Determination of total fluorine in five coal reference materials by proton-induced gamma-ray emission spectrometry.

The direct non-destructive proton-induced gamma-ray emission (PIGE) technique with a germanium detector was applied to the determination of total fluorine concentration in five coal reference materials (BCR 40, NIST 1632b, NIST 1635, SARM 20 and USGS CLB-1). Duplicate analyses were made from five randomly selected bottles of each coal. Individual data are presented and some problems (calibration, proton stopping power, effects of sample heating by the proton beam, background estimation) which were encountered during this study are discussed. Sensitivity and reproducibility of the determinations, and homogeneity of the coal samples with respect to fluorine contents by analysis of variance were investigated. The present data are also compared with the few published values for these reference samples, including other PIGE data. The use of synthetic standards and spiked samples in the present study suggested that the PIGE method was more accurate than other techniques.

Nonfibrous mineralogical analysis of bronchoalveolar lavage fluid from blast-furnace workers.

Steelworkers are exposed to many pollutants, and they are at risk for developing lung cancer. We demonstrated previously that steelworkers may be subject to an occult exposure to amphiboles in the plant environment. In the current study, we further analyzed bronchoalveolar lavage fluid of steelworkers by measuring intramacrophagic trace-metal content and nonfibrous mineral particles, using the particle-induced x-ray emission method and electron microscopy, respectively. Forty-seven blast-furnace workers and 45 healthy white-collar workers volunteered for this study. Significantly increased levels of iron, titanium, zinc, and bromine were found in the steelworkers, and levels of lead, chromium, arsenic, and strontium tended to increase in the macrophages and bronchoalveolar lavage fluid of the steelworkers. Nonfibrous particles, including illite, kaolinite, talc, chlorite, amorphous silica, quartz, iron (compounds), and titanium hydroxide, were found in both groups, but the particle number per ml bronchoalveolar lavage fluid (particularly iron hydroxides and silicates) was more pronounced in blast-furnace workers. These elements and particles may act synergistically with other occupational carcinogens and cigarette smoke, the result of which may be an increased incidence of lung cancer in the ironsteel industry.

Iron content in human alveolar macrophages.

Intracellular iron can be estimated semi-quantitatively by histochemical determination using the ferrocyanide reagent's score. Particle-induced X-ray emission (PIXE) allows accurate determination of various elements including iron in cells and biological fluids. Both techniques have been used to measure iron in alveolar macrophages gathered by bronchoalveolar lavage. The purpose of this study was to investigate the clinical usefulness of the PIXE technique in occupational respiratory medicine and in various pulmonary diseases. Using the PIXE method, we measured the iron content of alveolar macrophages in healthy subjects, with and without occupational exposure to iron dust, and in patients with pulmonary diseases (chronic obstructive pulmonary disease (COPD), lung cancer, Goodpasture's syndrome). Our results were then compared with those obtained with the ferrocyanide reagent. Intramacrophagic iron was 0.33 +/- 0.21 micrograms.10(-6) (mean +/- SD) cells in healthy non-smoking subjects without occupational exposure. Intramacrophagic iron was increased in smokers, iron-steelworkers, and in patients with COPD or lung cancer even in the absence of pulmonary haemorrhage. The two patients with Goodpasture's syndrome had high intramacrophagic iron content. About 80% of the whole bronchoalveolar lavage fluid iron content was in the cells. Mean iron content of blood monocytes, lymphocytes and neutrophils of eight healthy subjects was significantly lower than that of alveolar macrophages. A significant correlation was found between iron determination by the PIXE method and the ferrocyanide reagent's score (r = 0.89). We conclude that intramacrophagic iron may be increased in steelworkers and subjects with pulmonary haemorrhage, but also in asymptomatic smokers, in COPD and lung cancer patients without occupational exposure to iron dust.

Relationship of serum selenium levels to tumor activity in acute non-lymphocytic leukemia.

Serum selenium (Se) levels were measured before, during and after high-dose induction chemotherapy in 70 patients with acute non-lymphocytic leukemia (ANLL). Pre-treatment serum Se levels were lower in patients than in controls (0.082 +/- 0.033 micrograms/ml versus 0.097 +/- 0.035 micrograms/ml, P less than 0.01). Pretreatment serum Se correlated inversely with the absolute peripheral blast cell count (R = -0.62, P less than 0.001) and other measurements of the tumor burden. Seven days after the initiation of chemotherapy, serum Se increased significantly in proportion to the initial tumor burden (P less than 0.01). Thereafter, serum Se levels remained essentially normal in patients entering a complete remission while decreasing gradually in failures. In conclusion, these data do not lend support to the hypothesis that a low selenium status enhances the risk of developing ANLL, but indicate that serum Se levels in patients with acute leukemia are mostly dependent on tumor activity.

Observations of serum trace elements in chronic lymphocytic leukemia.

