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PubMed1984

Computer simulation of metal ion equilibria in biofluids. IV. Plutonium speciation in human blood plasma and chelation therapy using polyaminopolycarboxylic acids.

An investigation by computer simulation into the nature of Pu(IV) binding to low-molecular ligands in human blood plasma is described. Particular consideration is given to the interactions of various chelating agents which have been or might be used for treating plutonium intoxication. Formation constants of EDTA and DTPA with Cu(II), Mg(II), Mn(II), Zn(II), and Cd(II) have been measured under biologic conditions of temperature and background electrolyte. The relative ability of these and other chelating agents to cause excretion of plutonium and the concomitant loss of certain essential trace metals has thus been assessed.

Chelating Agents↗
PubMed1990

Aluminum speciation studies in biological fluids. Part 3. Quantitative investigation of aluminum-phosphate complexes and assessment of their potential significance in vivo.

Following the discovery that specific health disorders affecting patients with renal disease were due to their excessive body accumulation of aluminum, it was established that aluminum toxicity was mainly due to the ingestion of aluminum-containing phosphate binders. Suspicion of toxicity was thus cast on aluminum-containing antacids, and subsequent tests held on healthy subjects did reveal that aluminum hydroxide gels were also potential oral sources of aluminum, especially in the presence of citric acid. Nevertheless, authors of these tests concluded that there was only marginal absorption of aluminum phosphate. In contrast with these clinical conclusions, it has recently been contended on theoretical grounds that aluminum phosphate represents a serious health hazard. To help elucidate this issue, this paper first deals with a quantitative investigation of aluminum-phosphate equilibria under physiological conditions. Then appropriate computer simulations based on corresponding results are used to assess the actual extent to which phosphate can influence aluminum bioavailability. These simulations confirm that aluminum phosphate is not expected to induce absorption of high amounts of aluminum when administered by itself. Nevertheless, this result may no longer apply in the presence of food, whose various acidic components are likely to modify the involved chemical equilibria. Moreover, it is shown that rising blood plasma phosphate levels should tend to increase aluminum tissue penetration and hence favor its potential toxicity.

Aluminum↗
PubMed1986

Hydatidosis: changing concepts in epidemiology and speciation.

Hydatidosis, caused by dog tapeworms of the genus Echinococcus, is one of the most important cestode infections of man. It is widely distributed and recent information points to a spread of the disease into areas previously free of it. This article reviews recent advances in understanding the biology of Echinococcus, relating these developments to the epidemiology of hydatid disease and its control.

Journal Article↗
PubMed1996

Relationship between copper speciation in sediments and bioaccumulation by marine bivalves of Taiwan.

This paper evaluates the relationships between copper species in sediments and accumulation by the purple clam (Hiatula diphos) and venus clam (Gomphina aeguilatera) collected from the field and culture (aquaculture) ponds in the polluted coastal area of Lukang, Taiwan. Sediment was sampled along with the molluscs, including oysters (Crassostrea gigas), purple clams (Hiatula diphos), rock-shells (Thais clavigera), venus clams (Gomphina aeguilatera), and hard clams (Meretrix lusoria), from two unique environments of Lukang during the period from August 1993 to July 1994. The data indicate that the total copper concentrations in sediments from culture ponds (185 microg g(-1)) was higher than those of the field (44.0 microg g(-1)). Copper species in sediments were analyzed by a sequential leaching technique. Results show that concentrations of various copper species in the sediments are in the range of 1.14 +/- 0.59 to 13.2 +/- 22.4 microg g(-1) and 0.36 +/- 0.24 to 133 +/- 36.7 microg g(-1) for the two environments, respectively. Also the exchangeable copper in sediment from culture ponds was 15 times higher than that from the field. In addition, the sum of exchangeable and copper carbonates had the highest percentages of copper in both the pond sediment (86.6 %) and the field sediment (50.7 %). Maximum copper concentrations (309 +/- 35.1 microg g(-1)) in oysters were much higher than those in the other benthic organisms by about 4-127 times. Similarly, the data also showed that copper concentrations in Thais clavigera were 12-32 times higher than those in other benthic organisms. Copper concentrations in various benthic organisms differed significantly (p < 0.05) from that in Thais clavigera. This capacity makes Thais clavigera a potential candidate for monitoring copper in marine sediments. In terms of copper species, the best correlation was generally obtained between copper carbonates in sediments and copper concentrations in Hiatula diphos (r = 0.886*). A strong multiple regression correlation (p < 0.05, r2 = 0.7894) also indicates that the copper carbonates may dominate as the available form of copper to Hiatula diphos from various environments in the Lukang coastal area under natural physicochemical conditions.

