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.     

Geodynamic simulation of ore-bearing geological structural units by the example of the Strel’tsovka uranium ore field

Information on designing a 3D integrated model of the deflected mode (DM) of rock massif near the Strel’tsovka uranium ore field (SUOF) in the southeastern Transbaikal region is presented in the paper. This information is based on the contemporary stresses estimated by geostructural and tectonophysical techniques and by studying the seismotectonic deformation of the Earth’s surface using the data on earthquake source mechanisms and GPS geodesy focused on the recognition of active faults. A combination of the results of geostructural, geophysical, geotectonic, and petrophysical research, as well as original maps of faulting and the arrangement of seismic dislocations and seismotectonic regimes (stress tensors), allowed us to design models of the structure, properties, and rheological links of the medium and to determine the boundary conditions for numerical tectonophysical simulation using the method of terminal elements. The computed 2D and 3D models of the state of the rock massif have been integrated into 3D GIS created on the basis of the ArcGIS 10 platform with an ArcGIS 3D-Analyst module. The simulation results have been corroborated by in situ observations on a regional scale (the Klichka seismodislocation, active from the middle Pliocene to date) and on a local scale (heterogeneously strained rock massif at the Antei uranium deposit). The development of a regional geodynamic model of geological structural units makes it possible to carry out procedures to ensure the safety of mining operations under complex geomechanical conditions that can expose the operating mines and mines under construction, by the Argun Mining and Chemical Production Association (PAO PPGKhO) on a common methodical and geoinformational platform, to the hazards of explosions, as well as to use the simulation results aimed at finding new orebodies to assess the flanks and deep levels of the ore field.     

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 (…     

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.     

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.     

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.     

A comparative study of uranium–thorium accumulation at the western edge of the Arabian Peninsula and mineral deposits worldwide

Jordan, located at the western edge of the Arabian Plate, stands out from the remaining part of the Arabian Peninsula by its abundance in radioactive elements, mainly uranium, in a way so far not found elsewhere on the Arabian Peninsula. Uranium (U) and thorium in Jordan are concentrated in eight different types of ore mineralization: (1) intrusive-related (intramagmatic), (2) vein-type, (3) superficial, (4) sandstone-hosted (5) limestone-hosted, (6) U-Th-REE placer-type, (7) black shales, and (8) phosphorites. The major concentration of radioactive elements are synsedimentary and diagenetic in nature, mainly in near-shore marine depositional environments where uranium contents are abnormally high in the late Cretaceous to Paleogene phosphorites and increasing towards the mobile shelf of the Tethys ocean. These uraniferous phosphorites form the source of uranium that was redeposited within terrigenous chemical residues of lacustrine-fluvial depositional systems in Central Jordan (calcretes). Faultbound radiometric anomalies are caused by hot brines being vented along with the Jordan-Dead-Sea rifting. Presumably, low-grade U accumulation in (hot) black shales and marls of Silurian age are responsible for these radiometric anomalies. In the present paper, the Jordanian uranium concentrations are compared with reference types of uranium deposits elsewhere in the world to get an idea if the geological, chemical, and mineralogical features of analogue uranium mineralization in Jordan are indicative of economic targets. The uranium concentration in Jordanian phosphorites has been tracked beyond the border into Syria, Iraq, Israel, and Saudi Arabia. The uranium potential in neighboring countries is assessed based on the current geological data available for the Mediterranean Phosphorite Belt which is poised to become a another string to the bow with respect to energy supply on the Arabian Peninsula.     

Simulation of the effects of geochemical reactions on groundwater quality during planned flooding of the Königstein uranium mine, Saxony, Germany

Uranium mining in southeastern Germany resulted in significant environmental risks. Closure of the mines and subsequent rises of water levels may result in heavy-metal and radionuclide-bearing mine waters penetrating aquifers that are used for water supply. While there are certain (geo-)technical constraints on the schedule with which flooding of the mines can proceed, this process must not result in aggravating the problem of metal release. Evaluation of the likely 'natural' geochemical situation of Königstein mine after mining has ceased, and different scenarios for the release of metals indicates that rapid flooding, albeit avoiding unnecessary aeration of the waters, is likely to result in reducing conditions and consequently low U-solubilities.     

