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Partitioning of radionuclides and trace elements in phosphogypsum and its source materials based on sequential extraction methods.

Phosphogypsum is a waste produced by the phosphate fertilizer industry. Although phosphogypsum is mainly calcium sulphate dihydrate, it contains elevated levels of impurities, which originate from the source phosphate rock used in the phosphoric acid production. Among these impurities, radionuclides from 238U and 232Th decay series are of most concern due to their radiotoxicity. Other elements, such as rare earth elements (REE) and Ba are also enriched in the phosphogypsum. The bioavailability of radionuclides (226Ra, 210Pb and 232Th), rare earth elements and Ba to the surrounding aquatic system was evaluated by the application of sequential leaching of the phosphogypsum samples from the Brazilian phosphoric acid producers. The sequential extraction results show that most of the radium and lead are located in the "iron oxide" (non-CaSO4) fraction, and that only 13-18% of these radionuclides are distributed in the most labile fraction. Th, REE and Ba were found predominantly in the residual phase, which corresponds to a small fraction of the phosphate rock or monazite that did not react and to insoluble compounds such as sulphates, phosphates and silicates. It can be concluded that although all these elements are enriched in the phosphogypsum samples they are not associated with CaSO4 itself and therefore do not represent a threat to the surrounding aquatic environment.

Barium↗

Theoretical stability assessment of uranyl phosphates and apatites: selection of amendments for in situ remediation of uranium.

Addition of an amendment or reagent to soil/sediment is a technique that can decrease mobility and reduce bioavailability of uranium (U) and other heavy metals in the contaminated site. According to data from literature and results obtained in field studies, the general mineral class of apatites was selected as a most promising amendment for in situ immobilization/remediation of U. In this work we presented theoretical assessment of stability of U(VI) in four apatite systems (hydroxyapatite (HAP), North Carolina Apatite (NCA), Lisina Apatite (LA), and Apatite II) in order to determine an optimal apatite soil amendment which could be used for in situ remediation of uranium. In this analysis we used a theoretical criterion which is based on calculation of the ion-ion interaction potential, representing the main term of the cohesive energy of the matrix/pollutant system. The presented results of this analysis indicate (i) that the mechanism of immobilization of U by natural apatites depends on their chemical composition and (ii) that all analyzed apatites represent, from the point of view of stability, promising materials which could be used in field remediation of U-contaminated sites.

Adsorption↗

Further evidence for elevated human minisatellite mutation rate in Belarus eight years after the Chernobyl accident.

Analysis of germline mutation rate at human minisatellites among children born in areas of the Mogilev district of Belarus heavily polluted after the Chernobyl accident has been extended, both by recruiting more families from the affected region and by using five additional minisatellite probes, including multi-locus probe 33.6 and four hypervariable single-locus probes. These additional data confirmed a twofold higher mutation rate in exposed families compared with non-irradiated families from the United Kingdom. An elevated rate was seen at all three independent sets of minisatellites (detected separately by multi-locus probes 33.15, 33.6 and six single-locus probes), indicating a generalised increase in minisatellite germline mutation rate in the Belarus families. Within the Belarus cohort, mutation rate was significantly greater in families with higher parental radiation dose estimated for chronic external and internal exposure to caesium-137, consistent with radiation induction of germline mutation. The spectra of mutation seen in the unexposed and exposed families were indistinguishable, suggesting that increased mutation observed over multiple loci arises indirectly by some mechanism that enhances spontaneous minisatellite mutation.

Adult↗

A 40+ year record of Cd, Hg, Pb, and U deposition in sediments of Patroon Reservoir, Albany County, NY, USA.