Journal Article↗
PubMed1995

Urinary iron speciation in nephrotic syndrome.

In nephrotic syndrome, iron is presented to the tubule fluid in a nonreactive form in association with transferrin as a result of the glomerular protein leak. At an alkaline pH, iron remains bound to transferrin throughout the nephron and is excreted as such in the urine. As urine pH decreases below 6, iron is dissociated from transferrin. In the dissociated form, iron exists in the urine in a soluble, ultrafiltrable, and labile state. It is suggested that iron is maintained in this state by chelation to a relatively small organic compound, such as citrate. This non-transferrin-bound iron is capable of catalyzing bleomycin degradation of DNA, suggesting that this labile form of iron is able to catalyze free radical formation and cause tubule cell injury. Urine from proteinuric states represents one of the few, if not only, biologic fluids containing large amounts of reactive iron species. This may explain the mechanism by which proteinuric states cause tubulointerstitial disease and renal failure.

Animals↗
PubMed1995

Speciation of organotin compounds by capillary electrophoresis using indirect ultraviolet absorbance detection.

Capillary electrophoresis (CE) with indirect photometric detection was investigated for the separation of organotin species. Compounds such as dimethyltin (DMT), dibutyltin (DBT), and tributyltin (TBT) are important pollutants in the aqueous environment and techniques are needed to analyze directly aqueous environmental samples quickly and economically. By adjusting the mobile phase to pH 2.65 by HCl, tributyltin, dibutyltin and dimethyltin in aqueous solutions were separated by capillary electrophoresis using indirect ultraviolet (UV) absorbance detection. Pyridine was used as the UV absorption additive at 254 nm and separation was achieved in 6 min. Peak tailing obtained at higher pH suggests strong interaction between the dimethyltin cation and the negatively charged capillary wall. Cetyltrimethylammonium bromide (CTAB) was added to the mobile phase to improve the peak shapes when the pH of the mobile phase was greater than 3.5. Separations of organotin species in mobile phases with or without CTAB were compared. The change of electrophoretic mobility in mobile phases with different pH values indicates that DMT and DBT start to undergo hydrolysis at a pH 3.0. It was also found that the choice of the buffer anions is critical in the separation of the tin compounds as complexes appear to form with DMT and DBT in the presence of oxalate and citrate.

Electrophoresis, Capillary↗
PubMed1984

The role of digestion in the black sea bass, Centropristis striata, on the chemical speciation of organically bound cadmium.

The process of digestion (in vivo and in vitro) upon the chemical form of intrinsic cadmium (Cd) in oysters was examined. Analyses of stomach contents of adult black sea bass (Centropristis striata), 6 hr after consuming oysters previously exposed to Cd, indicated that Cd was associated with five protein fractions having approximate molecular weights of greater than 160,000, 74,000, 38,000, 11,000 and less than 4000. After 24 hr of in vivo digestion, analyses of intestinal contents indicated that most of the detectable Cd was associated with smaller molecular weight compounds. Similar results were obtained in an in vitro digestion system; the Cd was associated with somewhat larger complexes than those found in the in vivo digestion. Free amino acids were present in the low-molecular weight organo-Cd fraction, suggesting a possible role of amino acids in intestinal Cd transport.

