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PubMed2001

PAHs in dated sediments of Ashtabula River, Ohio, USA.

Polycyclic aromatic hydrocarbons (PAHs) in dated sediments from Ashtabula River, Ohio, were determined, and a chemical mass balance (CMB) model was used to apportion sources. Three cores (AR-1,AR-2,AR-3) were dated by correlating uranium-supported 210Pb peaks with 1964, 1972, 1977, and 1979 maxima in the discharge record for Ashtabula River. These cores had sedimentation rates between 7.1 and 4.4 cm/year, while a fourth (AR-4) exhibited a much higher rate of 27.8 +/- 18 cm/year. The highest PAH concentration was 11,500 ng/g found in layer 6 of AR-1 (1986), and the lowest was 621 ng/g found in layer 8 of AR-2 (1982). The source contributions to the total PAH concentrations estimated by the CMB model are 0.1-2.2%, 16.8-22.8%, and 78.1-83.8% for wood burning (WB), coke oven (CO), and highway dust (HWY), respectively. Petroleum generated PAHs have maximal contribution during 1977-79, and wood burning PAHs show minimal emissions during 1975-77 in accordance with U.S. consumption records and other studies. Among six PAH markers, only phenanthrene may be subjected to aerobic biodegradation or photolysis with an apparent half-life of 0.005-0.025 year. No anaerobic degradation was observed based on the CMB model. The model works well for the nonmarker compounds, fluoranthene, and benzo[b]fluoranthene/benzo[k]fluoranthene.

Biodegradation, Environmental↗

PubMed1992

[Chemically-induced scleroderma].

Scleroderma-like diseases can be induced by a number of chemical compounds, such as plastics, solvents and drugs. Contaminated rapeseed oil was the cause of the toxic oil syndrome and L-tryptophan induces the so-called eosinophilia-myalgia-syndrome. On the other hand, paraffin and silicon can trigger so-called adjuvant disease, while long-term exposure to silica can lead to idiopathic scleroderma (associated with silicosis in some cases). In addition to the clinical features, some pathogenetic data in the literature, such as genetic factors (HLA, chromosomal anomalies, enzyme deficiencies) and the metabolism of chlorinated ethylenes via reactive epoxide intermediate products, and our own findings are reported. Silica-induced scleroderma cannot be distinguished from the idiopathic form by epidemiological, clinical or immunological studies or by parameters referring to the blood vessels or collagen metabolism. In cell culture studies it has been shown that macrophages/monocytes release IL1, IL6 and TNF after ingestion of silica, which affects fibroblasts, T-helper cells and endothelial cells. Comparative results from the silicosis literature are reported. Finally, the possibly stimulating role of ionizing irradiation (uranium mining) in favouring the development of scleroderma is discussed.

Ethylenes↗

PubMed2003

Feasibility studies for assessing internal exposure to 233U.

The potential internal occupational exposure encountered as a consequence of the 232Th-233U fuel cycle are likely to arise predominantly from the inhalation of 232Th, 233U and (232Th + 233U) compounds of absorption Types M and S. In the past, although direct and indirect methods for assessments of internal exposure to 232Th and its daughters were developed, standardised and employed, no such attempts have been made with regard to 233U and 233U + 232Th. Therefore, feasibility studies for assessing internal exposure to 233U have been conducted using three methods: urine bioassay, in vivo counting and measurement of thoron gas in the exhaled breath of a worker. This paper describes details of these studies and discusses the results obtained.

Air Pollutants, Radioactive↗

PubMed2005

High-temperature, high-pressure hydrothermal synthesis, crystal structure, and solid-state NMR spectroscopy of Cs2(UO2)(Si2O6) and variable-temperature powder X-ray diffraction study of the hydrate phase Cs2(UO2)(Si2O6) x 0.5H2O.