Sediments of the Patroon Creek watershed (33 km(2)) are known to contain significant concentrations of heavy metals derived from two industrial sites within the watershed. Mercury Refining, Inc (Mereco) has stored and recycled Hg from 1955 to the present day, and National Lead Industries (NLI) manufactured aircraft components containing Cd, Pb, and U from 1958 to 1984. Here we present the first record of heavy metal deposition as preserved in a 3-m long sediment core collected in 1999 from Patroon Reservoir, a small water body (1.3 ha) downstream of the industrial sites. Bulk sediment samples were collected from the core at 0.05-m intervals and analyzed for total Cd, Pb, and U by ICP-MS and total Hg by CVAAS. Total Hg increases from less than 1 mg kg(-1) (dw) below 1.68 m, to a maximum of 6.2 mg kg(-1) at 0.80 m, and then declines to the sediment-water interface. Total Cd, Pb, and U concentrations increase abruptly above 1.68 m to maximum values of 25, 320, and 3600 mg kg(-1) (dw), respectively, and then decline gradually upwards. By correlating metal profiles with industrial history, we conclude that the 1.68 m horizon was deposited no earlier than 1958, the beginning of aircraft component manufacturing at NLI. The average, apparent sedimentation rate within the reservoir has a minimum value of approximately 0.04 m year(-1) for the 41-year period from 1958 to 1999. In the interval 0--1.68 m, average concentrations of Cd, Hg, Pb, and U are 1.69, 1.50, 461, and 13 mg kg(-1), respectively. These levels are comparable with other lake, reservoir and stream sediments that have been moderately to severely impacted by industrial pollution and are above levels expected to be detrimental to aquatic organisms.

Cadmium↗

Adsorbed U(VI) surface species on muscovite identified by laser fluorescence spectroscopy and transmission electron microscopy.

Time-resolved laser-induced fluorescence spectroscopy (TRLFS) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) were applied to investigate the species of uranyl(VI) adsorbed onto muscovite platelets and muscovite suspensions (grain size: 63-200 microm). TRLFS provided evidence for the presence of two adsorbed uranium(VI) surface species on edge-surfaces of muscovite. The two species showed different positions of the fluorescence emission bands and different fluorescence lifetimes indicating a different coordination environment for the two species. HAADF-STEM revealed that nanoclusters of an amorphous uranium phase were attached to the edge-surfaces of muscovite powder during batch sorption experiments. These U-nanoclusters were not observed on {00/} cleavage planes of the muscovite. The surface species with the shorter fluorescence lifetimes are interpreted as truly adsorbed bidentate surface complexes, in which the U(VI) binds to aluminol groups of edge-surfaces. The surface species with the longer fluorescence lifetimes are interpreted to be an amorphous U(VI) condensate or nanosized clusters of polynuclear uranyl(VI) surface species with a particle diameter of 1 to 2 nm. Depending on the size of these clusters the fluorescence lifetimes vary; i.e., the larger the nanosized clusters, the longer is the fluorescence lifetime.

Adsorption↗

Covalent attachment of metal chelates to proteins:the stability in vivo and in vitro of the conjugate of albumin with a chelate of 111indium.

Human serum albumin has been conjugated to 1-(p-bnezenediazonium)-(ethylenedinitrilo)tetraacetic acid, a powerful chelating agent, and radioactive 111indium ions have been added specifically to the chelating groups. The product, with a specific radioactivity of about 1 mCi/mg of protein, was employed as a radiotracer in scintillation scanning studies with human volunteers. Results show that 48 hr after injection, practically all of the label remains attached to albumin. This is confirmed by electrophoresis of serum proteins; 7 days after injection, 85% of the radioactivity in the serum is still in the albumin fraction. These observations agree with in vitro studies of the labeled albumin in human serum, where loss of the metal ion from the chelating group to the protein transferrin amounts to less than 3% after 1 week and less than 5% after 2 weeks. Measurements of the distribution of label in mice up to 23 days after injection suggest that metabolism of the labeled protein does not lead to binding of indium ions by transferrin. The binding of indium and other metal ions by transferrin has previously posed a major impediment to the use of metal chelates for in vivo diagnostic procedures. Demonstration of the kinetic inertness of the chelate in these experiments suggests the use of related chelates as physical probes of biological systems.

Animals↗

Dietary exposure to lead, cadmium, mercury and radionuclides of an adult urban population in Lebanon: a total diet study approach.

