Marine sponges with contrasting life histories can be complementary biomonitors of heavy metal pollution in coastal ecosystems.

In this study, we compared the usefulness of a long-living sponge (Hymeniacidon heliophila, Class Demospongiae) and a short-living one (Paraleucilla magna, Class Calcarea) as biomonitors of metallic pollution. The concentrations of 16 heavy metals were analyzed in both species along a gradient of decreasing pollution from the heavily polluted Guanabara Bay to the less impacted coastal islands in Rio de Janeiro, SE Brazil (SW Atlantic). The levels of most elements analyzed were higher in H. heliophila (Al, Co, Cr, Cu, Fe, Mn, Ni, Hg, Ni, and Sn) and P. magna (Ni, Cu, Mn, Al, Ti, Fe, Pb, Co, Cr, Zn, and V) collected from the heavily polluted bay when compared with the cleanest sites. Hymeniacidon heliophila accumulates 11 elements more efficiently than P. magna. This difference may be related to their skeleton composition, histological organization, symbiont bacteria and especially to their life cycle. Both species can be used as a biomonitors of metallic pollution, but while Hymeniacidon heliophila was more effective in concentrating most metals, Paraleucilla magna is more indicated to detect recent pollutant discharges due to its shorter life cycle. We suggest that the complementary use of species with contrasting life histories can be an effective monitoring strategy of heavy metals in coastal environments.

Disposition of antimony in rhesus monkeys infected with Leishmania braziliensis and treated with meglumine antimoniate.

Antimony (Sb) disposition and toxicity was evaluated in Leishmania braziliensis-infected monkeys (Macaca mulatta) treated with a 21-d course of low (LOW) or standard (STD) meglumine antimoniate (MA) dosage regimens (5 or 20 mg Sb(V)/kg body weight/d im). Antimony levels in biological matrices were determined by inductively coupled plasma mass spectrometry (ICPMS), while on-line ion chromatography coupled to ICPMS was used to separate and quantify Sb species in plasma. Nadir Sb levels rose steadily from 19.6 ± 4 and 65.1 ± 17.4 ng/g, 24 h after the first injection, up to 27.4 ± 5.8 and 95.7 ± 6.6 ng/g, 24 h after the 21st dose in LOW and SDT groups, respectively. Subsequently, Sb plasma levels gradually declined with a terminal elimination phase half-life of 35.8 d. Antimony speciation in plasma on posttreatment days 1-9 indicated that as total Sb levels declined, proportion of Sb(V) remained nearly constant (11-20%), while proportion of Sb(III) rose from 5% (d 1) to 50% (d 9). Plasma [Sb]/erythrocyte [Sb] ratio was >1 until 12 h after dosing and reversed thereafter. Tissue Sb concentrations (posttreatment days 55 and 95) were as follows: >1000 ng/g in thyroid, nails, liver, gall bladder and spleen; >200 and <1000 ng/g in lymph nodes, kidneys, adrenals, bones, skeletal muscles, heart and skin; and <200 ng/g in various brain structures, thymus, stomach, colon, pancreas. and teeth. Results from this study are therefore consistent with view that Sb(V) is reduced to Sb(III), the active form, within cells from where it is slowly eliminated. Localization of Sb active forms in the thyroid gland and liver and the pathophysiological consequences of marked Sb accumulation in these tissues warrant further studies.

Whitemouth croaker, Micropogonias furnieri, trapped in a freshwater coastal lagoon: a natural comparison of freshwater and marine influences on otolith chemistry