A new uranium(VI) silicate, Cs2(UO2)(Si2O6), has been synthesized by a high-temperature, high-pressure hydrothermal method and characterized by single-crystal X-ray diffraction and solid-state NMR spectroscopy. It crystallizes in the orthorhombic space group Ibca (No. 73) with a = 15.137(1) A, b = 15.295(1) A, c = 16.401(1) A, and Z = 16. Its structure consists of corrugated achter single chains of silicate tetrahedra extending along the c axis linked together via corner-sharing by UO6 tetragonal bipyramids to form a 3-D framework which delimits 8- and 6-ring channels. The Cs+ cations are located in the channels or at sites between channels. The 29Si and 133Cs MAS NMR spectra are consistent with the crystal structure as determined from X-ray diffraction, and the resonances in the spectra are assigned. Variable-temperature in situ powder X-ray diffraction study of the hydrate Cs2(UO2)(Si2O6) x 0.5H2O indicates that the framework structure is stable up to 800 degrees C and transforms to the structure of the title compound at 900 degrees C. A comparison of related uranyl silicate structures is made.

Journal Article↗

PubMed1993

Embryotoxicity and teratogenicity of uranium in mice following subcutaneous administration of uranyl acetate.

The effects of multiple maternal subcutaneous injections of uranyl acetate dihydrate (0.5, 1, and 2 mg/kg/d) from d 6 to d 15 of gestation were evaluated in Swiss mice. External, internal soft-tissue and skeletal examinations of fetuses were performed on gestation d 18. Maternal toxicity occurred in all uranium-treated groups as evidenced primarily by deaths as well as significant decreases in weight gain and in body weight at termination. Although it was not dose-related, embryotoxicity also occurred in all uranium-treated groups (significant increases in the number of nonviable implantations and in the percentage of postimplantation loss). Fetal body weight was significantly decreased at 1 and 2 mg/kg/d, whereas the number of total internal and total skeletal defects showed dose-dependent increases at 0.5, 1, and 2 mg/kg/d. Most morphological defects were developmental variations, whereas malformations were only detected at 1 and 2 mg/kg/d. On the basis of these data, both the maternal no-observable-adverse-effect level (NOAEL) and the NOAEL for embryotoxicity of uranyl acetate dihydrate were below 0.5 mg/kg/d, whereas the NOAEL for teratogenicity was 0.5 mg/kg/d.

Animals↗

PubMed1995

Phosphorus as a potential guide in the search for extinct life on Mars.

In contrast to the search for extant organisms, the quest for fossil remains of life on Mars need not be guided by the presence of water and organic compounds on the present surface. An appropriate tracer might be the element phosphorus which is a common constituent of living systems. Utilizing terrestrial analogues, it should preferentially exist in the form of sedimentary calcium phosphate (phosphorites), which would have readily resisted changing conditions on Mars. Moreover, higher ratios of P/Th in phosphorites in comparison to calcium phosphates from magmatic rocks give us the possibility to distinguish them from inorganically formed phosphorus deposits at or close to the Martian surface. Identification of anomalous phosphorus enrichments by remote sensing or in situ analysis could be promising approaches for selecting areas preferentially composed of rocks with remains of extinct life.

Calcium Phosphates↗

PubMed1984

Active-site-directed inactivators of the Zn2+-containing D-alanyl-D-alanine-cleaving carboxypeptidase of Streptomyces albus G.

Several types of active-site-directed inactivators (inhibitors) of the Zn2+-containing D-alanyl-D-alanine-cleaving carboxypeptidase were tested. (i) Among the heavy-atom-containing compounds examined, K2Pt(C2O4)2 inactivates the enzyme with a second-order rate constant of about 6 X 10(-2)M-1 X S-1 and has only one binding site located close to the Zn2+ cofactor within the enzyme active site. (ii) Several compounds possessing both a C-terminal carboxylate function and, at the other end of the molecule, a thiol, hydroxamate or carboxylate function were also examined. 3-Mercaptopropionate (racemic) and 3-mercaptoisobutyrate (L-isomer) inhibit the enzyme competitively with a Ki value of 5 X 10 X 10(-9)M. (iii) Classical beta-lactam compounds have a very weak inhibitory potency. Depending on the structure of the compounds, enzyme inhibition may be competitive (and binding occurs to the active site) or non-competitive (and binding causes disruption of the protein crystal lattice). (iv) 6-beta-Iodopenicillanate inactivates the enzyme in a complex way. At high beta-lactam concentrations, the pseudo-first-order rate constant of enzyme inactivation has a limit value of 7 X 10(-4)S-1 X 6-beta-Iodopenicillanate binds to the active site just in front of the Zn2+ cofactor and superimposes histidine-190, suggesting that permanent enzyme inactivation is by reaction with this latter residue.

