Environmental exposure to uranium in a population living in close proximity to gold mine tailings in South Africa.

BACKGROUND: Gold mining activities in South Africa resulted in contamination of residential environment with uranium-rich wastes from mine tailings. Health of the people living around the mine tailings could be affected by uranium exposure due to its hazardous chemotoxic and radiological properties. METHODS: We conducted a cross-sectional study to assess i) uranium (U) concentrations in individual hair samples of children and adults living in close proximity to mine tailings in Northeast- Soweto in Johannesburg, South Africa, and ii) the association between U concentrations in hair and various factors, including zone of residence, socio-demographic and housing characteristics. Sampling sites were divided into three zones based on the distance between a dwelling and a cluster of mine tailings (zone 1: <= 500 m, zone 2: 2-3 km away, zone 3: 4-5 km away). U concentrations in hair samples were measured using inductively coupled plasma mass spectrometry. To test the association between U concentrations and selected factors we used robust regression models with log-transformed U concentrations. RESULTS: Among 128 subjects with available U measurements, 63 (49%) were children (ages 7-15 years) of which 38 were girls, the remaining 65 (51%) were adult females. Mean (median) U concentration in hair samples was 143 (92) µg/kg. In the mutually adjusted analyses, only an inverse association between age and U concentration in hair remained statistically significant, with geometric mean in children being 2.1 times higher compared to adults (P < 0.001). There was no evidence of an association between zones and U concentration (P = 0.42). CONCLUSIONS: There was little evidence of association between U concentration in hair and distance from the mine tailings within the 5 km range, but overall concentrations were elevated compared to general population samples in other parts of the world. Children had statistically significantly higher geometric mean of uranium concentration in hair compared to adults. The results are important for improvement of mining waste policies and implementation of health monitoring and protective measures in populations at risk. ARTICLE CATEGORY: Research Article.

Plant cell (Brassica napus) response to europium(III) and uranium(VI) exposure.

Experiments conducted over a period of 6 weeks using Brassica napus callus cells grown in vitro under Eu(III) or U(VI) stress showed that B. napus cells were able to bioassociate both potentially toxic metals (PTM), 628 nmol Eu/gfresh cells and 995 nmol U/gfresh cells. Most of the Eu(III) and U(VI) was found to be enriched in the cell wall fraction. Under high metal stress (200 µM), cells responded with reduced cell viability and growth. Subsequent speciation analyses using both metals as luminescence probes confirmed that B. napus callus cells provided multiple-binding environments for Eu(III) and U(VI). Moreover, two different inner-sphere Eu3+ species could be distinguished. For U(VI), a dominant binding by organic and/or inorganic phosphate groups of the plant biomass can be concluded.

Human exposure to uranium in South African gold mining areas using barber-based hair sampling.

Uranium (U) measurements in water, soil, and food related to gold mining activities in populated areas in Gauteng Province, South Africa, suggest the possibility of exposure levels that may lead to adverse health consequences, including cancer. Theoretical considerations on pathways of human uptake of significant exposures are plausible, but few data on directly measured human exposure are available. A cross-sectional study was conducted using human measurements to compare U levels with other settings around the globe (based on literature review), to explore potential exposure variability within the province, and to test the feasibility of recruiting subjects partially coming from vulnerable and difficult-to-reach populations. Wards of potentially high (HE) and low exposure (LE) were identified. Composite hair samples representing the respective local populations were collected from regular customers of selected barber shops over a period of 1-2 months. A total of 70 U concentrations were determined in 27 composite samples from 1332 individuals. U concentrations ranged from 31 µg/kg to 2524 µg/kg, with an arithmetic mean of 192 µg/kg (standard deviation, 310 µg/kg) and a median of 122 µg/kg. Although HE wards collectively showed higher U levels than LE wards (184 vs 134 µg/kg), differences were smaller than expected. In conclusion, detected U levels were higher than those from most other surveys of the general public. The barber-based approach was an efficient hair collection approach. Composite hair samples are not recommended, due to technical challenges in measuring U, and individual hair samples are needed in follow-up studies to determine predictors of exposure.

Ultrafast Transient Absorption Spectroscopy of UO22+ and [UO2Cl].