Human exposure to toxic chemicals is suspected of being responsible for a wide range of human health disorders. This study is the first in Lebanon to evaluate the dietary exposure of an adult urban population to three heavy metals (lead, cadmium and mercury) and to radionuclides. Exposure assessment was performed by means of the total diet study approach as recommended by the Word Health Organization. Five 'total diets' were collected during 2003-04. Average and maximal consumer exposure estimates to heavy metals were calculated and compared with appropriate reference values and with intakes reported from other countries. The average dietary intakes of lead, cadmium and mercury represented 7, 17 and 5.6%, respectively, of the appropriate provisional tolerable weekly intakes (PTWI). The mean dietary intake of methylmercury represented 17.5% of the appropriate PTWI. Cs-134 and I-131 were not detected in any of the food samples. Traces of Cs-137 were only found in five food samples. The exposure assessment conducted places Lebanon among countries least exposed to heavy metals through the diet and it highlights the safety of the food supply from radioactive contamination.

Adult↗

Clearance by the rat of inhaled fly ash from fluidized-bed coal combustion.

Fly ash from a fluidized-bed coal combustor was neutron-activated and administered to male Fischer 344 rats by a single nose-only inhalation exposure. The activated fly ash contained 46Sc and smaller amounts of other gamma-emitting radionuclides. Whole-body clearance of radioactivity to 127 d was described by an exponential equation, with the long-term component having a biological half-life of 78 d. High-resolution gamma spectra of the lungs were obtained with a Ge(Li) detector and the relative activities of several fly ash constituents were compared. The activities of 152Eu, 134Cs, 54Mn, and 60Co significantly decreased with time relative to those of 46Sc and 59Fe. These results indicate that the clearance of fly ash is similar to that of other relatively insoluble particles and that some elements may have been preferentially dissolved from the fly ash particles in vivo.

Air Pollutants↗

Chemical and radiological profile of the coal ash landfill in Kastel Gomilica.

The objective of this study was to determine the chemical, radiological and leaching properties of slag and ash produced by a thermoelectric unit of a former factory Adriavinil and deposited in the area of Kasktel Gomilica near Split, Croatia. A total of 33 samples were analysed. The bioavailable fraction of the slag and ash was estimated using different leaching tests. The waste material was characterized by a high activity of naturally occurring radionuclides 238U, 235U and 226Ra and by elevated concentrations of heavy metals. The concentrations of most heavy metals were three to four times as high as in the common soil. Uranium slag and ash concentration was almost 40 times higher than in control soil. More than 37% of the total U could be removed from the slag and ash with the sea water.

Coal↗

[Evaluating comprehensive quality of sediment in Dianchi Lake using adjusted AHP method and 137Cs dating].

It is difficult to evaluate comprehensive quality of sediment and to understand development trend of pollution because of absence of monitoring data, especially history data. Combining the method of 137Cs dating with the ways of general sampling and measurement can easily resolve the problem of absence of data and also provide the possibility for calculating weighted environmental quality comprehensive index using the adjusted analytical hierarchy process (AHP) method. In order to overcome the willfulness the judgment matrix is formed objectively based on calculating monitoring data. Based on the monitoring data of sediment pollution and the weights of various factors gained by adjusted AHP method the comprehensive quality of sediment in each zone of Dianchi Lake was evaluated and the results indicated that the pollution of sediments in each zone at the present be serious more than that in the history. The condition may be related to the industrial development and distribution of industries in Dianchi Lake basin. Therefore, in order to improve the comprehensive quality of sediment in Dianchi Lake and to prevent the secondary pollution of heavy metals in sediment from happening, it is necessary to control the pollutants discharge and to remove the pollutants with various ways.

Cesium Radioisotopes↗

Ocular trace metal kinetics and toxicology. I. The distribution of intravitreally injected 67Cu++ within intraocular compartments and its loss from the globe.

Radioactive copper (67Cu++) was injected into the center of the vitreous body of rabbits. The relatively rapid initial loss of 67Cu from the vitreous was associated with its accumulation in intraocular tissues. At 24 hr, 20% of the injected 67Cu was found in the retina, representing the highest 67Cu concentration among all ocular tissues, and this high 67Cu concentration was maintained in this tissue throughout the 10-day observation period. Significant amounts of 67Cu were not detected in the aqueous humor at any time. About one-half of the injected 67Cu was lost from the whole globe in 5 days, but the remaining Cu was retained in the globe during the next 5 days. Eyes that received a large dose of CuSO4 in addition to the tracer showed decreased 67Cu activity in the retina and a slight increase in the aqueous humor. Endotoxin-induced ocular inflammation decreased the rate of 67Cu loss from the vitreous, reduced its accumulation by the retina, and increased 67Cu entry into the aqueous humor. It is concluded that 67Cu is retained in the vitreous and the globe due to its binding by, and/or uptake into, intraocular tissues, especially the retina. Cu does not effectively enter the anterior chamber from the vitreous, apparently due to its effective removal by the ciliary processes, thus ruling out the possibility of identifying the existence of Cu-containing intraocular foreign bodies in the posterior segment of the eye by analysis of Cu in the aqueous humor.