Binding Sites↗

PubMed1983

Effect of experimental acute renal failure on intrinsic renal tubular secretory clearance of organic cations in rats.

Effect of experimental acute renal failure (EARF) on the intrinsic renal tubular secretory clearance (CLscnint) of tetraethylammonium bromide (TEA) and N1-methylnicotinamide (NMN) was examined in rats treated with glycerol, folate, salicylate, uranium and gentamicin. The values of CLscnint was calculated by an equation incorporating the determinants of the renal clearance (CLr), i.e., renal tubular secretory clearance (CLscnr), glomerular filtration rate (GFR), renal plasma flow (RPF), free fraction of the drug in plasma (fp) and fraction (Freabs) of the drug reabsorbed after filtration and secretion in the urine. In the EARF-rats, the values of CLscnint of NMN and TEA were decreased by 0.017-0.575 times and by 0.005-0.737 times as compared to those of the normal rats, respectively. It was suggested that the decreases in CLscnr of both NMN and TEA were due not to the decrease in RPF, but to that in CLscnint.

Acute Kidney Injury↗

PubMed2001

Actinide interactions with microbial chelators: the dioxobis[pyridine-2,6-bis(monothiocarboxylato)]uranium(VI) ion.

The title complex, bis(tetraphenylphosphonium) dioxobis(pyridine-2,6-dicarbothioato-O,N,O')uranium(VI), (C(24)H(20)P)(2)[UO(2)(C(7)H(3)NO(2)S(2))(2)], was prepared by reacting two equivalents of pyridine-2,6-bis(monothiocarboxylate) (pdtc) with uranyl nitrate. The geometry of the eight-coordinate U atom is hexagonal bipyramidal, with the uranyl O atoms in apical positions. This is the first reported complex in which this ligand binds a metal through the O and not the S atoms. Principal bond lengths include uranyl lengths of 1.774 (2) A, U--O distances of 2.434 (2) and 2.447 (3) A, and two U--N distances of 2.647 (3) A. The anion lies on an inversion centre.

Actinoid Series Elements↗

PubMed1982

Further studies on the absorption of actinide elements from the gastrointestinal tract of neonatal animals.

Plutonium retention was measured after intragastric administration to neonatal rats, dogs and swine. At 1 week after administration, substantially more of the actinide remained in swine and dogs than in rats. The quantity of 238Pu absorbed by piglets was markedly influenced by such factors as compound solubility, mass of plutonium administered, oxidation state of the actinide, and age of the animal at gavage. Cortisone treatment reduced absorption, but was less effective in piglets than in neonatal rats. Measurements of 238Pu transport from ligated segments of the neonatal swine intestine indicated highest absorption from the duodenum, where the actinide was shown, autoradiographically, to be deposited in the epithelial region; in the ileum, deposition was predominantly in the lacteal region. Absorption of actinides by neonatal swine decreased in the order of 233U greater than 238Pu greater than 237Np greater than 244Cm greater than 241Am. Measurements at 1 yr after gavage showed a much higher retention by swine than by rats.

Actinoid Series Elements↗

PubMed2006

Exposure of pregnant rats to uranium and restraint stress: effects on postnatal development and behavior of the offspring.