Structural and biological control of the Cenozoic epithermal uranium concentrations from the Sierra Pe?a Blanca, Mexico

Epithermal uranium deposits of the Sierra Pe?a Blanca are classic examples of volcanic-hosted deposits and have been used as natural analogs for radionuclide migration in volcanic settings. We present a new genetic model that incorporates both geochemical and tectonic features of these deposits, including one of the few documented cases of a geochemical signature of biogenic reducing conditions favoring uranium mineralization in an epithermal deposit. Four tectono-magmatic faulting events affected the volcanic pile. Uranium occurrences are associated with breccia zones at the intersection of fault systems. Periodic reactivation of these structures associated with Basin and Range and Rio Grande tectonic events resulted in the mobilization of U and other elements by meteoric fluids heated by geothermal activity. Focused along breccia zones, these fluids precipitated under reducing conditions several generations of pyrite and uraninite together with kaolinite. Oxygen isotopic data indicate a low formation temperature of uraninite, 45–55°C for the uraninite from the ore body and ～20°C for late uraninite hosted by the underlying conglomerate. There is geochemical evidence for biological activity being at the origin of these reducing conditions, as shown by low δ³⁴S values (～?24.5‰) in pyrites and the presence of low δ¹³C (～?24‰) values in microbial patches intimately associated with uraninite. These data show that tectonic activity coupled with microbial activity can play a major role in the formation of epithermal uranium deposits in unusual near-surface environments.     

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 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.     

The uranium content in Dictyonema shale of the Kaibolovo–Gostilitsy Area in the Baltic basin (Leningrad Region)

This paper reports the data on the uranium content in Dictyonema shale and phosphate rock in the Kaibolovo–Gostilitsy Area of the Baltic Basin (Leningrad Region). Specific features of the uranium ore in the studied area and stratigraphic rock sequence of the Early Ordovician Pakerort horizon are considered. A high uranium concentration in the Dictyonema shale layer has been determined, the correlation of uranium with other elements was defined, probable conditions of uranium ore genesis are described, and predicted uranium resources within the studied area are estimated.     

Magmatic and hydrothermal behavior of uranium in syntectonic leucogranites: The uranium mineralization associated with the Hercynian Guérande granite (Armorican Massif,France)

Most of the hydrothermal uranium (U) deposits from the European Hercynian belt (EHB) are spatially associated with Carboniferous peraluminous leucogranites. In the southern part of the Armorican Massif (French part of the EHB), the Guérande peraluminous leucogranite was emplaced in an extensional deformation zone at ca. 310 Ma and is spatially associated with several U deposits and occurrences. The apical zone of the intrusion is structurally located below the Pen Ar Ran U deposit, a perigranitic vein-type deposit where mineralization occurs at the contact between black shales and Ordovician acid metavolcanics. In the Métairie-Neuve intragranitic deposit, uranium oxide-quartz veins crosscut the granite and a metasedimentary enclave.Airborne radiometric data and published trace element analyses on the Guérande leucogranite suggest significant uranium leaching at the apical zone of the intrusion. The primary U enrichment in the apical zone of the granite likely occurred during both fractional crystallization and the interaction with magmatic fluids. The low Th/U values (< 2) measured on the Guérande leucogranite likely favored the crystallization of magmatic uranium oxides. The oxygen isotope compositions of the Guérande leucogranite (δ¹⁸O_{whole rock} = 9.7–11.6‰ for deformed samples and δ¹⁸O_{whole rock} = 12.2–13.6‰ for other samples) indicate that the deformed facies of the apical zone underwent sub-solidus alteration at depth with oxidizing meteoric fluids. Fluid inclusion analyses on a quartz comb from a uranium oxide-quartz vein of the Pen Ar Ran deposit show evidence of low-salinity fluids (1–6 wt.% NaCl eq.), in good agreement with the contribution of meteoric fluids. Fluid trapping temperatures in the range of 250–350 °C suggest an elevated geothermal gradient, probably related to regional extension and the occurrence of magmatic activity in the environment close to the deposit at the time of its formation. U-Pb dating on uranium oxides from the Pen Ar Ran and Métairie-Neuve deposits reveals three different mineralizing events. The first event at 296.6 ± 2.6 Ma (Pen Ar Ran) is sub-synchronous with hydrothermal circulations and the emplacement of late leucogranitic dykes in the Guérande leucogranite. The two last mineralizing events occur at 286.6 ± 1.0 Ma (Métairie-Neuve) and 274.6 ± 0.9 Ma (Pen Ar Ran), respectively. Backscattered uranium oxide imaging combined with major elements and REE geochemistry suggest similar conditions of mineralization during the two Pen Ar Ran mineralizing events at ca. 300 Ma and ca. 275 Ma, arguing for different hydrothermal circulation phases in the granite and deposits. Apatite fission track dating reveals that the Guérande granite was still at depth and above 120 °C when these mineralizing events occurred, in agreement with the results obtained on fluid inclusions at Pen Ar Ran.Based on this comprehensive data set, we propose that the Guérande leucogranite is the main source for uranium in the Pen Ar Ran and Métairie-Neuve deposits. Sub-solidus alteration via surface-derived low-salinity oxidizing fluids likely promoted uranium leaching from magmatic uranium oxides within the leucogranite. The leached out uranium may then have been precipitated in the reducing environment represented by the surrounding black shales or graphitic quartzites. As similar mineralizing events occurred subsequently until ca. 275 Ma, meteoric oxidizing fluids likely percolated during the time when the Guérande leucogranite was still at depth. The age of the U mineralizing events in the Guérande region (300–275 Ma) is consistent with that obtained on other U deposits in the EHB and could suggest a similar mineralization condition, with long-term upper to middle crustal infiltration of meteoric fluids likely to have mobilized U from fertile peraluminous leucogranites during the Late Carboniferous to Permian crustal extension events.     