Amino Acids↗
PubMed1988

Speciation of organisms within the Mycobacterium avium-Mycobacterium intracellulare-Mycobacterium scrofulaceum (MAIS) complex based on restriction fragment length polymorphisms.

A DNA probe which hybridizes to all pathogenic species of slow-growing mycobacteria has been used to identify restriction-fragment-length-polymorphisms (RFLPs) in Bam Hl digests of chromosomal DNA from members of the Mycobacterium avium-Mycobacterium intracellulare-Mycobacterium scrofulaceum complex. The RFLP patterns so produced were found to fall into distinct categories which were representative of each of the three species. Except for two doubtful isolates, strains of M. avium were found to fall into two related RFLP-types, one of which contained the vast majority of the strains tested. In contrast, M. intracellulare strains were found to be more heterogeneous. For these strains, we found one major RFLP-type and one subsidiary type which appears to be a sub-set of the first. We also found two further RFLP-types which contained serovars 7 and 18 respectively. We conclude from this that M. avium, M. intracellulare and M. scrofulaceum are three distinct species and that serovars belonging to the 'intermediate group' of Meissner and Anz belong to the species M. avium. Utilizing these criteria, we examined a number of isolates from the 'ambiguous' serovar 9 and found that of eight strains tested, six typed as M. avium and two typed as M. intracellulare.

Acquired Immunodeficiency Syndrome↗
PubMedDate not supplied

Source-term characterisation and solid speciation of plutonium at the Semipalatinsk NTS, Kazakhstan.

New data on the concentrations of key fission/activation products and transuranium nuclides in samples of soil and water from the Semipalatinsk Nuclear Test Site are presented and interpreted. Sampling was carried out at Ground Zero, Lake Balapan, the Tel'kem craters and reference locations within the test site boundary well removed from localised sources. Radionuclide ratios have been used to characterise the source term(s) at each of these sites. The geochemical partitioning of plutonium has also been examined and it is shown that the bulk of the plutonium contamination at most of the sites examined is in a highly refractory, non-labile form.

Journal Article↗
PubMed2005

60Co aqueous speciation and pH effect on the adsorption behavior on inorganic materials.

The adsorption of radioactive cobalt from aqueous solution on MgO, MnO(2), TiO(2), SnO, activated carbon and calcined hydrotalcite was studied under static conditions as a function of pH (1, 3, 5, 7, and 10) of the (60)Co solution. It was found that under the experimental conditions, (60)Co was significantly adsorbed on MnO(2), TiO(2) and activated carbon and in smaller quantities on MgO, SnO and calcined hydrotalcite. The adsorption of (60)Co species on MgO, MnO(2), TiO(2) and SnO can be attributed to the direct exchange of ions with a specific group on the adsorbing surface, in accordance with the concept of zero point charge (zpc). The radionuclide content was determined by gamma-spectrometry. The (60)Co chemical species present in aqueous solutions with different pH values were surveyed by using high-voltage electrophoresis. It was also found that (60)Co was present only as a cationic species at pH 1, 3, 5 and 7 and a neutral species at alkaline pH.

Adsorption↗
PubMed2005

Speciation and biosynthetic variation in four dictyoceratid sponges and their cyanobacterial symbiont, Oscillatoria spongeliae.

Four species of marine sponges (Phylum Porifera, Order Dictyoceratida), which contain the filamentous cyanobacterial symbiont Oscillatoria spongeliae, were collected from four locations in Palau. The halogenated natural products associated with the symbiont were characterized from each sample, revealing that each species contained either chlorinated peptides, brominated diphenyl ethers, or no halogenated compounds. Analysis of the host sponges and the symbionts indicated that each species of sponge contained a distinct strain of morphologically similar cyanobacteria. Although cospeciation may be present in this group, we have identified that at least one host switching event has occurred in this symbiosis. Only the strain of O. spongeliae in the sponge containing the chlorinated compounds possessed genes involved in the biosynthesis of chlorinated leucine precursors, indicating that the chemical variation observed in these animals has a genetic foundation.