For the only water coordinated "free" uranyl(VI) aquo ion in perchlorate solution we identified and assigned several different excited states and showed that the 3Δ state is the luminescent triplet state from transient absorption spectroscopy. With additional data from other spectroscopic methods (TRLFS, UV/vis) we generated a detailed Jablonski diagram and determined rate constants for several state transitions, like the inner conversion rate constant from the 3Φ state to the 3Δ state transition to be 0.35 ps-1. In contrast to luminescence measurements, it was possible to observe the highly quenched uranyl(VI) ion in highly concentrated chloride solution by TAS and we were able to propose a dynamic quenching mechanism, where chloride complexation is followed by the charge transfer from the excited state uranyl(VI) to chloride. This proposed quenching route is supported by TD-DFT calculations.

Calorimetrically Determined U(VI) Toxicity in Brassica napus Correlates with Oxidoreductase Activity and U(VI) Speciation.

Radioecological studies depend on the quantitative toxicity assessment of environmental radionuclides. At low dose exposure, the life span of affected organisms is barely shortened, enabling the transfer of radionuclides through an almost-intact food chain. Lethality-based toxicity estimates are not adequate in this regime because they require higher concentrations. However, increased radionuclide concentration alters its speciation, rendering the extrapolation to the low dose exposure chemically inconsistent. Here, we demonstrate that microcalorimetry provides a sensitive real-time monitor of toxicity of uranium (in the U(VI) oxidation state) in a plant cell model of Brassica napus. We introduce the calorimetric descriptor "metabolic capacity" and show that it correlates with enzymatically determined cell viability. It is independent of physiological models and robust against the naturally occurring fluctuations in the metabolic response to U(VI) of plant cell cultures. In combination with time-resolved laser-induced fluorescence spectroscopy and thermodynamic modeling, we show that the plant cell metabolism is affected predominantly by hydroxo-species of U(VI) with an IC50 threshold of ∼90 µM. The data emphasize the yet-little-exploited potential of microcalorimetry for the speciation-sensitive ecotoxicology of radionuclides.

Uranium contaminated drinking water linked to leukaemia-Revisiting a case study from South Africa taking alternative exposure pathways into account.

The paper presents results of a follow-up to an earlier study which established a geospatial link between naturally elevated uranium (U) levels in borehole water and haematological abnormalities in local residents serving as a proxy for leukaemia prevalent in the area. While the original study focussed on drinking water only, this paper also explores alternative exposure pathways including the inhalation of dust and the food chain. U-levels in grass and tissue of sheep generally reflect U-levels in nearby borehole water and exceed background concentrations by 20 to nearly 500 times. U-levels in sheep tissue increase with age of the animal. Wool showed the highest U-concentration followed by other non-consumable tissue such as hooves, teeth and bones. Lower levels occur in edible parts such as meat and inner organs. The U-deposition rate in wool is several orders of magnitudes higher than in bone as a known target organ. Wool is an easy-to-sample non-invasive bioindicator for U-levels in meat. Depending on the original water content, dried samples show up to 5 times higher U-levels than identical fresh material. Contaminated drinking water is the main exposure pathway for farm residents resulting in U-uptake rates exceeding the WHO's tolerable daily intake (TDI) limit by up to 900%. This is somewhat mitigated by the fact that U-speciation is dominated by a neutral calcium-uranyl-carbonate complex of relatively low toxicity. Commercially available household filters are able to significantly reduce U-levels in well water and are thus recommended as a short-term intervention. Based on average consumption rates sheep meat, as local staple food, accounts for 34% of the TDI for U. Indoor levels of radon should be monitored, too, since it is linked to both, U and leukaemia. With elevated U-levels being present in other geological formations across South Africa boreholes in these areas should be surveyed.

Speciation of uranium in compartments of living cells.

Depleted uranium used as ammunition corrodes in the environment forming mineral phases and then dissolved uranium species like uranium carbonates (Schimmack et al., in Radiat Environ Biophys 46:221-227, 2007) and hydroxides. These hydroxide species were contacted with plant cells (canola). After 24 h contact time the cells were fractionated and the uranium speciation in the fraction was determined by time resolved laser-induced fluorescence spectroscopy at room temperature as well at 150 K. It could be shown that the uranium speciation in the fractions is different to that in the nutrient solution. Comparison of the emission bands with literature data allows assignment of the uranium binding forms.