Strontium and barium incorporation into otoliths was compared between whitemouth croaker, Micropogonias furnieri, collected from an entrapped freshwater population (Mirim Lagoon) and a normal marine/estuarine population in southern Brazil. Chemical analysis was performed using LA-ICPMS with the objective of validating the effects of marine and freshwater environments on Sr and Ba incorporation as a basis for further investigation of marine and freshwater connectivity of M. furnieri. The freshwater population was dominated by older fish with mean ±SD age of 34±1 y, whereas the coastal samples were dominated by younger fish of 14±7 y. Comparison of strontium and barium incorporation among otolith life-history profiles indicated significantly higher barium and lower strontium for the freshwater population compared to the marine population. Furthermore, comparison of otolith material deposited in the freshwater, estuarine and marine life-history phases demonstrated clear differences among these environments. Mean concentrations of strontium and barium in otoliths of M. furnieri were respectively 710 and 112 µg g-1 for freshwater, 2069 and 16.7 µg g-1 for estuarine, and 2990 and 2.7 µg g-1 for marine life-history phases. Barium concentrations in otoliths from the freshwater population of M. furnieri appeared high relative to other freshwater species. Strontium levels across life-history profiles of marine fish increased with age from 2000 to 2900 µg g-1, possibly indicating more time spent in marine than estuarine waters with age. In contrast, for the freshwater population, strontium levels decreased during the first year of life approximately to 700 µg g-1, and remained low and stable thereafter, consistent with the early life-history occurring in an estuarine environment prior to entrapment in Mirim Lagoon. The results confirm the strong and opposite effects of marine and freshwater environments on incorporation of barium and strontium into...

Estrôncio e bário foram determinados em otólitos de corvina Micropogonias furnieri coletados em habitats de água doce (lagoa Mirim) e costeiros no Sul Brasil. As análises foram realizadas utilizando-se LA-ICPMS, com o objetivo de estabelecer assinaturas químicas específicas para os diferentes habitats e avaliar a aplicabilidade da química de otólitos para o estudo de mudanças de habitat na espécie em questão para futuros estudos sobre conectividade de populações. Os animais coletados na lagoa Mirim apresentaram idade média de 34±1 anos, não sendo observados adultos jovens ou juvenis. Foi verificada uma variação significativa nas concentrações de Sr e Ba em otólitos para áreas marinhas e de água doce. Para ambientes marinhos, a idade média foi de 14±7 anos. Os valores médios de Sr e Ba foram estimados, respectivamente, em 710 e 112 µg g-1 para água doce, 2069 e 16,7 µg g-1 para água estuarina e 2990 e 2,7 µg g-1 para águas costeiras. Nos otólitos provenientes dos indivíduos de água doce, o Ba apresentou concentrações mais altas quando comparado a valores observados para outras espécies. Observou-se que a incorporação de Ba nos otólitos ao longo da vida sofre certa influência ontogenética, com valores mais altos medidos no início da vida. As concentrações de Sr em otólitos de animais costeiros aumentaram em média de 2000 a 2900 µg g-1 ao longo da vida, indicando a mudança de habitats estuarinos para marinhos. Para água doce, a concentração de Sr decresce antes do primeiro ano até valores em torno de 700 µg g-1 mantendo essa concentração por toda a vida, indicando um ambiente de água doce estável. Estes resultados confirmam o forte efeito inverso que ambientes marinhos e de água doce promovem na incorporação de Sr e Ba em otólitos e permitem sugerir que a corvina encontrada na lagoa Mirim é representada por um grupo isolado de animais com baixa probabilidade de reprodução que, portanto, será possivelmente extinto nos próximos anos.

Intake and excretion of disodium monomethylarsonate in horses: a speciation study.

Capillary electrophoresis coupled to inductively coupled plasma mass spectrometry was used in a speciation study on disodium monomethylarsonate (DS-MMA(V)) and its metabolites in horses, to which the drug was administered by intramuscular injection on five consecutive days at a single arsenic dosage of 270 mg day(-1). Samples of urine, whole blood, plasma, and mane hair were analyzed before, during, and after drug administration. The data show that blood clearing and urinary excretion of MMA is a fast process following first-order kinetics with biological half-lives of about 38 h and 44 h for urine and plasma, respectively. In the time period of 9 days studied, the only metabolite detected in urine was dimethylarsinic acid (DMA(V)), which 4 days after the last drug administration accounted for up to 75% of the total excreted arsenic species. This shows, for the first time, that biomethylation of MMA(V) to DMA(V) is the principal metabolic pathway of this drug in horses. Although DS-MMA(V) was administered only during a short 5-day period, an up to six fold increase of arsenic could be measured in the newly grown mane hair.

