Reactive transport modeling of uranium 238 and radium 226 in groundwater of the Königstein uranium mine, Germany

Knowledge of the transport behavior of radionuclides in groundwater is needed for both groundwater protection and remediation of abandoned uranium mines and milling sites. Dispersion, diffusion, mixing, recharge to the aquifer, and chemical interactions, as well as radioactive decay, should be taken into account to obtain reliable predictions on transport of primordial nuclides in groundwater. This paper demonstrates the need for carrying out rehabilitation strategies before closure of the Königstein in-situ leaching uranium mine near Dresden, Germany. Column experiments on drilling cores with uranium-enriched tap water provided data about the exchange behavior of uranium. Uranium breakthrough was observed after more than 20 pore volumes. This strong retardation is due to the exchange of positively charged uranium ions. The code TReAC is a 1-D, 2-D, and 3-D reactive transport code that was modified to take into account the radioactive decay of uranium and the most important daughter nuclides, and to include double-porosity flow. TReAC satisfactorily simulated the breakthrough curves of the column experiments and provided a first approximation of exchange parameters. Groundwater flow in the region of the Königstein mine was simulated using the FLOWPATH code. Reactive transport behavior was simulated with TReAC in one dimension along a 6000-m path line. Results show that uranium migration is relatively slow, but that due to decay of uranium, the concentration of radium along the flow path increases. Results are highly sensitive to the influence of double-porosity flow.     

Associations and mobility of uranium in soils near a depleted uranium （DU） weapons testing site, SW Scotland

Natural uranium has three isotopes, ^238U, ^235U and ^234U, with natural abundances of 99.27 atom %, 0.72% and 0.0055%, respectively. Only ^235U is fissile and the production of nuclear fuel and nuclear weapons involves enrichment of uranium in ^235U. This process also results in separation of ^234U from ^238U, leaving depleted uranium （DU）, with typical ^234U/^238U and ^235U/^238U activity ratios of about 0.19 and 0.013, respectively, as a waste product. The high density, high melting and boiling points and chemical stability of uranium and the availability of DU in relatively pure form mean that DU has many uses, including armour-piercing munitions. Such munitions have been developed in the UK since the 1960s and testing has been carried out by the Ministry of Defence （MoD） at firing ranges such as Dundrennan, SW Scotland and Eskmeals, NW England. The firing of DU munitions can result in the dispersion of DU and its combustion products （oxides） as aerosols or as larger fragments, with the potential for human exposure either directly at the site of detonation or via post-depositional migration in the environment. The aim of this work was to investigate the potential environmental mobility of DU by characterizing the associations of U in soil porewaters with increasing distance from a firing site. To this end, several soil cores located down-wind of the firing site at Dundrennan, near Kirkcudbright, SW Scotland, were collected in May 2006. These were sectioned on-site into 1- or 2-cm depth intervals and porewaters were isolated by centfifugation （10 minutes; 8873 g） on return to the laboratory. Following filtration through 0.2-micron cellulose nitrate filters, the porewaters were analyzed by ICP-QMS （U concentration） and ICP-OES （Fe, Al, Ca, Mg, Mn concentrations）. Sub-samples were also subjected to centrifugal ultrafiltration （100, 30, and 3 kD） and to gel electrophoretic fractionation （agarose; 0.045 M Tris-borate; 20 mA, 30 minutes）. Results showed that U was present at up to 4 μg/L in the soil porewater and that the associations of U varied with sample location and soil depth.     

Geochemical characteristics of Dongsheng sandstone-type uranium deposit, Ordos Basin

Generally, sandstone-type uranium deposits can be divided into three zones according to their redox conditions: oxidized zone, ore zone and reduced zone. The Dongsheng uranium deposit belongs to this type. In order to study its geochemical characteristics, 11 samples were taken from the three zones of the Dongsheng uranium deposit. Five samples of them were collected from the oxidized zone, four samples from the ore zone and two samples from the reduced zone. These samples were analyzed using organic and inorganic geochemical methods. The results of GC traces and ICP-MASS indicate that the three zones show different organic and inorganic geochemical characteristics.     