Uranium(VI) Binding Forms in Selected Human Body Fluids: Thermodynamic Calculations versus Spectroscopic Measurements.

Human exposure to uranium increasingly becomes a subject of interest in many scientific disciplines such as environmental medicine, toxicology, and radiation protection. Knowledge about uranium chemical binding forms(speciation) in human body fluids can be of great importance to understand not only its biokinetics but also its relevance in risk assessment and in designing decorporation therapy in the case of accidental overexposure. In this study, thermodynamic calculations of uranium speciation in relevant simulated and original body fluids were compared with spectroscopic data after ex-situ uranium addition. For the first time, experimental data on U(VI) speciation in body fluids (saliva, sweat, urine) was obtained by means of cryogenic time-resolved laser-induced fluorescence spectroscopy (cryo-TRLFS) at 153 K. By using the time dependency of fluorescence decay and the band positions of the emission spectra, various uranyl complexes were demonstrated in the studied samples. The variations of the body fluids in terms of chemical composition, pH, and ionic strength resulted in different binding forms of U(VI). The speciation of U(VI) in saliva and in urine was affected by the presence of bioorganic ligands, whereas in sweat, the distribution depends mainly on inorganic ligands. We also elucidated the role of biological buffers, i.e., phosphate (H(2)PO(4−)/HPO(4)(2−)) on U(VI) distribution, and the system Ca(2+)/UO(2)(2+)/PO(4)(3−) was discussed in detail in both saliva and urine. The theoretical speciation calculations of the main U(VI) species in the investigated body fluids were significantly consistent with the spectroscopic data. Laser fluorescence spectroscopy showed success and reliability for direct determination of U(VI) in such biological matrices with the possibility for further improvement.

Combining luminescence spectroscopy, parallel factor analysis and quantum chemistry to reveal metal speciation - a case study of uranyl(vi) hydrolysis.

This study of aqueous metal speciation is an advanced combination of theoretical and experimental methods. Continuous wave (CW) and time-resolved laser-induced fluorescence spectroscopy (TRLFS) data of uranyl(vi) hydrolysis were analyzed using parallel factor analysis (PARAFAC). Distribution patterns of five major species were thereby derived under a fixed uranyl concentration (10-5 M) over a wide pH range from 2 to 11. UV (180 nm to 370 nm) excitation spectra were extracted for individual species. Time-dependent density functional theory (TD-DFT) calculations revealed ligand excitation (water, hydroxo, oxo) in this region and ligand-to-metal charge transfer (LMCT) responsible for luminescence. Thus excitation in the UV region is extreme ligand sensitive and specific. Combining findings from PARAFAC and DFT the [UO2(H2O)5]2+ cation (aquo complex 1 : 0) and four hydroxo complexes (1 : 1, 3 : 5, 3 : 7 and 1 : 3) were identified. The methodological concept used here is applicable to luminescent metals in general and thus enables acquisition of refined structural and thermodynamical data of lanthanide and actinide complexation.

EGF receptor-targeting peptide conjugate incorporating a near-IR fluorescent dye and a novel 1,4,7-triazacyclononane-based (64)Cu(II) chelator assembled via click chemistry.