Developmental toxicity of meglumine antimoniate and transplacental transfer of antimony in the rat.

Meglumine antimoniate (MA), a pentavalent antimonial (SbV) drug, has been used for the treatment of leishmaniases for over half a century but there is almost no data on its safety and kinetics during pregnancy. This study was undertaken to investigate the developmental toxicity of MA as well as the transplacental transfer of antimony (Sb) in rats. Wistar rats (approximately 20 per group) were treated subcutaneously (s.c.) with MA (0, 75, 150, 300 mg SbV/(kg BW day)) during pregnancy (days 1-20). An untreated control group was evaluated as well. Caesarean sections were performed on day 21 and implantations, living and dead fetuses, and resorptions were recorded. Fetuses were weighed and fixed in Bouin's solution and one-third of each litter was examined for soft-tissue anomalies. The remaining fetuses were cleared and stained with Alizarin red S for skeleton evaluation. No adverse effect of MA on the mothers was noted at any dose level. No embryotoxicity was observed at the lowest dose but, at the highest dose, MA increased embryolethality, reduced fetal weight and augmented the occurrence of some soft-tissue and skeleton variations. Therefore, the no-observed-adverse-effect level for MA-induced embryotoxicity was 75 mg SbV/(kg BW day). In a separate group of rats treated with 300 mg SbV/(kg BW day) s.c. during whole pregnancy, blood (0.2 mL) was taken from the tail vein 1, 2, 4, 6, 12 and 24 h after treatment on day 1 and thereafter every other day immediately before drug injection. Blood was also taken from fetuses removed on day 21, 24h after the last injection of MA. Blood levels of Sb were determined by ICP-MS and results showed that most of administered Sb was eliminated rapidly (in less than 6 h), but nadir blood concentrations increased gradually during treatment from 1 to 2 microg/g, 24h after the first dose, up to approximately 38 microg/g after the 20th dose. Levels of Sb in fetal blood were as high as 10-15 microg/g, i.e. approximately 30% their mothers' nadir levels near term. These findings indicated that repeated administration of MA during gestation led to an accumulation of Sb in mothers and fetuses.

Distribution of lead in human milk fractions: relationship with essential minerals and maternal blood lead.

The purpose of this study was to determine the concentration and distribution of lead, calcium, iron, zinc, and copper in major fractions (fat, casein, whey) of mature milk from 38 nursing adult women with low environmental lead exposure. The potential associations between milk lead and maternal blood lead and between milk and blood lead and essential mineral data (nutritional status, dietary intake, and milk concentration) were investigated. Maternal blood lead (geometric mean, 60 microg/L) was negatively associated, although modestly, with dietary calcium intake (r=-0.32, p=0.02). Lead in whole milk (geometric mean, 1.2 microg/L) was positively associated with calcium in whole milk (r=0.56, p=0.005). Distribution of lead in milk fractions was 63%, 28%, and 9%, in whey, fat, and casein, respectively. Milk distribution of essential minerals was 67-76%, 17-18%, and 7-17% in whey, fat, and casein, respectively. Lead in milk whey was positively associated with lead in maternal blood (r=0.49, p=0.02). However, milk lead was not affected by nutritional status, dietary intake, and milk composition of the essential minerals. The high percentage of lead in the milk whey fraction, as seen for the essential minerals, suggests that most lead in human milk is bioavailable to the infant.

Multi-element analysis of saline matrices by inductively coupled plasma mass spectrometry following on-line preconcentration using a knotted reactor.

