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.     

U–Pb Zircon geochronology of the Cambro-Ordovician metagranites and metavolcanic rocks of central and NW Iberia

New U–Pb zircon data from metagranites and metavolcanic rocks of the Schist-Graywacke Complex Domain and the Schistose Domain of Galicia Tras-os-Montes Zone from central and NW Iberia contribute to constrain the timing of the Cambro-Ordovician magmatism from Central Iberian and Galicia Tras-os-Montes Zones which occurred between 498 and 462 Ma. The crystallization ages of the metagranites and metavolcanic rocks from the northern Schist-Graywacke Complex Domain are as follows: (a) in west Salamanca, 489 ± 5 Ma for Vitigudino, 486 ± 6 Ma for Fermoselle and 471 ± 7 Ma for Ledesma; (b) in northern Gredos, 498 ± 4 Ma for Castellanos, 492 ± 4 Ma for San Pelayo and 488 ± 3 Ma for Bercimuelle; (c) in Guadarrama, 490 ± 5 Ma for La Estación I, 489 ± 9 Ma for La Cañada, 484 ± 6 Ma for Vegas de Matute (leucocratic), 483 ± 6 Ma for El Cardoso, 482 ± 8 Ma for La Morcuera, 481 ± 9 Ma for Buitrago de Lozoya, 478 ± 7 Ma for La Hoya, 476 ± 5 Ma for Vegas de Matute (melanocratic), 475 ± 5 Ma for Riaza, 473 ± 8 Ma for La Estación II and 462 ± 11 Ma for La Berzosa; and (d) in Toledo, 489 ± 7 Ma for Mohares and 480 ± 8 Ma for Polán. The crystallization ages of the metagranites from the Schistose Domain of Galicia Tras-os-Montes Zone are 497 ± 6 Ma for Laxe, 486 ± 8 Ma for San Mamede, 482 ± 7 Ma for Bangueses, 481 ± 5 Ma for Noia, 480 ± 10 for Rial de Sabucedo, 476 ± 9 Ma for Vilanova, 475 ± 6 Ma for Pontevedra, 470 ± 6 Ma for Cherpa and 462 ± 8 Ma for Bande. This magmatism is characterized by an average isotopic composition of (⁸⁷Sr/⁸⁶Sr)_485Ma ≈ 0.712, (ε_Nd)_485Ma ≈ ?4.1 and (T_DM) ≈ 1.62 Ga, and a high zircon inheritance, composed of Ediacaran–Early Cambrian (65 %) and, to a lesser extent, Cryogenian, Tonian, Mesoproterozoic, Orosirian and Archean pre-magmatic cores. Combining our geochronological and isotopic data with others of similar rocks from the European Variscan Belt, it may be deduced that Cambro-Ordovician magmas from this belt were mainly generated by partial melting of Ediacaran–Early Cambrian igneous rocks.     

Fingerprinting the Late Pleistocene tephras of Ciomadul volcano,eastern–central Europe

Late Pleistocene tephras derived by large explosive volcanic eruptions are widespread in the Mediterranean and surrounding areas. They are important isochronous markers in stratigraphic sections and therefore it is important to constrain their sources. We report here tephrochronology results using multiple criteria to characterize the volcanic products of the Late Pleistocene Ciomadul volcano in eastern–central Europe. This dacitic volcano had an explosive eruption stage between 57 and 30 ka. The specific petrological character (ash texture, occurrence of plagioclase and amphibole phenocrysts and their compositions), the high-K calc-alkaline major element composition and particularly the distinct trace element characteristics provide a strong fingerprint of the Ciomadul volcano. This can be used for correlating tephra and cryptotephra occurrences within this timeframe. Remarkably, during this period several volcanic eruptions produced tephras with similar glass major element composition. However, they differ from Ciomadul tephras by glass trace element abundances, ratios of strongly incompatible trace elements and their mineral cargo that serve as discrimination tools. We used (U-Th)/He zircon dates combined with U-Th in situ rim dates along with luminescence and radiocarbon dating to constrain the age of the explosive eruptions of Ciomadul that yielded distal tephra layers but lack of identified proximal deposits.     