The effects on postnatal development and behavior were assessed in the offspring of female rats concurrently exposed to uranium (U) and restraint stress. Adult female rats were administered uranyl acetate dihydrate (UAD) in the drinking water at doses of 0, 40 and 80 mg/(kg day) for 4 weeks before mating with untreated males, as well as during pregnancy and lactation. One-half of female rats in each group were concurrently subjected to restraint (2h/day). On gestation day 14, one-half of restrained and unrestrained rats were sacrificed in order to evaluate maternal toxicity and gestational parameters. Pups were evaluated for physical development, neuromotor maturation, and behavior. Uranium concentrations were also determined in various tissues of dams and fetuses. In all uranium-treated groups, the highest concentrations of this element were found in kidney and bone, being considerably higher than those in brain. Uranium levels in tissues of dam or fetuses were not significantly affected by restraint. No significant interactions between uranium and restraint could be observed in maternal toxicity. Moreover, no relevant effects of uranium, maternal restraint, or their combination were noted on developmental landmarks in the offspring. In the passive avoidance test, at 40 and 80 mg UAD/(kg day) restraint significantly modified passive avoidance acquisition (T1) and retention time (T2) 24h later. However, no significant differences were observed on the Morris water maze test. The results of the present study indicate that, in general terms, exposure of female rats to UAD before mating with untreated males, as well as during gestation and lactation, did not cause relevant dose-related adverse effects on postnatal development and behavior of the offspring. The influence of stress was very limited.

Animals↗

PubMedDate not supplied

[The genotoxic action of uranyl ions on DNA in vitro caused by the generation of reactive oxygen species].

8-Oxoguanine (8-OG) is an important biomarker of oxidative DNA damage induced by reactive oxygen species (ROS). By using ELISA with monoclonal antibodies against 8-OG, the formation of 8-OG in DNA by the action of uranyl ions, gamma-irradiation, and heating at 37 degrees C and their combined action was investigated in view of environmental pollution by uranium oxides as a result of the use of armor piercing shells with depleted uranium. The content of 8-OG in DNA induced by the action of gamma-irradiation, 5 microM uranyl ions and heating changes with time in a complicated manner. These results suggest that, by the action of uranyl ions, an additional generation of ROS occurs, which leads both to the formation of 8-OG in DNA and its further oxidation. Uranyl ions at a conceptration of 5 microM increase the thermal deamination of cytosine in DNA several times but do not influence DNA thermal depurination. It is shown that uranyl ions essentially increase the production of hydrogen peroxide and hydroxyl radicals by the action of heat on water. The results indicate a high chemical genotoxicity of uranyl ions and their enhancing effect on DNA base damage by the action of heat and gamma-irradiation.

Animals↗

PubMed2005

X-Ray microanalytical techniques based on synchrotron radiation.

The development of 3rd generation synchrotron radiation sources like European Synchrotron Radiation Facility (ESRF) in parallel with recent advances in the technology of X-ray microfocusing elements like Kirkpatrick-Baez (KB) mirrors, diffractive (Fresnel zone plates, FZP) and refractive (compound refractive lenses, CRL) optics, makes it possible to use X-ray microscopy techniques with high energy X-rays (energy superior to 4 keV). Spectroscopy, imaging, tomography and diffraction studies of samples with hard X-rays at micrometre and sub-micrometre spatial resolutions are now possible. The concept of combining these techniques as a high-energy microscopy has been proposed and successfully realized at the ESRF beamlines. Therefore a short summary of X-ray microscopy techniques is presented first. The main emphasis will be put on those methods which aim to produce sub-micron and nanometre resolution. These methods fall into three broad categories: reflective, refractive and diffractive optics. The basic principles and recent achievements will be discussed for all optical devices. Recent applications of synchrotron based microanalytical techniques to characterise radioactive fuel particles (UO(2)) released from the Chernobyl reactor are reported.

Environmental Monitoring↗

PubMed2001

Neoplastic transformation of human osteoblast cells to the tumorigenic phenotype by heavy metal-tungsten alloy particles: induction of genotoxic effects.