Animals↗

Diamine ligand release from the cisplatin analogue [meso-1,2-bis(2,6-dichloro-4- hydroxyphenyl)ethylenediamine]dichloroplatinum(II) in cell culture medium.

The stability of the five-membered chelate ring of the cisplatin analogue [meso-1,2-bis(2,6-dichloro-4- hydroxyphenyl)ethylenediamine]dichloroplatinum(II) was investigated under typical cell culture conditions (IMEM-Richter's medium with 10% fetal calf serum, 37 degrees C). For this purpose, the platinum compound was radiolabeled with tritium in the meta position of the aromatic ring by an acid-catalyzed tritium-exchange reaction, and a reversed-phase HPLC assay with radiochemical detection was developed to monitor for the presence of the free diamine ligand in the cell culture medium. A gradual increase in radioactivity attributed to the free diamine was found in medium containing the dichloroplatinum(II) complex (ca. 25% after 24 h), indicating that the diamine ligand was being released from the metal atom. When 1 mM glutathione (GSH) was included in the incubation medium, the amount of free diamine nearly doubled after 24 h, while the amount of radioactivity attributed to serum protein-platinum adducts decreased relative to incubations without GSH. On the other hand, the omission of serum from the incubations resulted in a dramatic decrease in the amount of radioactivity eluting under the diamine peak, while the concentrations of the two methionine-Pt adducts, which formed in a 1:1 ratio, rose. Through the use of liquid secondary ion mass spectroscopy, the two methionine-Pt adducts were identified as monomethionine metabolites of the title compound, whereby the two chloride ligands have been replaced by the amino acid. These compounds are probably diastereomers since the sulfur of methionine can coordinate to platinum with equal probability either cis or trans to the R-configured benzylamine carbon. On the basis of the chemical shifts of the MeS groups in the 250-MHz 1H NMR, it is concluded that a S,N-five-membered chelate ring is present in these methionine-Pt adducts.

Cells, Cultured↗

Influence of trivalent electrolytes on the humic colloid-borne transport of contaminant metals: competition and flocculation effects.

With the objective to assess the relevance of competitive effects in respect of the humic colloid-borne migration of actinides in case of release, the influence of Al(III) on humate complexation of La(III) as an analogue of trivalent actinides was investigated for various humic materials by using 140La as a radioactive tracer, allowing measurements in very dilute systems to simulate realistic settings. Generally, competition by aluminium is not detectable unless the metal-loading capacity of the humic colloids is nearly exhausted. For average contents of organic carbon, a threshold value of 10(-6) M Al(III) can be specified. The metal exchange turned out to be kinetically hindered. Effects on co-adsorption of La(III) and humic acid were found to be less important. Immobilization by the concomitantly induced flocculation process outweighs the role of displacement effects. Comparative studies on complexation and flocculation of humic acid with Al(III), Ga(III), In(III), Sc(III), Y(III), and La(III) were undertaken in order to evaluate the influence of specific properties apart from ion charge and to characterize the mechanism of flocculation. In spite of considerable variations in the binding affinities among these metals, it can be inferred that the possibility of significant competitive effects in natural aquatic systems is confined to Al(III). Complex stabilities and flocculation efficiencies proved to be interrelated. Precipitation is thus attributed to homocoagulation of humic colloids induced by charge compensation, which is further supported by flocculation experiments with Al(III) depending on pH, ionic strength, and humic acid concentration.

Adsorption↗

Synthesis of the first diethylenetriaminepentahydroxamic acid (DTPH) bifunctional chelating agent.