Late Quaternary volcanic record from lakes of Michoacán,central Mexico

This paper describes the initial stages of the development of a tephrochronology for the region of the Michoacán–Guanajuato volcanic field (MGVF) in central Mexico. There are two elements to this: the geochemical characterisation of volcanic glass and the linkage of tephra deposits to eruptions of known age. The MGVF is dominated by cinder cones and shield volcanoes which erupt only once. There are only two stratovolcanoes (multiple eruptions) which are common elsewhere in the Trans-Mexican Volcanic Belt. Tephras were sampled from sub-aerial sites close to cones of known age and from lake sediment cores from the Zirahuén, Pátzcuaro and Zacapu basins in the State of Michoacán. Multiple samples were collected to ensure that each tephra was well represented. The glass was analysed by electron microprobe and found to be calc-alkaline in composition. SiO₂ abundances varied from 52% to 75%. Full results are available at http://www.geo.ed.ac.uk/tephra/. The ages of the dated cones ranged from the 20th century AD to ca 17,000 ¹⁴C years BP. Tephras from eruptions of El Jabali (3840 ¹⁴C years BP), Jorullo (1759–1774) and Paricutín (1943–1952) have been identified in lake cores. These provide a means of correlating between basins and have the potential to provide a basis for understanding the volcanic history of this area and for dating a wider range of sediment sequences.     

Environmental problems at the Nevşehir (Kozakli) geothermal field,central Turkey

The Kozakli–Nev?ehir geothermal field extends a long a NW–SE direction at SE of the Centrum of Kozakli. The area is not rugged and average elevation is 1,000 m. The Kozanözü Creek flows towards north of the area. In the Kozakli thermal Spa area, thermal waters are manifested along a valley with a length of 1.5 km and 200 m width. In this resort some hot waters are discharged with no use. The thermal water used in the area comes from wells drilled by MTA. In addition, these waters from wells are also utilized by hotels, baths and motels belonging to City Private Management, Municipality and private sector. The measured temperature of Kozakli waters ranges from 43–51°C in springs and 80–96°C in wells. Waters are issued in a wide swampy area as a small group of springs through buried faults. Electrical conductivity values of thermal spring and well waters are 1,650–3,595 μS/cm and pH values are 6.72–7.36. Kozakli cold water has an electrical conductivity value of 450 μS/cm and pH of 7.56. All thermal waters are dominated by Na⁺ and Cl–SO₄ while cold waters are dominated by Ca⁺² and HCO₃ ^?. The aim of this study was to investigate the environmental problems around the Kozakli geothermal field and explain the mechanisms of karstic depression which was formed by uncontrolled use of thermal waters in this area and bring up its possible environmental threats. At the Kozakli geothermal field a sinkhole with 30 m diameter and 15 m depth occurred in January, 17th 2007 at the recreation area located 20 m west of the geothermal well which belongs to the government of Nev?ehir province. The management of the geothermal wells should be controlled by a single official institution in order to avoid the creation of such karstic structures affecting the environment at the source area.     

Late Cretaceous palynoflora from the central part of the Adriatic Carbonate Platform (Islands of Hvar and Šćedro), southern Croatia

This paper provides the first palynological data from four Upper Cretaceous localities from the Islands of Hvar and Šćedro (southern Croatia), in the central part of the Adriatic Carbonate Platform. Studied material represents palynomorphs produced by coastal vegetation and transported to the shallow marine platform areas. Determined vegetation includes diverse hygrophilous, understory vegetation, range of evergreen needle trees attributable to Pinaceae and Podocarpaceae, as well as Araucarian conifers; ginkgo, cycads and/or bennettites. Flowering plants were likely represented by herbaceous forms. The palynoflora is generally indicative of a temperate, warm and humid climate. The occurrence of the Normapolles group with the presence of Plicapollis sp. and Pseudoculopollis sp. point to Turonian or probable Turonian–Coniacian age, and represent the southernmost record of occurrence within the Normapolles palynological province. Dominance of angiosperms and low abundance of ferns suggests an early-Late Cretaceous age. These findings are supported by the micropaleontological analyses and previously determined age of the sauropod dinosaur footprints described on the Island of Hvar. Based on the paleobotanical and palynological data, the dinosaur diet probably included araucarian conifers, ginkgo and angiosperms, and ferns to a lesser extent.     

