutron activation analysis and atomic absorption spectrophotometry. Median levels of antimony, arsenic, cadmium, chromium cobalt, lanthanum, lead or selenium in kidney, liver or lungs in the exposed worker group were found to be about 2 to 16 times as great as the corresponding levels for the control group. Long biological half-life values were observed for these elements, especially in lung tissue.

Levels of antimony, arsenic, cadmium, copper, lead, mercury, selenium, silver, tin and zinc in bone tissue of industrially exposed workers

The contents of the elements antimony, arsenic, cadmium, copper, lead, mercury, selenium, silver, tin and zinc in bone tissue from autopsy specimens of the femur of workers who had been exposed to a large number of metals in a smeltery and refinery in Northern Sweden as well as of a control group have been quantitatively assayed. The analytical techniques used were atomic absorption spectrophotometry, neutron activation analysis and particle induced X-ray emission analysis (PIXE) in a proton microprobe. Increased levels of lead in the bone tissue of exposed workers compared to a non-exposed control group were observed. The median level of lead in the group of exposed workers exceeded the corresponding value of the control group about 5 times. Using the proton microprobe in the PIXE-mode, concentration profiles of copper, lead and zinc were examined within the Haversian system of the bone samples.

Multielemental assay of tissues of deceased smelter workers and controls

Concentrations of 23 elements in lung, liver and kidney from deceased smelter workers are compared with those from rural and urban controls. The analyses were made by neutron activation analysis and atomic absorption spectrophotometry. Significantly higher levels of antimony, arsenic, cadmium, chromium, cobalt, lanthanum, lead and selenium were found in the smelter workers lungs (n = 85) compared with the rural controls (n = 15). Significantly higher concentrations of antimony, arsenic and lead were observed among all smelter workers compared with urban controls (n = 10). The highest increase, about 11-fold, was found for antimony in smelter workers compared with non-exposed controls. A six-fold increase was noted for arsenic. Workers who died from lung cancer (n = 7) had the lowest lung selenium content relative to concentrations of other metals, both compared with other disease categories among the workers (GI-cancer, other cancers, cardiovascular diseases, cerebrovascular diseases, other causes) and with the two control groups. The low lung selenium concentrations may have influenced the development of lung cancer. The highest lung tissue levels of cadmium were found in the lung cancer group. Smokers and ex-smokers were over-represented in this group and tobacco is a known cadmium source. The highest, or one of the highest, lung values for some of the other metals (antimony, arsenic, cadmium, lanthanum and lead) were observed in one or several of the lung cancer cases. Metal concentrations in liver (metabolism) and kidney (excretion) reflect the systemic distribution. The highest cadmium levels in the liver and the lowest selenium content in the kidney were found among the lung cancer cases. A multifactorial genesis for the development of lung cancer is concluded from this study, which visualizes the need for systematic health surveillance and follow-ups both in active and retired workers.

Man's mercury loading from a dental amalgam.

The release of mercury from an amalgam surface in natural saliva during cyclic loading, as well as under static conditions, simulating the clinical conditions of chewing and rest, has been studied using a nuclear tracer technique. Cyclic loading strongly promoted degradation of the amalgam surface in the saliva environment. Corrosion products were found to be loosely bound on the amalgam surface and could be removed by brushing similar to toothbrushing. Most of the mercury released from the surface was present in amalgam particles, produced during the cyclic loading procedure. The daily release of ionic mercury was estimated to be approximately 3 micrograms/cm2, according to the model experiment. Extrapolating the present findings to clinical conditions, mans ionic mercury intake from dental restorations may be at the same level as the total mercury intake from food and drink.

Protective effect of selenium on lung cancer in smelter workers.