A versatile preconcentration system for trace element determination by ICPMS was developed. It is composed of a commercial flow injection analysis system (FIAS) retrofitted with a home-made control unit containing three solenoid valves and working concomitantly with the FIAS, permitting selection and segmentation of sample, reagent, washing solution and elution flow. The knotted reactor used had a length of 200 cm and was made from 0.05 cm i.d. PTFE tubing. The method applies ammonium 1-pyrrolidinedithiocarbamate (APDC) as complexant, allowing the preconcentration and quantitative multi-element determination of Cu, Ni, V, Co, Nb, Mo, In, Sb and Bi. Ethanol and 4-methyl-2-pentanone were tested as eluents. Recovery tests using complex matrices and spike concentrations of 200 ng L(-1) showed typical values in the range of 90% to 110%. Relative standard deviations were < 7% for elution with ethanol and < 5% with methyl isobutyl ketone. For simulated freshwater samples using 4-methyl-2-pentanone as an eluent, a sample loading rate of 5.0 ml min(-1), and a preconcentration time of 60 s, detection limits (ng L(-1)) were in the range of 0.02 (Bi) to 30 (Cu). Under these conditions, analytical frequency was about 15 samples per hour. The feasibility of the method was demonstrated by the succesful analysis of wastewater and seawater certified reference materials.

Determination of thorium and light rare-earth elements in soil water and its high molecular mass organic fractions by inductively coupled plasma mass spectrometry and on-line-coupled size-exclusion chromatography.

Inductively coupled plasma mass spectrometry (ICP-MS) has been used for the determination of thorium and light rare-earth elements (LREEs) in soil and soil water samples from a mineral deposit (Morro do Ferro, Minas Gerais, Brazil). Size-exclusion chromatography (SEC) on-line coupled to ICP-MS and UV-detection was applied to verify possible association/complexation of these elements with organic matter in soil water separated by a centrifugation technique. Concentrations of DOC in soil waters are in the range of 10 to 500 mg L(-1) and correlate with the organic carbon content of the soil (r=0.950; p<0.001). Concentrations of 30 to 40 microg L(-1) for the LREEs (La, Ce, Nd) and up to 14 microg L(-1) for Th were measured in soil waters of highest DOC content. SEC chromatograms of these waters showed the association of elements with different nominal high-molecular-mass ranges, characteristic of soil humic and fulvic acids: >10,000 Da, with a retention time of about 10 min; 7000 to 8000 Da with retention times of 13 to 15 min; and 2000 to 4000 Da with retention times around 23 min. Elemental peaks associated with dissolved organic matter below 1000 Da were not observed, suggesting that complexation with simple plant organic acids or inorganic ligands is of minor importance in the environment studied in this work.

Calcium supplementation during lactation blunts erythrocyte lead levels and delta-aminolevulinic acid dehydratase zinc-reactivation in women non-exposed to lead and with marginal calcium intakes.

The purpose of this study was to evaluate the effect of calcium supplementation during lactation on changes in blood lead indices from late pregnancy to early lactation in women with low calcium intakes and low lead-exposure. Forty-seven women, non-occupationally exposed to lead and with habitually low calcium intake ( approximately 600 mg/d), participated in the study from 29 to 38 weeks of pregnancy to 7-8 weeks post-partum, non-supplemented (n=25) and supplemented (n=22) with calcium (500 mg/d) during 6 weeks after delivery. Erythrocyte lead (PbRBC) and in vitro reactivation with zinc of blood delta-aminolevulinic acid dehydratase (Zn-delta-ALAD% reactivation) were used as lead indices. In the non-supplemented group, PbRBC and Zn-delta-ALAD% reactivation increased significantly (P<0.001) from pregnancy (0.202+/-0.049 microg Pb/g protein and 18.3+/-6.0%) to lactation (0.272+/-0.070 microg Pb/g protein and 22.7+/-6.2%). No significant changes of these indices were observed in the calcium-supplemented group from pregnancy (0.203+/-0.080 microg Pb/g protein and 15.8+/-4.5%) to lactation (0.214+/-0.066 microg Pb/g protein and 16.3+/-4.1%). PbRBC levels and Zn-delta-ALAD% reactivation at lactation were lower (P<0.05) and hematocrit levels were higher (P<0.05) in the calcium-supplemented compared to the non-supplemented women. Calcium supplementation during lactation appears to blunt the lactation-induced increase in maternal blood lead and its inhibitory effect on delta-ALAD and possibly on maternal erythropoiesis.