Serum trace elements (STE) were measured in 50 patients with chronic lymphocytic leukemia (CLL) and 100 normal subjects. Copper was higher in patients than in controls (1.50 +/- 0.06 versus 1.10 +/- 0.02 micrograms/ml, P less than 0.001), increased steadily from Stage 0 to Stage 4 (P = 0.002), and correlated with the lymphocyte count and serum lactate dehydrogenase (P less than 0.01) but not with acute phase reactants. Zinc was lower in patients than in controls (0.94 +/- 0.03 versus 1.10 +/- 0.02 micrograms/ml, P less than 0.001). Zinc (NS), selenium (P = 0.039), and calcium (P = 0.033), were decreased in Stages 3-4 as compared to Stages 0-2. The copper-to-zinc ratio (CZR) increased continuously from Stage 0 to Stage 4 (P less than 0.001). Discriminant analysis between two groups, Stage 0-2 and Stage 3-4, based on serum copper, zinc, calcium, and protein levels, allowed for a correct classification of 94% of the patients. Moreover, the clinical staging of the remaining 6% was modified retrospectively according to the results of discriminant analysis. It was concluded that (1) serum copper and CZR are useful indices of the extent of disease, (2) they are independent of a nonspecific acute phase reaction, (3) STE determination could be helpful in the staging of a limited number of CLL patients, and (4) zinc deficiency could contribute to immune dysfunction in CLL.

Serum zinc and copper as prognostic factors in acute nonlymphocytic leukemia.

A total of 44 patients were treated with intensive induction chemotherapy for acute nonlymphocytic leukemia (ANLL). A complete remission (CR) was obtained in 29/44 (66%) patients. Serum zinc (Zn) and copper (Cu) were studied as possible prognostic factors in the determination of the chance of a patient attaining remission. Pretreatment Zn was higher in patients attaining a remission (0.99 +/- 0.05 microgram/ml) than in patients failing to attain a CR (0.78 +/- 0.06 microgram/ml) (P = 0.0216). There was no further difference between the two groups during aplasia. However, when response to treatment was evaluated about day 28, the difference reappeared: 1.06 +/- 0.05 microgram/ml for CR patients vs 0.77 +/- 0.07 microgram/ml for failures (p = 0.0012). Pretreatment Cu was higher in responding (1.44 +/- 0.07 microgram/ml) than in nonresponding (1.06 +/- 0.05 microgram/ml) patients (p = 0.0002). The difference between the two groups remained highly significant at days 7, 14, 21, and 28. At the time of response evaluation, the values were 1.46 +/- 0.05 microgram/ml for CR patients vs 1.19 +/- 0.08 microgram/ml for non-CR patients (P = 0.0070). We conclude that the measurement of serum Zn and Cu may be helpful in the prediction of response to chemotherapy in patients treated for ANLL.

[Assay of trace elements in the serum by the PIXE method in patients with Crohn's disease]. / Dosage des oligoéléments dans le sérum, par la méthode PIXE, chez des patients atteints de la maladie de Crohn.

Concentrations of trace elements were determined by the PIXE method (particle induced X-ray emission) in 43 serum samples from 29 Crohn's disease patients and compared with the results obtained from a control group of 100 healthy subjects. Most of the patients were outpatients whose disease was quiescent or moderately active. Half of them had a good nutritional state. Mean serum selenium level was significantly higher in the Crohn's disease group than in the control group. A negative correlation was found between serum selenium and C-reactive protein levels. Mean serum bromine was normal in the Crohn's disease group, but there was a positive correlation between serum bromine and fibrinogen and C-reactive protein levels and leucocytosis. Mean serum copper concentration was higher in women than in men in both groups. In Crohn's disease patients, copper serum concentration was increased and correlated positively to fibrinogen and C-reactive protein concentrations, erythrocyte sedimentation rate and thrombocytosis, and negatively to hematocrit. Copper serum level could be used as a marker of Crohn's disease activity. Mean serum zinc level was decreased in the Crohn's disease group. There was a positive correlation between serum zinc level and erythrocyte sedimentation rate and fibrinogen concentration.

Distribution of metals in human lung: analysis by particle induced x-ray emission.

Thirty-five lung pairs obtained during autopsy from randomly selected patients were investigated by particle induced X-ray emission for overall and regional elemental content determination. In each case the interbronchial lymph node was simultaneously processed. While homogenous distribution has been consistently observed for potassium, calcium, iron, copper, zinc, and rubidium, a very different distribution was recorded for titanium, chromium, nickel, and strontium. The significance of these results is discussed with regard to pollution hazards. Regional accumulation of this second group of elements seems to be related to air pollution peculiar to Liège. Advantages and limitations of the technique and the need for further research are stressed.

Determination of rare earths and thorium in apatites by thermal and epithermal neutron-activation analysis.

A procedure is described for the non-destructive determination of Na, Mn, La, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu and Th in apatites by thermal and epithermal neutron-activation of independent portions of the material. The method was applied to three apatites with different contents. The precision obtained was better than +/-5% for La, Ce, Sm, Eu, Gd, Tb and Dy and +/-20% for Yb, Nd, Ho, Er and Lu for an apatite with a total rare-earth oxide content of the order of 1%. Determination of Ce, Tb and Yb could only be carried out with thermal neutron-activation analysis, while Gd, Ho and Er could only be determined after irradiation with epithermal neutrons.