A possible protective effect of selenium against lung cancer has been indicated in recent studies. Workers in copper smelters are exposed to a combination of airborne selenium and carcinogens. In this study lung tissue concentrations of selenium, antimony, arsenic, cadmium, chromium, cobalt, lanthanum, and lead from 76 dead copper smelter workers were compared with those of 15 controls from a rural area and 10 controls from an urban area. The mean exposure time for the dead workers was 31.2 years, and the mean retirement time after the end of exposure 7.2 years. Lung cancer appeared in the workers with the lowest selenium lung tissue levels (selenium median value 71 micrograms/kg wet weight), as compared with both the controls (rural group, median value 110; urban group, median value 136) and other causes of death among the workers (median value 158). The quotient between the metals and selenium was used for comparison: a high quotient indicating a low protective effect of selenium and vice versa. The median values of the quotients between antimony, arsenic, cadmium, lanthanum, lead, chromium, and cobalt versus selenium were all numerically higher among the cases of lung cancer, the first five significantly higher (p less than 0.05) in 28 of the 35 comparisons between the lung cancer group and all other groups of smelter workers and controls. The different lung metal concentrations for each person were weighted according to their carcinogenic potency (Crx4 + Asx3 + Cdx2 + Sbx1 + Cox1 + Lax1 + Pbx1) against their corresponding selenium concentrations. From these calculations the protective effect of selenium was even more pronounced.

Microprobe analysis of lead in human femur by proton induced X-ray emission (PIXE)

A method is described for the measurement of the distribution of lead in bone tissue. Two cases of human femur have been analyzed; one worker was exposed to lead in heavy metal industry, the other case presents a reference worker from the same environment not excessively exposed to lead. Lead was determined through proton induced X-ray emission using microprobe technique. The mean lead concentration in the poisoned and the reference case was 70 and 30 ppm, respectively. The reference case showed an even lead distribution in the femur, while the poisoned case exhibited peaks in the distribution indicating that exposure to lead was not evenly distributed. The described technique has potential for microanalysis within the Haversian system for recording the history of exposure.

Proton-Induced X-Ray Analysis of Steel Surfaces for Microprobe Purposes

A study of the detection limits for the elements with Z = 15-92 in thick target steel surfaces using proton-induced X-ray technique has been performed. Samples were irradiated with a broad proton beam of 2 mm diameter and the X-rays were detected by a Si(Li) detector. Detection limits at levels down to the order of 10 ppm were achieved with simultaneous measurement of several elements. Mylar and chromium absorbers were introduced in front of the semiconductor detector and irradiations at two different proton energies (1.0 and 2.5 MeV) were carried out in order to elucidate their effects on detection limits. The results are valid for microbeam analysis.

Arsenic and selenium in lung, liver, and kidney tissue from dead smelter workers.

Concentrations of arsenic and selenium in lung, liver, and kidney tissue from dead smelter workers and from a control group have been determined with the aid of neutron activation analysis. A sevenfold increase of arsenic was found in lung tissue from the exposed workers compared with the control group. The median value of arsenic in lung tissue from workers dead from respiratory cancer was not higher than corresponding values from workers dead from other malignancies or from cardiovascular or other diseases. With increasing period of retirement the malignancies or from cardiovascular or other diseases. With increasing period of retirement the arsenic content diminished in liver tissue but not in lung tissue, indicating a long biological half life of arsenic in lung tissue. The workers dead from malignancies had a higher As/Se quotient than workers dead from other diseases, which does not contradict the protective theory of selenium. Accumulation of antimony, cadmium, lead and lanthanum was observed in lung tissue from the exposed workers. Six of the workers died from lung cancer and the highest concentrations of any of the elements were always observed in the lung tissue from these six cases. This observation speaks in favour of a multifactorial cause behind the excess mortality from lung cancer in smelter workers.

The ICOH and IUPAC international programme for establishing reference values of metals

In cooperation with the ICOH Scientific Committee on the Toxicology of metals and IUPAC Commission on Toxicology, we have developed evaluation criteria for derivation of reference values for metal concentrations in human tissues and fluids. In a first attempt to illustrate how these criteria may be used, tentative reference values for mercury in human blood were derived. For persons who do not eat fish, a mean value of 10 mumol/1 (2 micrograms/1) was suggested. It was pointed out, however, that this value was based on information that did not meet the desired quality requirements, which, unfortunately were not met by any of the published reports.

A proton semi-microbeam device for surface analysis

Abstract A proton semi-microbeam arrangement has been developed to study the distribution of elements in surfaces. Proton microbeams with square cross-sections of 25 μm and currents of the order of 1 nA have been produced. Focusing is achieved by means of four quadrupole lenses. Collimation is adjustable with the aid of two sets of micrometer-screw arrangements. The sample is mounted on a target holder which affords yX and Y translations in steps of 1 μm by means of a step motor. The point of impact of the beam on the sample is located using proton X-ray technique.