A new Boc-protected 1,4,7-triazacyclononane (TACN)-based pro-chelator compound featuring a "clickable" azidomethylpyridine pendant has been developed as a building block for the construction of multimodal imaging agents. Conjugation to a model alkyne (propargyl alcohol), followed by deprotection, generates a pentadentate ligand, as confirmed by X-ray crystallographic analysis of the corresponding distorted square-pyramidal Cu(II) complex. The ligand exhibits rapid (64)Cu(II)-binding kinetics (>95% radiochemical yield in <5 min) and a high resistance to demetalation. It may thus prove suitable for use in (64)Cu(II)-based in vivo positron emission tomography (PET). The new chelating building block has been applied to the construction of a bimodal (PET/fluorescence) peptide-based imaging probe targeting the epidermal growth factor (EGF) receptor, which is highly overexpressed on the surface of several types of cancer cells. The probe consists of a hexapeptide sequence, Leu-Ala-Arg-Leu-Leu-Thr (designated "D4"), followed by a Cys-ß-Ala-ß-Ala spacer, then a ß-homopropargylglycine residue with the TACN-based chelator "clicked" to its side chain. A sulfonated near-infrared (NIR) fluorescent cyanine dye (sulfo-Cy5) was introduced at the N-terminus to study the EGF receptor-binding ability of the probe by laser-fluorescence spectroscopy. Binding was also confirmed by coimmunoprecipitation methods, and an apparent dissociation constant (Kd) of ca. 10 nM was determined from radioactivity-based measurements of probe binding to two EGF receptor-expressing cell lines (FaDu and A431). The probe is shown to be a biased or partial allosteric agonist of the EGF receptor, inducing phosphorylation of Thr669 and Tyr992, but not the Tyr845, Tyr998, Tyr1045, Tyr1068, or Tyr1148 residues of the receptor, in the absence of the orthosteric EGF ligand. Additionally, the probe was found to suppress the EGF-stimulated autophosphorylation of these latter residues, indicating that it is also a noncompetitive antagonist.

Mobile uranium(IV)-bearing colloids in a mining-impacted wetland.

Tetravalent uranium is commonly assumed to form insoluble species, resulting in the immobilization of uranium under reducing conditions. Here we present the first report of mobile U(IV)-bearing colloids in the environment, bringing into question this common assumption. We investigate the mobility of uranium in a mining-impacted wetland in France harbouring uranium concentrations of up to 14,000 p.p.m. As an apparent release of uranium into the stream passing through the wetland was observable, we examine soil and porewater composition as a function of depth to assess the geochemical conditions leading to this release. The analyses show the presence of U(IV) in soil as a non-crystalline species bound to amorphous Al-P-Fe-Si aggregates, and in porewater, as a distinct species associated with Fe and organic matter colloids. These results demonstrate the lability of U(IV) in these soils and its association with mobile porewater colloids that are ultimately released into surface water.

Investigation of uranium binding forms in selected German mineral waters.

Cryogenic time-resolved laser-induced fluorescence spectroscopy was successfully used to identify uranium binding forms in selected German mineral waters of extremely low uranium concentrations (<2.0 µg/L). The measurements were performed at a low temperature of 153 K. The spectroscopic data showed a prevalence of aquatic species Ca2UO2(CO3)3 in all investigated waters, while other uranyl-carbonate complexes, viz, UO2CO3(aq) and UO2(CO3)2 (2-), only existed as minor species. The pH value, alkalinity (CO3 (2-)), and the main water inorganic constituents, specifically the Ca(2+) concentration, showed a clear influence on uranium speciation. Speciation modeling was performed using the most recent thermodynamic data for aqueous complexes of uranium. The modeling results for the main uranium binding form in the investigated waters indicated a good agreement with the spectroscopy measurements.

Impact of uranium (U) on the cellular glutathione pool and resultant consequences for the redox status of U.

Uranium (U) as a redox-active heavy metal can cause various redox imbalances in plant cells. Measurements of the cellular glutathione/glutathione disulfide (GSH/GSSG) by HPLC after cellular U contact revealed an interference with this essential redox couple. The GSH content remained unaffected by 10 µM U whereas the GSSG level immediately increased. In contrast, higher U concentrations (50 µM) drastically raised both forms. Using the Nernst equation, it was possible to calculate the half-cell reduction potential of 2GSH/GSSG. In case of lower U contents the cellular redox environment shifted towards more oxidizing conditions whereas the opposite effect was obtained by higher U contents. This indicates that U contact causes a consumption of reduced redox equivalents. Artificial depletion of GSH by chlorodinitrobenzene and measuring the cellular reducing capacity by tetrazolium salt reduction underlined the strong requirement of reduced redox equivalents. An additional element of cellular U detoxification mechanisms is the complex formation between the heavy metal and carboxylic functionalities of GSH. Because two GSH molecules catalyze electron transfers each with one electron forming a dimer (GSSG) two UO(2) (2+) are reduced to each UO(2) (+) by unbound redox sensitive sulfhydryl moieties. UO(2) (+) subsequently disproportionates to UO(2) (2+) and U(4+). This explains that in vitro experiments revealed a reduction to U(IV) of only around 33% of initial U(VI). Cellular U(IV) was transiently detected with the highest level after 2 h of U contact. Hence, it can be proposed that these reducing processes are an important element of defense reactions induced by this heavy metal.

