Comparative efficacies of two antimony regimens to treat Leishmania braziliensis-induced cutaneous Leishmaniasis in rhesus macaques (Macaca mulatta).

This study compared the efficacies of two N-methylglucomine antimoniate (MA) dose regimens for treating macaques with Leishmania braziliensis-induced chronic skin disease. Whereas all animals treated with the full dose (20 mg MA/kg/day) were cured, 50% of the monkeys receiving a low-dose regimen (5 mg MA/kg/day) relapsed. The antimony concentrations in macaque plasma and tissue samples were greater in the full-dose group than in that receiving a subtherapeutic MA regimen. Our data also suggest the presence of drug-induced hepatic pathology.

Trace metals in mussel shells and corresponding soft tissue samples: a validation experiment for the use of Perna perna shells in pollution monitoring.

The uptake of Cr, Mn, Ni, Cu, Zn, Cd and Pb in soft tissue of Perna perna mussels and their shells has been studied in aquarium experiments in which mussels were exposed for 30 or 60 days to seawater spiked with different concentrations of these contaminants (125 and 500 microg L(-1)). Tissue samples were analyzed after acid digestion by conventional solution nebulization ICP-MS. Laser ablation ICP-MS was used for the quantitative determination of trace elements in different areas of the corresponding shells. With the exception of Mn and Zn, all other elements studied showed a significant concentration enhancements in soft tissue, with the magnitude of this enhancement following the order: Cr > Ni > Cd > Cu > Pb. A corresponding increase in most contaminants, although less pronounced, was also observed in the newly formed growth rings of mussel shells, contributing to the validation of Perna perna mussel shell as a bioindicator of toxic elements.

Environmental impact studies of barium and radium discharges by produced waters from the "Bacia de Campos" oil-field offshore platforms, Brazil.

Produced water samples from different E&P offshore petroleum platforms, belonging to the Bacia de Campos oil field, Brazil, were analyzed for barium, 226Ra and 'Ra. The concentrations measured are in the range of 0.36-25.7 mg l(-1) for barium, 0.012-6.0 Bq l(-1) for 226Ra and <0.05-12.0 Bq l(-1) for 1Ra. A strong correlation between the concentration of barium and radium isotopes was observed (226Ra: r2=0.926: 228Ra: r2=0.785). Additionally, seawater and sediment samples were taken at different distances (from 250 to 1,000 m) from the two selected platforms. Water samples were analyzed for dissolved and particulate barium, 226Ra and 225Ra and the sediment samples for total and leachable barium, 226Ra and 228Ra. The results showed that even for the shortest sampling distance (250 m) from the discharge point, barium, 226Ra and 228Ra concentrations are similar to the local background, indicating that dispersion by local currents is enough to minimize environmental impacts.

Monitoring of total antimony and its species by ICP-MS and on-line ion chromatography in biological samples from patients treated for leishmaniasis.

Results from a study are reported in which patients with leishmaniasis were monitored by whole blood, blood plasma, urine, and hair analysis, before, during, and after intramuscular administration of N-methyl meglumine antimoniate. Quadrupole ICP-MS was used for the detection of antimony and on-line ion chromatography for the separation of its species. After typically 30 consecutive daily injections of 5 mg antimony per kg of body weight, Sb concentrations of up to 250 microg L(-1) in whole blood and plasma, and 60 mg of Sb per gram of creatinine in urine, were measured 24 h after drug administration. Antimony in hair samples of these patients showed concentrations of up to 24 microg g(-1). Speciation studies of Sb5+ and Sb3+ in drug, urine, and plasma samples were performed by ion chromatography using a Hamilton PRP-100X anion exchange column and EDTA (2 or 20 mM, pH 4.7) as the mobile phases. Repeatability of elution time and peak area measurements for a 0.125 ng spike were <1.2% and <3.5%, respectively. Method detection limits for both species, using a 1:10 diluted urine or plasma sample, were typically 1.6 microg L(-1). The procedure was capable of separating the very intense drug peak from its inorganic species, thus permitting the first studies on the bio-transformation of N-methyl meglumine antimoniate to Sb5+ and Sb3+ in the human body.