Animals↗
PubMed2005

Contrasting lead speciation in forest and tilled soils heavily polluted by lead metallurgy.

The concentration trends and chemical fractionation of Pb was studied in eight tilled and forest soil profiles heavily polluted by Pb metallurgy in the Pribram district, Czech Republic. The highest Pb concentrations were observed in surface and subsurface horizons attaining 35,300 mg kg-1 in forest soils and 1233 mg kg-1 in tilled soils. Total Pb concentrations were one order of magnitude lower in tilled soil due to intensive ploughing and annual crop off-take. The results of the Tessier sequential extraction procedure showed the preferential binding of Pb in forest soils to operationally-defined exchangeable positions and soil organic matter (oxidisable fraction). The Pb exchangeable fraction is thought to correspond to weak electrostatic binding on the functional groups of organic matter. In tilled soil, Pb is predominantly bound to operationally-defined Fe and Mn oxides (reducible fraction). A comparison with the background Pb concentration values showed a strong contamination even in mineral horizons IIC and confirmed a strong vertical mobility of Pb within the soil profiles. The calculated mobility factors (MF) showed that up to 72% of Pb is mobile and bioavailable in forest soils. In contrast, the bioavailability of Pb in tilled soils was significantly lower as the MF accounted for up to 30%. In the most polluted horizon of forest soil profile, the X-ray powder diffraction (XRPD) analysis confirmed the presence of anglesite (PbSO4), derived likely from the smelter emissions.

Agriculture↗
PubMed2005

The effect of copper speciation on the formation of chlorinated aromatics on real municipal solid waste incinerator fly ash.

A limited amount of information exists regarding the relationship between the chemical form of copper and the formation of chlorinated aromatics in fly ash. To understand the effects of the various forms of copper on the formation of chlorinated aromatics in real fly ash, we determined the chemical forms of copper present in various types of real fly ash using X-ray absorption near edge structure (XANES) and evaluated the relationship between the chemical forms of copper and the formation of chlorinated aromatics. Copper chloride hydroxide (CuCl2 x 3Cu(OH)2) and cuprous chloride (CuCl) were the predominant copper species found in real fly ash. Although pure cupric chloride (CuCl2) is known to be the most active catalyst for the formation of chlorinated aromatics under experimental conditions with synthetic fly ash, CuCl2 was not found in every real fly ash sample. The amount of copper chloride hydroxide was positively correlated with the formation of chlorinated aromatics in real fly ash and is, consequently, considered to be one of the key species involved in the formation of chlorinated aromatics.

Air Pollutants, Occupational↗
PubMed2005

Speciation of inorganic arsenic in alimentary and environmental aqueous samples by using derivative anodic stripping chronopotentiometry (dASCP).

The purpose of this research was to develop a sensitive and accurate chronopotentiometric method at a gold film electrode, to determine trace and ultra trace levels of As(III) and As(V) in alimentary and environmental water systems. As(III) was directly determined in the aqueous matrix at a deposition potential of -300 mV for 180 s and at a constant anodic current of 2.5 microA, without any sample pre-treatment; moreover the chronopotentiometric method did not require a time-consuming de-oxygenation step prior to the analysis. A 3M HCl solution was chosen as the best stripping medium. The direct analysis of As(V) required the application of a high negative over-potential and, thus, measurements were characterized by poor reproducibility; therefore As(V) was determined after reduction to As(III) with KI in a strong hydrochloric acid solution. Under the optimised electrochemical conditions, detection limits of 0.08 microg As(III) l(-1) were achieved and no significant interferences from Cd, Cu, Pb, Zn and organic substances were observed. As(V) was the most abundant species in all the studied environmental and alimentary aqueous matrices. Amongst the beverages, tea and coffee presented the As(V) highest concentration ranges (934-1740 microg l(-1) and 850-1290 microg l(-1), respectively) while bottled mineral water the lowest (<1.61 microg l(-1)); whereas As(III) levels lower than 5.0 microg l(-1) were detected only in wine samples.

Arsenic↗