Geomicrobiological in-situ containment of uranium in subsurface and its long-term stability

Uranium is a redox-sensitive element. While U （Ⅵ）, the oxidized form of uranium, is soluble and thus mobile in groundwater, U （Ⅳ） readily forms UO2（s） and is precipitated. Recent geomicrobiological researches demonstrated that dissimilatory metal reducing bacteria can effectively remove uranium fi＇om contaminated groundwater by reducing soluble U （Ⅵ） to relatively insoluble U （Ⅳ）. This novel form of microbial reduction of U （Ⅵ） is reported to be much faster than abiological reduction. The objective of this work was to investigate U （Ⅵ） reduction by indigenous bacteria in uranium-bearing black shale sediment and to determine whether microbially-precipitated uranium has long-term stability in subsurface. Through this study, fundamental information on the effects of microorganisms on the fate of redox-sensitive elements in natural settings will be provided. Soil and sediment samples were collected from uranium-bearing black shale in the Dukpyung area in Korea. Microbial inoculum was prepared from soil and sediment slurry supernatant. The reactors were purged with N2 ： CO2 gas （80 ; 20） to maintain anaerobic condition. Glucose, acetate or lactate was added as an electron donor at a final concentration of 5 mM.     

Age of dispersed uranium mineralization in rocks of the framework of the Strel’tsovka uranium ore field and the Yamsky site,Eastern Transbaikal region

An isotopic geochronological study of dispersed uranium mineralization was performed in the granitic rocks of the Urtui pluton in the framework of the Strel’tsovka uranium ore field and in the Yamsky site of the Urov-Uryumkan granite-gneiss arch. Two stages of such mineralization—783 ± 26 Ma in the Urtui granitic pluton and 138.6 ± 2.3 Ma in the Yamsky site—have been established. The emplacement of granite pertaining to the Unda Complex disturbed the U-Pb isotopic system in uraninite from the Urtui granitic pluton and resulted in redeposition of uranium phase dated at 262 ± 34 Ma. The young, probably, recent process gave rise to the redistribution of radiogenic lead in the U-bearing phases developing after uraninite.     

Geochemistry of lamprophyres associated with uranium mineralization, Southeastern Desert, Egypt

Two brecciated shear zones (NNW-SSE) are found crosscutting cataclastic rocks. The cataclastic rocks (3.0 km2) occupy the core of the granitic pluton and enclose a roof pendant of mafic-ultramafic rocks. The NNW-SSE-extending lamprophyre dykes vary in thickness from 0.5 m to 1 m and up to 800 m long, cutting the cataclastic rocks and are composed mainly of plagioclases, amphiboles, relics of pyroxenes and K-feldspar phenocrysts embedded in fine-grained groundmass. They are characterized as being peraluminous, calc-alkaline in composition (chemical trap) and enriched in calcite, sulfide and P2O5. The lamprophyres were affected by hydrothermal alteration (chlorite-carbonate alteration) while the cataclastic rocks were affected by diagenetic alteration (K-feldspar-albite alteration). Uranium mineralization is the product of hydrothermal events and has been investigated by X-ray diffraction (XRD) and environmental scanning electron microscopy (ESEM), involving primary uranium minerals (U3O8) and secondary uranium minerals (uranophane and beta-uranophane, kasolite, torbernite, autonite and meta-autonite) in addition to U- bearing minerals (astrocyanite, betafite and fergusonite). The presence of different mineral parageneses associated with clay minerals indicates that the lamprophyres were subjected to acidic and alkaline mineralizing solutions. Moreover, the U-Zr/U, U-Ce/U values show negative correlations, confirming U-enrichment in both cataclastic rocks and shear zones while the Th-eU/eTh, Th-Zr/Th and Th-Ce/Th values show negative correlations, indicating that the U-bearing solutions are rich in Th in the cataclastic rocks only.     