Determination of uranium(VI) sorbed species in calcium silicate hydrate phases: a laser-induced luminescence spectroscopy and batch sorption study.

Batch sorption experiments and time-resolved luminescence spectroscopy investigations were carried out to study the U(VI) speciation in calcium silicate hydrates for varying chemical conditions representing both fresh and altered cementitious environments. U(VI) uptake was found to be fast and sorption distribution ratios (R(d) values) were very high indicating strong uptake by the C-S-H phases. In addition a strong dependence of pH and solid composition (Ca:Si mol ratio) was observed. U(VI) luminescence spectroscopy investigations showed that the U(VI) solid speciation continuously changed over a period up to 6 months in contrast to the fast sorption kinetics observed in the batch sorption studies. Decay profile analysis combined with factor analysis of series of spectra of U(VI)-C-S-H suspensions, recorded with increasing delay times, revealed the presence of four luminescent U(VI) species in C-S-H suspensions, in agreement with the batch sorption data. Along with the aqueous UO(2)(OH)(4)(2-) species and a Ca-uranate precipitate, two different sorbed species were identified which are either bound to silanol groups on the surface or incorporated in the interlayer of the C-S-H structure.

First fluorescence spectroscopic investigation of Am(III) complexation with an organic carboxylic ligand, pyromellitic acid.

For the first time Am(III) complexation with a small organic ligand could be identified and characterized with time-resolved laser-induced fluorescence spectroscopy (TRLFS) at room temperature and trace metal concentration. With pyromellitic acid (1,2,4,5-benzene-tetracarboxylic acid, BTC) as ligand spectroscopic characteristics for the Am-BTC complex system were determined at pH 5.0, an ionic strength of 0.1 M (NaClO4) and room temperature. The fluorescence lifetimes were determined to be 23.2±2.2 ns for Am3+(aq) and 27.2±1.2 ns for the Am-BTC 1:1 complex; the emission maximum for the 5D1-(7)F1 transition is 691 nm for both species. The complex stability constant for the Am-BTC 1:1 complex was calculated to be logß110=5.42±0.16.

Sugar-decorated dendritic nanocarriers: encapsulation and release of the octahedral rhenium cluster complex [Re6S8(OH)6]4-.

The encapsulation of a nanometer-sized octahedral anionic rhenium cluster complex with six terminal hydroxo ligands [Re(6)S(8)(OH)(6)](4-) in maltose-decorated poly(propylene amine) dendrimers (POPAM, generation 4 and 5) has been investigated. Ultrafiltration experiments showed that maximal loading capacity of the dendrimers with the cluster complex is achieved after about ten hours in aqueous solution. To study the inclusion phenomena, three different methods have been applied: UV/Vis, time-resolved laser-induced fluorescence spectroscopy (TRLFS), and laser-induced liquid bead ion desorption mass spectrometry (LILBID-MS). From the results obtained, it could be concluded that: a) the hydrolytic stability of the rhenium cluster complex is significantly enhanced in the presence of dendritic hosts; b) the cluster anions are preferentially bound inside the dendrimers; c) the number of cluster complexes encapsulated in the dendrimers increases with rising dendrimer generation. On average, four to five cluster anions can preferentially be captured in the interior of sugar-coated dendritic carriers. An asymptotic progression of the release of cluster complexes from the loaded dendrimers was observed under physiologically relevant conditions (isotonic sodium chloride solution: approximately 93 % within 4 days for loaded POPAM-G4-maltose; approximately 86 % within 4 days for loaded POPAM-G5-maltose). These encapsulation and release properties of maltose-decorated nanocarriers imply the possibility for the development of the next generation of dendritic nanocarriers with specific targeting of destined tissue for therapeutic treatments.