Synthesis of a new pentahydroxamic acid bifunctional chelating agent (BCA), constructed on the aminoazaalkyl core of diethylenetriaminepentaacetic acid (DTPA), is reported. Rational modifications in the structure of DTPA, which could result in an enhancement of its chelation properties, add to the collection of diagnostic and therapeutic metals bound by this chelator, and might implement significant improvements in the in vivo behavior of this compound, are described. Further improvements in the stability of the ligand-metal complexes of DTPA may improve both diagnostic and therapeutic outcomes such as tumor-to-normal tissue ratios and target-delivered radioactivity. A combination of hydroxamate functions with the azaalkyl backbone of DTPA might be a suitable approach to generate such higher stabilities. This rationale may be justified by the well-known affinity of hydroxamates against different transition metals and favorable properties of DTPA as a versatile chelator. Thus, the N(4),N(alpha),N(alpha),N(epsilon),N(epsilon)-pentakis[[((N-hydroxy-N-methyl]carbonyl)methyl]-2, 6-diamino-4-azahexanoic hydrazide (5, DTPH) was designed and synthesized through a convergent synthesis and in 40.7% overall yield. Conjugation of this compound to the monoclonal antibody (MAb) Delta Ch2HuCC49, used as a model protein, was carried out to evaluate the efficiency of this molecule as a BCA. Radiolabeling of the DTPH-Delta CH2HuCC49 conjugate with lutetium-177 ((177)Lu) and biodistribution of the labeled conjugate in athymic nude mice, bearing LS174T human colon carcinoma xenografts, are reported.

Animals↗

Analytical microscopy and environment. Current developments using bioindicators of pollution by stable and radioactive elements.

Ecotoxicological investigations were performed on three sets of bioindicators. The first one concerns marine pollution of invertebrates (molluscs: the mussel Mytilus edulis and related species, crustaceans: the crab Liocarcinus puber and related species), contaminated by stable or radioactive elements originating from wastes discharged into sea water. The second one concerns freshwater pollution of vertebrates (fish: the brown trout Salmo trutta fario), contaminated by aluminium dissolved in rivers, as a consequence of an atmospheric pollution by acid rain. The third one concerns the atmospheric pollution of trees by plutonium (Casuarina equisetifolia). Mechanisms involved in the uptake, storage and elimination processes of these toxicants were studied, with a special emphasis on cellular and subcellular aspects of concentration sites. Two microanalytical methods were employed: Secondary Ion Mass Spectrometry (SIMS), using the ion microscope and the ion microprobe, and X-ray spectrometry using the electron microprobe (EMP). In marine organisms, the target organs and tissues of bioaccumulation of stable and radioactive elements (238U, 239Pu and 241Am), were shown to be mainly digestive gland, gill and exoskeleton. The target organelles were shown to be spherocrystals and lysosomes. Amoebocytes, enzymatically equipped with lysosomal phosphatase, were involved in the phagocytic clearance of metal pollutants. In trout, insolubilisation of Al phosphate within lysosomes and a high metal concentration within bones were observed. The tree Casuarina equisetifolia exhibits a particular ability to concentrate atmospheric plutonium within its leaves.

Air Pollution↗

Sponge 'sentinel' of heavy metals.

The possibility of monitoring siliceous sponges as an ideal bioindicator of 17 trace metals and halogens was investigated. Of the two species of Demosponge from the Indian coastal waters receiving stable and radioactive nuclides (54Mn, 63Ni, 65Zn, 60Co, 75Se, 113Sn, 90Sr, 131I, 137Cs), Spirastrella cuspidifera was found to accumulate Cd, Cr, and Sn in the range of 15-2000 micrograms g-1 dry tissue, some 5-7 orders of magnitude higher than in the ambient waters. Prostylyssa foetida, from the same microecological niche, was found to be totally free of these three metal ions. The bioaccumulation of Ni was also significantly higher in S. cuspidifera (400-2250 micrograms g-1) than in P. foetida (7-15 micrograms g-1). The former species was also found to be an ideal sentinel for detecting levels of Co, Zn, and Ti; levels of Cu, Mn, Pb Fe and Sr were higher in P. foetida, but those of the halogens I and Br were practically identical in both species. Furthermore, bioaccumulation of metal ions was found to be a function of sponge tissue itself, rather than that of either obligate or facultative symbiont microflora. In view of the high degree of species specificity which sponges exhibit while accumulating many trace metal ions, a 'sponge watch programme' is proposed on a global scale for monitoring the health of coastal ecosystems against a variety of potentially toxic pollutants.

Animals↗