The Strel’tsovka uranium district: Isotopic geochronological (U-Pb,Rb-Sr,Sm-Nd) characterization of granitoids and their place in the formation history of uranium deposits

An isotopic geochronological study of Russia’s largest Strel’tsovka uranium district has been carried out. Polychronous granite generation, which determined the structure of the pre-Mesozoic basement, had important implications for the formation of volcanotectonic structural elements bearing economic uranium mineralization. The study of U-Pb, Rb-Sr, and Sm-Nd isotopic systems of whole-rock samples and minerals of granitic rocks allowed us to estimate the deportment of these systems in spatially conjugated granite-forming and hydrothermal processes differing in age and gave grounds for revising the age of granites pertaining to the Urulyungui Complex and refining the age of the Unda Complex.     

REE/trace element characteristics of sandstone-type uranium deposits in the Ordos Basin

1 Introduction The Ordos Basin is the second largest sedimentary basin in China. During the last 10 years, a great progress has been achieved in the aspects of tectonic evolution, dynamics process, inner and outer geological processes during Mesozoic-Cen…     

Sorption of uranium(VI) at the clay mineral–water interface

Batch experiments were conducted to study the sorption of uranium on selected clay minerals (KGa-1b and KGa-2 reference kaolinite, SWy-2 and STx-1b reference montmorillonite, and IBECO natural bentonite) as a function of pH (4–9) and 0.001, 0.01, and 0.025 M NaCl in equilibrium with the CO₂ partial pressure of the atmosphere. Uranium concentrations were kept below 100 μg L⁻¹ to avoid precipitation of amorphous Uranium-hydroxides. Solely PTFE containers and materials were used, because experiments showed significant sorption at higher pH on glass ware. All batch experiments were performed over a period of 24 h, since kinetic experiments proved that the common 10 or 15 min are in many cases by far not sufficient to reach equilibrium. Kaolinite showed much greater uranium sorption than the other clay minerals due to the more aluminol sites available. Sorption on the poorly crystallized KGa-2 was higher than on the well-crystallized KGa-1b. Uranium sorption on STx-1b and IBECO exhibited parabolic behavior with a sorption maximum around pH 6.5. Sorption of uranium on montmorillonites showed a distinct dependency on sodium concentrations because of the effective competition between uranyl and sodium ions, whereas less significant differences in sorption were found for kaolinite. The presence of anatase as impurity in kaolinite enhanced the binding of uranyl-carbonate complexes with surface sites. The kinetic of uranium sorption behavior was primarily dependent on the clay minerals and pH. A multisite surface complexation model without assuming exchange is based on the binding of the most dominant uranium species to aluminol and silanol edge sites of montmorillonite, respectively to aluminol and titanol surface sites of kaolinite. For eight surface species, the log_k was determined from the experimental data using the parameter estimation code PEST together with PHREEQC.     

Isotope geochemistry of ore fluids for the Dongsheng sandstone-type uranium deposit, China