Late Ordovician Reefs and the Biological Crisis at the Ordovician–Silurian Boundary

Reef formation in the Late Ordovician was relatively widespread in the Sandbian and Katian times. In the late Katian, it gradually reduced and ended in the Hirnantian, before the end of the Ordovician. In parallel, reef-building skeleton frame-building biota disappeared and was replaced with algae and calcimicrobes.     

Late Glacial, Early Holocene and Late Holocene life at the interface of a distinct landscape — relationship of humans and environments in the Sub-Carpathian region (N Hungary)

Relationships between the communities and environment surrounding these communities can be disclosed by the application of different archeological, geological and environmental historical methods. This includes the deployment of numerous tools in scientific investigation including the application of chronological, sedimentological, geochemical and paleoecological analytical methods on sequences accumulated in historical catchment basins of peat-bog. The Nádas-tó at Nagybárkány is a small peatbog in the northern part of Hungary, on the Sub-Carpathian region. The formation of the lake can be traced back to the Late Glacial period. The sediments deposited in the lakebed provide a record of climatic and hydrologic changes. A higher water level could be demonstrated from the Late Glacial to the Mid-Holocene, when the reed-beds covered a small area only. This was followed by a hiatus spanning ca. 4400 years, caused by the deepening and cleaning of the lakebed during the Late Iron / Imperial Age, between 2100 - 1900 cal BP years. After this change the water level decreased and the water quality was more eutrophic. A reed-bed evolved around the lake. Paludification started with a bulrush floating mat phase at the close of the Middle Age, ca. 1500 cal AD years. The endowments and settlement pattern persisted from the Neolithic onwards until the terminal Modern Age, when measures aimed to ordain the area substantially altered the natural landscape. Although some anthropogenic disturbances can be reconstructed in the development of the peatland, some climatic effects and authogenic processes might be separated by paleoecological analyses.     

Late Quaternary episodic displacement on a sackung scarp in the central Spanish Pyrenees. Secondary paleoseismic evidence?

A sackung scarp has been investigated by trenching in the central Spanish Pyrenees. This feature is located 18 km to the SW of the North Maladeta Fault, which is the most probable source of the M_w 5.3 Vielha earthquake of 1923. Three displacement events have been inferred for the trenched sackung based on colluvial wedge stratigraphy and fault truncation. The increasing amount of deformation in each successive faulting event may be related to the progressive weakening of the slope through time. A minimum vertical slip rate of 0.19 mm/yr has been calculated for the sackung scarp. Several arguments suggest that the episodic displacement of the analysed sackung is controlled by strong seismic shaking: (a) Spatial association of the sackung features with the North Maladeta Fault; (b) Episodic displacement with a millennial recurrence (5.6 kyr) consistent with the expectable earthquake recurrence interval for a low slip rate fault, like the neighbouring North Maladeta Fault. Demonstrating in future investigations that the sackung features in the area constitute archives of large paleoearthquakes would be of great interest for seismic hazard assessments. They might help to improve the catalogue of paleoearthquakes and might provide information on earthquake recurrence intervals and the age of the most recent event (MRE).     

Environmental impacts from mining at Taojiang Mn ore deposit, central Hunan, China