Heavy metal-tungsten alloys (HMTAs) are dense heavy metal composite materials used primarily in military applications. HMTAs are composed of a mixture of tungsten (91-93%), nickel (3-5%) and either cobalt (2-4%) or iron (2-4%) particles. Like the heavy metal depleted uranium (DU), the use of HMTAs in military munitions could result in their internalization in humans. Limited data exist, however, regarding the long-term health effects of internalized HMTAs in humans. We used an immortalized, non-tumorigenic, human osteoblast-like cell line (HOS) to study the tumorigenic transforming potential of reconstituted mixtures of tungsten, nickel and cobalt (rWNiCo) and tungsten, nickel and iron (rWNiFe). We report the ability of rWNiCo and rWNiFe to transform immortalized HOS cells to the tumorigenic phenotype. These HMTA transformants are characterized by anchorage-independent growth, tumor formation in nude mice and high level expression of the K-ras oncogene. Cellular exposure to rWNiCo and rWNiFe resulted in 8.90 +/- 0.93- and 9.50 +/- 0.91-fold increases in transformation frequency, respectively, compared with the frequency in untreated cells. In comparison, an equivalent dose of crystalline NiS resulted in a 7.7 +/- 0.73-fold increase in transformation frequency. The inert metal tantalum oxide did not enhance HOS transformation frequency above untreated levels. The mechanism by which rWNiCo and rWNiFe induce cell transformation in vitro appears to involve, at least partially, direct damage to the genetic material, manifested as increased DNA breakage or chromosomal aberrations (i.e. micronuclei). This is the first report showing that HMTA mixtures of W, Ni and Co or Fe cause human cell transformation to the neoplastic phenotype. While additional studies are needed to determine if protracted HMTA exposure produces tumors in vivo, the implication from these in vitro results is that the risk of cancer induction from internalized HMTAs exposure may be comparable with the risk from other biologically reactive and insoluble carcinogenic heavy metal compounds (e.g. nickel subsulfide and nickel oxide).

Alloys↗

PubMed2006

A search for cellular and molecular mechanisms involved in depleted uranium (DU) toxicity.

Addition of U(VI) (uranyl acetate) to isolated rat hepatocytes results in rapid glutathione oxidation, reactive oxygen species (ROS) formation, lipid peroxidation, decreased mitochondrial membrane potential, and lysosomal membrane rupture before hepatocyte lysis occurred. Cytotoxicity was prevented by ROS scavengers, antioxidants, and glutamine (ATP generator). Hepatocyte dichlorofluorescein oxidation was inhibited by mannitol (a hydroxyl radical scavenger) or butylated hydroxyanisole and butylated hydroxytoluene (antioxidants). Glutathione depleted hepatocytes were resistant to U(VI) toxicity and much less dichlorofluorescein oxidation occurred. Reduction of U(VI) by glutathione or cysteine in vitro was also accompanied by oxygen uptake and was inhibited by Ca(II) (a U(IV) or U(VI) reduction inhibitor). U(VI)-induced cytotoxicity and ROS formation was also inhibited by Ca(II), which suggests that U(IV) and U(IV) GSH mediate ROS formation in isolated hepatocytes. The U(VI) reductive mechanism required for toxicity has not been investigated. Cytotoxicity was also prevented by cytochrome P450 inhibitors, particularly CYP 2E1 inhibitors, but not inhibitors of DT diaphorase or glutathione reductase. This suggests that P450 reductase and reduced cytochrome P450 contributes to U(VI) reduction to U(IV). In conclusion, U(VI) cytotoxicity is associated with mitochondrial/lysosomal toxicity by the reduced biological metabolites and ROS.

Animals↗

PubMed1986

Loss of glomerular responses to vasoconstrictor agents in rabbits recovering from ARF.