The Dongsheng sandstone-type uranium deposit is one of the large-sized sandstone-type uranium deposits discovered in the northern part of the Ordos Basin of China in recent years. Geochemical characteristics of the Dongsheng uranium deposit are significantly different from those of the typical interlayered oxidized sandstone-type uranium ore deposits in the region of Middle Asia. Fluid inclusion studies of the uranium deposit showed that the uranium ore-forming temperatures are within the range of 150–160℃. Their 3He/4He ratios are within the range of 0.02–1.00 R/Ra, about 5–40 times those of the crust. Their 40Ar/36Ar ratios vary from 584 to 1243, much higher than the values of atmospheric argon. The δ18OH2O and δD values of fluid inclusions from the uranium deposit are -3.0‰– -8.75‰ and -55.8‰– -71.3‰, respectively, reflecting the characteristics of mixed fluid of meteoric water and magmatic water. The δ18OH2O and δD values of kaolinite layer at the bottom of the uranium ore deposit are 6.1‰ and -77‰, respectively, showing the characteristics of magmatic water. The δ13CV-PDB and δ18OH2O values of calcite veins in uranium ores are -8.0‰ and 5.76‰, respectively, showing the characteristics of mantle source. Geochemical characteristics of fluid inclusions indicated that the ore-formation fluid for the Dongsheng uranium deposit was a mixed fluid of meteoric water and deep-source fluid from the crust. It was proposed that the Jurassic-Cretaceous U-rich metamorphic rocks and granites widespread in the northern uplift area of the Ordos Basin had been weathered and denudated and the ore-forming elements, mainly uranium, were transported by meteoric waters to the Dongsheng region, where uranium ores were formed. Tectonothermal events and magmatic activities in the Ordos Basin during the Mesozoic made fluids in the deep interior and oil/gas at shallow levels upwarp along the fault zone and activated fractures, filling into U-bearing clastic sandstones, thus providing necessary energy for the formation of uranium ores.     

REE/trace element characteristics of sandstone-type uranium deposits in the Ordos Basin

Erratum:Chin. J. of Geochem. DOI: 10.1007/s11631-006-0354-y Table 3 on page 360 is incorrect and should be replaced by the table below.Table 3. The results of analysis of trace elements for the sandstone-type uranium deposit samples from the Ordos Basin (…     

Wall-rock argillic alteration and uranium mineralization of the northwestern Strel’tsovka caldera

Alteration of rocks and localization of uranium mineralization in the northwestern Strel’tsovka caldera are exemplified in the Dal’nee deposit. In the main parameters of hydrothermal mineralization (temperature, pH, pressure, and composition of solution), the Dal’nee deposit differs from the deposits of the Strel’tsovka ore field located in the central part of the caldera. The localization of high-grade stratiform orebodies are interpreted in light of kinematic relations between steeply and gently dipping faults that formed in the tectonic setting of the NE-SW-trending, long-living, right-lateral, strike-slip faulting. The wide halos of argillic alteration and the structural control of uranium mineralization are caused by the fact that the deposit is located at the margin of the geological block, which has developed since the Late Triassic in a regime of extension (pull-apart) to form a depression, which is arranged en echelon relative to the main caldera and comparable to it in area. Currently, this depression is overlapped by sediments of the Sukhoi Urulyungui Basin. Such a structure markedly increases the probability of finding hidden uranium ores associated with low-temperature argillic alteration in the volcanosedimantary rocks and granitoid basement of the northwestern Strel’tsovka caldera.     

Constraints on granite-related uranium mineralization in the Sanjiu uranium ore field,SE China provided by pyrite mineralogy,major and trace elements,S–He–Ar isotopes

Acta Geochimica - The Sanjiu uranium ore field, located in the central of Zhuguangshan granitic batholith, is a newly discovered granite-related uranium ore field in South China. The main sulfide...     