Elemental anomalies in hair as indicators of endocrinologic pathologies and deficiencies in calcium and bone metabolism.

Analytical results obtained by ICP-MS of hair samples from a group of women from Rio de Janeiro city show that abnormal Ca and P concentrations in this compartment can be an indication of pathologies affecting the metabolism of these elements. The study was conducted initially on 900 women (outpatients, >40 years). From this group, approx. 24% showed anomalously high or low Ca concentrations in hair, in some cases correlated to anomalies of other elements. In 144 cases (16%), very high concentrations of Ca (up to 8,285 mg/kg) were measured, frequently correlated with a high concentration of P (up to 4,720 mg/kg), exceeding by far the reference intervals for this age/sex group. Follow-up studies of a few individuals from this group gave first indications that their abnormal hair compositions were related to endocrinologic pathologies affecting calcium/bone metabolism. Very low hair Ca-concentrations were observed in older women (72 cases, age >60 years) and related to senile osteoporosis. Complementary investigations of patients with recognized endocrinologic pathologies (hyperthyroidism, hyper- and hypoparathyroidism) and osteomalacia gave statistical support for the hypothesis that hair concentrations of Ca, P and various other trace elements are influenced characteristically by these diseases. In patients with hyperparathyroidism and hyperthyroidism, both elements showed significant increase in hair, whereas patients with rickets/osteomalacia had only elevated Ca concentrations, together with suspiciously high toxic levels of Cd and various other elements (Fe, Mn, Mg, Sr, Ba). Patients with hypoparathyroidism had significantly decreased Ca and P concentrations in hair. Statistical evaluation of these data by multivariant analysis (MANOVA) using a contrast matrix and by discriminant analysis showed that elemental hair anomalies can be used to diagnose correctly the above-mentioned pathologies, demonstrating the usefulness of hair analysis as a complementary tool for the detection of disturbances in calcium/bone metabolism.

Improvements in calibration procedures for the quantitative determination of trace elements in carbonate material (mussel shells) by laser ablation ICP-MS.

A better repeatability and accuracy in the quantitative determination of trace elements in mussel shells or carbonate-based materials by LA-ICP-MS was achieved by using a series of multielement calibration standards prepared by co-precipitation of twelve elements into a CaCO3 matrix in order to improve the homogeneity of the resulting powder samples. Pressed powder discs of good mechanical stability could be obtained at a pressure of 50 MPa, without the addition of a binder. An UV laser (modified Nd:YAG, 266 nm) was used in the Q-switched mode at a repetition rate of 10 Hz and an energy level of 3.5 mJ. Correlation coefficients (R) for the linear calibration graphs (concentration range: 1.5-400 microg/g) for Cr, Mn, Co, Cu, Zn, As, Cd, Sn, Ba, and Pb are generally better than 0.997. The detection limits for all elements investigated are in the sub-microg/g range. Incorporation of elements into the matrix by co-precipitation has shown as a superior method for producing calibration standards than the simple mixture of the analytes (in carbonate or oxide form) with the matrix (CaCO3) or addition of standard solutions to a carbonate powder base. Two examples of the quantitative determination of toxic elements in mussel shells will be presented.

How reliable are human hair reference intervals for trace elements?

Inductively coupled plasma mass spectrometry (ICP-MS) was used for the determination of major and trace element concentrations in scalp hair samples from a population group (N = 1091) of Rio de Janeiro city. From these results, preliminary 'normal' or reference intervals were calculated which are for several trace elements (e.g. B, V, Co, Ge, Mo, Au, As, Se, Sb, Th), but also for some minor elements (e.g. Ca, Mg) in disaccord with data published by five clinical laboratories which used inductively coupled plasma atomic emission spectrometry (ICP-AES). The limitations of ICP-AES in routine hair analysis is shown by comparison of detection limits for both methods and by results from two laboratory intercomparison exercises. It is evident from these data that published reference intervals have to be used with extreme caution and that their urgent revision, based on reliable data produced by the ICP-MS technique, is of extreme importance.