Glomerular responses to angiotensin II (AII), arginine vasopressin (AVP), and norepinephrine (NE) were estimated in rabbits recovering from uranium-mediated nephropathy or ischemic acute renal failure (ARF) to examine roles of intraglomerular events in resistance to ARF. Uranyl acetate (UA, 0.8 mg/kg) produced ARF in some animals but did not in others. Rabbits recovering from UA-induced ARF were highly resistant to a rechallenge with a larger dose of the agent (2 mg/kg). Their glomeruli did not respond to AII, AVP and NE in vitro. In animals having not experienced ARF following the initial insult, however, resistance to the rechallenge was lower than in animals recovering from ARF, and the glomerular response to contractile stimuli was well sustained. A two hour clamping of the renal artery induced ARF in uninephrectomized rabbits. These animals were not resistant to an additional ischemia in the recovery phase, despite inhibited glomerular contractile responses to AII. These data indicate a nonspecific inhibition of glomerular responses to contractile stimuli in the recovery phase of ARF. It is unlikely, however, that resistance to ARF can be attributed to the loss of the glomerular contractile response.

Acute Kidney Injury↗

PubMed1984

Estimation of renal secretory function for organic cations by endogenous N1-methylnicotinamide in rats with experimental renal failure.

To assess whether the secretory clearance of N1-methylnicotinamide (NMN), an endogenous organic cation, represents renal tubular secretion of the organic cation, the relationship between the secretory clearance of NMN, CLscn(NMN), and that of tetraethylammonium bromide (TEA), CLscn(TEA), was examined in normal and experimental renal failure (ERF) rats. TEA was selected as a representative organic cation secreted by the kidney. ERF was induced by glycerol, folate, salicylate, uranium, and gentamicin, substances which have been demonstrated to produce specific damage to the kidney by pathophysiological studies. Glomerular filtration rate (GFR), CLscn(NMN), and CLscn(TEA) decreased significantly in most of ERF rats, while blood urea nitrogen (BUN) increased significantly in all ERF rats. There was a statistically significant correlation (r = 0.952, p less than 0.001) between the endogenous CLscn(NMN) and CLscn(TEA) in both the normal and ERF rats. Correlation analysis revealed that CLscn(NMN) was superior to GFR in the degree of relationship to CLscn(TEA), but BUN could not be used as an index for the secretion of NMN or TEA. Although the plasma concentration of NMN in most of the ERF rats was much higher than that in the normal rats, it affected neither the urinary clearance of NMN itself nor the excretion of TEA. From these findings, we propose that CLscn(NMN) can be used as an index to assess renal tubular function for the secretion of organic cations that are excreted by both filtration and secretion without reabsorption.

Acute Kidney Injury↗

PubMed2004

Co(II), Ce(III) and UO2VI) bis-salicylatothiosemicarbazide complexes: binary and ternary complexes, thermal studies and antimicrobial activity.

A series of new metal complexes of Co(II), Ce(III) and UO(2)(VI), with the Schiff base ligand, H2L, bis-salicylatothiosemicarbazide have been prepared in presence of different molar ratios of LiOH.H2O as a deprotonating agent. Also, the ternary complexes were prepared by using 2-aminopyridine (2-Ampy) or oxalic acid (Ox) as a secondary ligand. All synthesized compounds were identified and confirmed by elemental analyses, molar conductivities, spectral (UV-Vis, IR, 1H NMR, mass) and magnetic moment measurements as well as TG-DSC technique. The changes in the selected vibrational absorption bands in IR and NMR spectra of the Schiff base ligand upon coordination indicate that, the ligand behaves as a neutral, monoanionic and/or dianionic tetradentate manner with ONNO donor sites. Conductance measurements suggest the non-electrolytic and 1:1 electrolytic nature of the metal complexes. Thermal studies suggest a mechanism for degradation of the metal complexes as function of temperature supporting the chelation modes, moreover, show the possibility of obtaining new complexes pyrolytically in the solid state which cannot be synthesized from solution. Antimicrobial screening of the free ligand and its binary complexes showed that, the free ligand and some metal complexes possess antimicrobial activities towards four type of bacteria and five types of fungi and these results were compared with eleven type of known antibiotics.

Anti-Bacterial Agents↗