Self-assembly of neutral hexanuclear circular copper(II) meso-helicates: topological control by sulfate ions.

Bis-pyridylimine ligands with different linking elements are capable of forming unique hexanuclear circular Cu(II) meso-helicates; the self-assembly is controlled by coordination of sulfate ions to the metal centres.

Fluorescence properties of a uranyl(V)-carbonate species [U(V)O(2)(CO(3))(3)](5-) at low temperature.

Fluorescence properties of a uranyl(V)-carbonate species in solution are reported for the first time. The fluorescence characteristics of the stable aqueous uranyl(V)-carbonate complex [U(V)O(2)(CO(3))(3)](5-) was determined in a frozen solution (T=153K) of 0.5mM uranium and 1.5M Na(2)CO(3) at pH 11.8 by time resolved laser-induced fluorescence spectroscopy (TRLFS). Two different wavelengths of 255nm and 408nm, respectively were used to independently of each other excite the uranyl(V)-carbonate species. The resulting U(V) fluorescence emission bands were detected between 380nm and 440nm, with a maxima at 404.7nm (excitation with 255nm) and 413.3nm (excitation with 408nm), respectively. It was found that by using an excitation wavelength of 255nm the corresponding extinction coefficient was much higher and the fluorescence spectrum better structured than the ones excited at 408nm. The fluorescence lifetime of the uranyl(V)-carbonate species was determined at 153K as 120micros. TRLFS investigations at room temperature, however, showed no fluorescence signal at all.

Spectroscopic investigations of U(VI) species sorbed by the green algae Chlorella vulgaris.

The green alga Chlorella vulgaris has the ability to bind high amounts of uranium(VI) in the pH range from 3 to 6. At pH 3 up to 40% of the uranium are bound by the algal cells. The uranium removal is almost complete at pH 5 and 6 under the given experimental conditions. Scanning electron microscopy and laser-induced fluorescence spectroscopy were used to characterize uranyl species formed in the selected pH range. The micrographs show a regular distribution of U(VI) on the cell surface. Fluorescence spectroscopic investigations of formed algal uranyl complexes indicate that the binding of U(VI) to carboxyl groups plays a dominating role at pH 3, whereas a minor impact of organic phosphate compounds on the U(VI) sorption cannot be excluded. In contrast, at pH 5 and 6 the phosphate groups are mainly responsible for the removal and binding of U(VI) by formation of organic and/or inorganic uranyl phosphates.

Cluster core controlled reactions of substitution of terminal bromide ligands by triphenylphosphine in octahedral rhenium chalcobromide complexes.

Reactions of rhenium chalcobromides Cs4[{Re6(mu3-S)8}Br6].2H2O, Cs3[{Re6(mu3-Se)8}Br6].2H2O, Cs3[{Re6(mu3-Q)7(mu3-Br)}Br6].H2O (Q = S, Se), and K2[{Re6(mu3-S)6(mu3-Br)2}Br6] with molten triphenylphosphine (PPh3) have resulted in a family of novel molecular hybrid inorganic-organic cluster compounds. Six octahedral rhenium cluster complexes containing PPh3 ligands with general formula [{Re6(mu3-Q)8-n(mu3-Br)n}(PPh3)4-nBrn+2] (Q = S, n = 0, 1, 2; Q = Se, n = 0, 1) have been synthesized and characterized by X-ray single-crystal diffraction and elemental analyses, 31P{1H} NMR, luminescent measurements, and quantum-chemical calculations. It was found that the number of terminal PPh3 ligands in the complexes is controlled by the composition and consequently by the charge of the cluster core {Re6Q8-nBrn}n+2. In crystal structures of the complexes with mixed chalcogen/bromine ligands in the cluster core all positions of a cube [Q8-nBrn] are ordered and occupied exclusively by Q or Br atoms. Luminescence characteristics of the compounds trans-[{Re6Q8}(PPh3)4Br2] and fac-[{Re6Se7Br}(PPh3)3Br3] (Q = S, Se) have been investigated in CH2Cl2 solution and the broad emission spectra in the range of 600-850 nm were observed.