The Taojiang Mn ore deposit was exploited in the early 1960s, and waste rocks were developed since then. Because the Mn ores were hosted within the metal-enriched black shales （Peng et al., 2004）, the continuous mining has led to the exposure of an immense quality of black shales, which might cause serious impacts on environments. The present study deals with this environmental issue with samples from the waste rocks, and from the surrounding soils and surface water. The mineralogy of the waste rock was studied using EMPA, then a large number of elements in all waste rock, soil, and water samples were analyzed at a wide range of concentrations with high accuracy using an Elan6000 ICP-MS machine at Guangzhou Institute of Geochemistry, Chinese Academy of Sciences. The waste rock is composed mostly of black shales, with minor Mn carbonates. Both black shales and Mn carbonates of the waste rock contain many sulfide minerals, mainly pyrite, with minor galena, sphalerite, chalcopyrite, and others. The waste rocks are enriched in many metals including Sc, V, Cr, Co, Ni, Fe, Mn, Cu, Zn, Pb, Th, U, Mo, Sb, Sn, Tl, and others, and the metals are mostly hosted within the sulfides. Weathering of waste rocks might cause emission of the following metals： V, Cd, Ni, Th, U, Mo, Sb, Tl, Sc, Cr, Cu, Zn, Sn, and minor Co, and Pb. The surrounding soils are highly enriched in Cr, Co, Cu, Zn, Mn, Mo, Cd, Tl, and Pb, with the enrichment factors of 2.67.3.8, 7.26, 7.27, 8.2, 5.7, 13, and 5.4, respectively. The element ratios （Rb/Cs, Fe/Mn, Nb/Zr, Hf/Zr, and Ba/Sr） and REE distribution patterns of the soils are similar to those of the waste rocks and bedrocks.     

对金矿(334)?资源量如何划分的探讨

我国固体勘查规范体系中各规范之间存在矛盾,在评审金矿地质勘查报告的过程中,对金矿(33-4)?如何划分的标准不统一,文章以五台山东腰庄金矿外围普查报告中划分(334)?资源量为例.对如何划分(334)?资源量进行探讨.并根据实际情况对金矿(334)?如何确定提出了自己的认识.     

Studying travertines for neotectonics investigations: Middle–Late Pleistocene syn-tectonic travertine deposition at Serre di Rapolano (Northern Apennines, Italy)

Middle–Late Pleistocene tectonic activity has been inferred through studies on travertine deposits exposed in a tract of the hinterland Northern Apennines. A detailed study on the relationships between tectonics and travertine deposition coupled with ²³⁰Th/²³⁴U age determination of travertines at Cava Oliviera quarry, located close to Serre di Rapolano village (southern Tuscany, Northern Apennines), allowed us to recognise Pleistocene faults, whose activity has been referred to 157–24 ka, at least. Travertine deposition was tectonically controlled by WSW-ENE striking, oblique and normal faults, associated to a main fault (named as the Violante Fault). This structure dissected a regional normal fault (known as the Rapolano Fault) Early–Middle Pliocene in age, which bounded the eastern side of the Pliocene Siena Basin, and gave rise to space accommodation for clayey and sandy marine sediments. Hydrothermal circulation (and related travertine deposition) was favoured by the damaging enhancement due to the fault–fault intersection. Tectonic activity has been also documented by deformation recorded by travertines, which suggest a main tectonic event between 64 ± 5 and 40 ± 5 ka. The tectonic activity described for the study area agrees with the Quaternary tectonic evolution documented in the surrounding areas (e.g. Mt. Amiata and Mt. Vulsini), as well as the Tyrrhenian margin of the Central Apennines, indicating that a widespread tectonic activity affected the inner part of the Apennines until the latest Quaternary.     

关于煤炭预测的资源量(334)?问题的讨论

通过对煤炭预测的资源量(334)?问题产生的原因以及煤与非煤矿产资源差异化管理的历史和现状进行梳理和分析,认为煤炭预测的(334)?资源量从《煤、泥炭地质勘查规范》的工程控制要求来看,与《固体矿产资源/储量分类》、《固体矿产地质勘查规范总则》中推断的内蕴经济的333基本相当。建议在现有固体矿产资源储量相关标准、规范不变的前提下,对煤炭资源实行差异化管理,由国家资源储量管理部门行文,明确规定将煤炭预测的资源量(334)?纳入查明矿产资源之中,对其按查明资源储量进行管理。     

Stratigraphy and palaeoclimatic significance of Late Quaternary loess–palaeosol sequences of the Last Interglacial–Glacial cycle in central Alaska