Agricolaite, a new mineral of uranium from J��chymov, Czech Republic

The new mineral agricolaite, a potassium uranyl carbonate with ideal formula K₄(UO₂)(CO₃)₃, occurs in vugs of ankerite gangue in gneisses in the abandoned Giftkiesstollen adit at Jáchymov, Czech Republic. The name is after Georgius Agricola (1494?C1555), German scholar and scientist. Agricolaite occurs as isolated equant irregular translucent grains to 0.3?mm with yellow color, pale yellow streak, and vitreous luster. It is brittle with uneven fracture and displays neither cleavage nor parting. Agricolaite is non-fluorescent. Mohs hardness is ~4. It is associated with aragonite, brochantite, posnjakite, malachite, rutherfordine, and ??pseudo-voglite??. Experimental density is higher than 3.3?g.cm^?3, Dcalc is 3.531?g.?cm^?3. The mineral is monoclinic, space group C2/c, with a 10.2380(2), b 9.1930(2), c 12.2110(3) ?, ?? 95.108(2)°, V 1144.71(4) ?³, Z?=?4. The strongest lines in the powder X-ray diffraction pattern are d(I)(hkl): 6.061(55)(002), 5.087(57)(200), 3.740(100)(202), 3.393(43)(113), 2.281(52)(402). Average composition based on ten electron microprobe analyses corresponds to (in wt.%) UO₃ 48.53, K₂O 31.49, CO₂(calc) 22.04 which gives the empirical formula K_3.98(UO₂)_1.01(CO₃)_3.00. The crystal structure was solved from single-crystal X-ray diffraction data and refined to R ₁?=?0.0184 on the basis of the 1,308 unique reflections with F _o?>?4??F _o. The structure of agricolaite is identical to that of synthetic K₄(UO₂)(CO₃)₃ and consists of separate UO₂(CO₃)₃ groups organized into layers parallel to (100) and two crystallographically non-equivalent sites occupied by K⁺ cations. Both the mineral and its name were approved by the IMA-CNMNC.     

The Schlema–Alberoda five-element uranium deposit,Germany: An example of self-organizing hydrothermal system

As a result of integrating geological, mineralogical, and geochemical data on the unique Schlema–Alberoda five-element uranium deposit situated in Federal Republic of Germany and explored in detail down to a depth of 2 km, it has been shown that its formation for more than 100 Ma has been caused by combination of internal and external factors. The latter comprise favorable metallogenic specialization of the region, injection of intrusive bodies bearing the necessary stock of energy, and periodic pulses of tectonic reactivation. The internal factors of self-development involve evolutionary processes, which occur in host rocks at the consecutive stages of prograde and retrograde metamorphism giving rise to alteration of rocks in consistence with physical and chemical laws at variable temperature and degree of system opening.     

Influence of some essential environmental factors on the reductive precipitation of uranium by sulfate reducing bacteria

The rapid kinetics of microbial U （Ⅵ） reduction and low solubility of uraninite make this process a promising strategy for removing uranium from groundwater and preventing its further migration. Nevertheless, some environmental factors that can influence U（Ⅵ） bioreduction, such as pH, the concentration of coexistent anions（sulfate, nitrate） and toxicity of heavy metal cations[Cu（ Ⅱ ）, Zn（ Ⅱ ）, etc], are not well defined. In this paper, anaerobic batch experiments were performed to evaluate their effects on the enzymatic reduction of U （Ⅵ） by mixed cultures of sulfate-reducing bacteria （SRB）. Kinetics investigations under variable pH conditions demonstrated that U （Ⅵ） was mainly reduced during the first 48h. The yield of this bacterial reduction depended strongly on the pH and increased from 4.3% to 99.4% when the pH was raised from 2.0 to 6.0. No inhibition of U （Ⅵ） bioreduction occurred and the formation Of uraninite was concurrent with the precipitation of metal sulfide （ZnS/CuS） at an initial concentration of 20 mg/L Zn （ Ⅱ ） or 10 mg/L Cu （ Ⅱ ）. But addition of 25 mg/L of Zn （ Ⅱ ） or 15 mg/L of Cu （ Ⅱ ） to the bacterial medium stopped U （Ⅵ） reduction due to their toxicities to SRB. Assessment tests for heavy metal toxicity implied that Cu （ Ⅱ ） toxicity probably proceeds by a mechanism different from that of Zn （ Ⅱ ） toxicity. The Zn （ Ⅱ ）-induced inhibition of microbial activity can be eliminated, but Cu （ Ⅱ ） toxicity can generate permanent and irreversible damage to SRB. The sulfate concentration as high as 4000 mg/L did not appreciably interfere with U （Ⅵ） reduction, however, the anion level greater than 5000 mg/L significantly slowed the rate of U （Ⅵ） reduction. Moreover, it was found that U （Ⅵ） was not reduced by H2S produced during dissimilatory sulfate reduction.     