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.     

Geochemical background of potentially toxic trace elements in reclaimed soils of the abandoned pyrite–uranium mine (south-central Poland)

Spatial distribution patterns of As, Ba, Cd, Cr, Cu, Mn, Ni, Pb, U and Zn were determined in topsoil samples collected after 40 years of chemical remediation conducted in the inoperative “Staszic” pyrite–uranium mine in the Holy Cross Mountains, south-central Poland. Soil samples were taken from 58 sites using a systematic random sampling design. Selected samples were subjected to an X-ray diffractometry analysis on bulk soils and separated clay fractions. Hematite, goethite and gypsum are common mineral phases in soil samples. Technogenic soils developed on reclaimed mine spoils show uniform spatial element distribution patterns and additionally a distinct enrichment in As, Pb, Mn, U and Zn. Mineral and chemical composition of soils vs. rocks points to the lithogenic source of the determined elements. The results of chemical analysis have been used for evaluation of geochemical background of trace elements in the study area with the iterative 2σ-technique. This investigation shows that using mean crustal element concentrations (Clarke values) as proxies of threshold values in soils are not useful for determination of strongly positive geochemical anomalies. A modified enrichment factor, i.e. a local enrichment factor, is proposed for identification of sites where soils are contaminated.     

In-situ SIMS uraninite U–Pb dating and genesis of the Xianshi granite-hosted uranium deposit,South China

The southeastern part of the Nanling metallogenic province, China is host to numerous granite-hosted vein-type hydrothermal uranium deposits. The geology and geochemistry of these deposits have been extensively studied. However, accurate and precise ages for the uranium mineralization are scarce because the uranium minerals in these deposits are usually fine grained, and may have formed in several stages. Therefore, the ages previously obtained by the bulk dating techniques are possibly a mixed age.The Xianshi uranium deposit, located in the southeastern part of the Guidong granite complex, is a major uranium deposit in South China. The uranium mineralization from this deposit is mainly fine grained uraninite in quartz or calcite veins which are spatially associated with the Cretaceous mantle-derived mafic dykes. Micro-Raman spectroscopy and X-ray diffraction analyses indicate that the dominant uranium mineral occurs as a rare form of uraninite (U₃O₇). Three distinct generations of uranium minerals have been identified based on petrographic and field relations. Stage 1 uraninite has the lowest UO₂ and highest PbO contents whereas Stage 3 uraninite has the highest UO₂ and lowest PbO contents.Uraninite from the Xianshi deposit was dated using an in-situ SIMS U–Pb dating technique. The results show three distinct age groups: 135 ± 4 Ma, 113 ± 2 Ma and 104 ± 2 Ma, which are in excellent agreement with the ages of three episodes of mantle-derived mafic dykes. Therefore, the Xianshi uranium deposit has experienced at least three hydrothermal events that are responsible for the deposition of uranium ores, which are genetically related to the emplacement of three sets of mafic dykes.