Loess is one of the most widespread subaerial deposits in Alaska and adjacent Yukon Territory and may have a history that goes back 3 Ma. Based on mineralogy and major and trace element chemistry, central Alaskan loess has a composition that is distinctive from other loess bodies of the world, although it is quartz-dominated. Central Alaskan loess was probably derived from a variety of rock types, including granites, metabasalts and schists. Detailed stratigraphic data and pedologic criteria indicate that, contrary to early studies, many palaeosols are present in central Alaskan loess sections. The buried soils indicate that loess sedimentation was episodic, or at least rates of deposition decreased to the point where pedogenesis could keep ahead of aeolian input. As in China, loess deposition and pedogenesis are likely competing processes and neither stops completely during either phase of the loess/soil formation cycle. Loess deposition in central Alaska took place before, and probably during the last interglacial period, during stadials of the mid-Wisconsin period, during the last glacial period and during the Holocene. An unexpected result of our geochronological studies is that only moderate loess deposition took place during the last glacial period. Our studies lead us to conclude that vegetation plays a key role in loess accumulation in Alaska. Factors favouring loess production are enhanced during glacial periods but factors that favour loess accumulation are diminished during glacial periods. The most important of these is vegetation; boreal forest serves as an effective loess trap, but sparsely distributed herb tundra does not. Thus, thick accumulations of loess should not be expected where tundra vegetation was dominant and this is borne out by modern studies near the treeline in central Alaska. Much of the stratigraphic diversity of North American loess, including that found in the Central Lowlands, the Great Plains, and Alaska is explained by a new model that emphasizes the relative importance of loess production factors versus loess accumulation factors.     

Uranium(VI) in aqueous solutions at 25°C and a pressure of 1 bar: Insight from experiments and calculations

The behavior of the 0.1 mNaCl + 0.002 mHCl + 1.9 × 10^?5 mUO₂(NO₃)₂ solution was studied at pH from 2.7 to 11.0, 25°C, and 1 bar in an argon atmosphere. The curve of variations in U concentration exhibits two minima at pH = 6.6 ± 0.7 and 10.0 ± 0.5. These minima are related to the precipitation of schoepite and clarkeite, respectively. The experimental data were used to refine the stability constants of U(VI) (hydroxo) complexes. For the polymer species of U(VI) with charges from +2 to ?1, the method of additivity of thermochemical increments was used, and increments of the linear relation were determined for the calculation of the Gibbs free energies of formation (Δ_fG _298.15 ⁰ ) of respective homologue series. The proposed method was applied to calculate the Δ_fG _298.15 ⁰ of formation of U(VI) (hydroxo)complexes containing from one to five uranium atoms.     

Surface complexation of U(VI) on goethite (α-FeOOH)

Sorption of U(VI) to goethite is a fundamental control on the mobility of uranium in soil and groundwater. Here, we investigated the sorption of U on goethite using EXAFS spectroscopy, batch sorption experiments and DFT calculations of the energetics and structures of possible surface complexes. Based on EXAFS spectra, it has previously been proposed that U(VI), as the uranyl cation , sorbs to Fe oxide hydroxide phases by forming a bidentate edge-sharing (E2) surface complex, >Fe(OH)₂UO₂(H₂O)_n. Here, we argue that this complex alone cannot account for the sorption capacity of goethite (α-FeOOH). Moreover, we show that all of the EXAFS signal attributed to the E2 complex can be accounted for by multiple scattering. We propose that the dominant surface complex in CO₂-free systems is a bidentate corner-sharing (C2) complex, (>FeOH)₂UO₂(H₂O)₃ which can form on the dominant {101} surface. However, in the presence of CO₂, we find an enhancement of UO₂ sorption at low pH and attribute this to a (>FeO)CO₂UO₂ ternary complex. With increasing pH, U(VI) desorbs by the formation of aqueous carbonate and hydroxyl complexes. However, this desorption is preceded by the formation of a second ternary surface complex (>FeOH)₂UO₂CO₃. The three proposed surface complexes, (>FeOH)₂UO₂(H₂O)₃, >FeOCO₂UO₂, and (>FeOH)₂UO₂CO₃ are consistent with EXAFS spectra. Using these complexes, we developed a surface complexation model for U on goethite with a 1-pK model for surface protonation, an extended Stern model for surface electrostatics and inclusion of all known UO₂-OH-CO₃ aqueous complexes in the current thermodynamic database. The model gives an excellent fit to our sorption experiments done in both ambient and reduced CO₂ environments at surface loadings of 0.02-2.0 wt% U.