Study on treatment of wastewater from acid in-situ leaching of uranium ore with sulfate reducing bacteria

Synthetic surfactants are among the most widely used chemicals in the world （around 10 millions of tons are produced per year）, mainly as key components in detergent formulation, apart from other applications such as wetting agents or emulsifiers. Coastal ecosystems receive large quantities of these compounds and, after a relatively fast partial degradation in water, the remaining quantities end up in the sediments due to their high affinity for organic carbon in the particulate phase. We therefore focused our studies on sediments because they can be assumed to play an important environmental role acting as a sink for these contaminants. Moreover, because of their widespread use and source specificity, surfactants can usefully be employed as molecular indicators in sediments for more general contamination caused by human activities. This work deals with the vertical distribution in sediment cores of the main anionic surfactants, both linear alkylbenzene sulfonates （LAS） and alkyl ethoxysulfates （AES）, and non-ionic surfactants, including nonylphenol polyethoxylates （NPEOs） and alcohol polyethoxylates （AEOs）. In the case of LAS their degradation metabolites sulfophenyl carboxylic acids （SPCs） are also studied. The processes considered are degradation, sorption and diffusion occurring along the sedimentary column for the different homologues contained in the commercial surfactant mixtures. The most hydrophobic surfactants such as NPEOs and AEOs remain strongly attached to the particulate phase whereas polar metabolites such SPCs tend to be present in the pore water. Highest values of surfactants are found near the surface and, in most cases, there is a decrease in their concentration down the sediment core. Furthermore, the reduction in the average length of the ethoxylated chain in polyethoxylated surfactants, as well as the increase in the concentrations of SPCs at depths showing redox potential from -300 to -400 mV, suggests that surfactants may be degraded anaerobically in the sediment. In the case of LAS, these field results are compared with the data from laboratory experiments carried out in order to determine sorption capacity and anaerobic degradation.     

Formation conditions of paleovalley uranium deposits hosted in upper Eocene–lower Oligocene rocks of Bulgaria

The uranium deposits of Bulgaria related to the Late Alpine tectonomagmatic reactivation are subdivided into two groups: exogenic–epigenetic paleovalley deposits related to the basins filled with upper Eocene–lower Oligocene volcanic–sedimentary rocks and the hydrothermal deposits hosted in the coeval depressions. The geological and lithofacies conditions of their localization, the epigenetic alteration of rocks, mineralogy and geochemistry of uranium ore are exemplified in thoroughly studied paleovalley deposits of the Maritsa ore district. Argumentation of the genetic concepts providing insights into both sedimentation–diagenetic and exogenic–epigenetic mineralization with development of stratal oxidation zones is discussed. A new exfiltration model has been proposed to explain the origin of the aforementioned deposits on the basis of additional analysis with consideration of archival factual data and possible causes of specific ningyoite uranium ore composition.     

REE geochemical characteristics of the No. 302 uranium deposit in northern Guangdong, South China

The No. 302 uranium deposit, located in Guangdong Province, is a typical granite-type uranium ore deposit REE geochemical characteristics of the wall rocks, pitchblende, altered rocks, calcite and fluorite from this deposit have been systematically studied in this paper. The result showed that the alkali-metasomatic granites and other altered rocks have the same REE distribution patterns as Indosinian granites. It is indicated that the hydrothermal ore-forming solution had altered the Indosinian granites, and ore-forming materials may directly originate from the Indosinian granites. Calcite and fluorite of different stages are the products derived from the same source but different stages. The evolution and degassing of the mineralizing solution might induce LREE enrichment to varying degree. Mantle fluid and a large volume of mineralizer may be the crucial factors controlling uranium mineralization, and the hydrothermal solution with mineralizer played an important role in U transport and concentration. Meanwhile, the degassing of CO2 might promote U and REE precipitation.