Structural investigation of the synthetic CaAn(PO4)2 (An = Th and Np) cheralite-like phosphates

The crystallographic structures of the synthetic cheralite, CaTh(PO₄)₂, and its homolog CaNp(PO₄)₂ have been investigated by X-ray diffraction at room temperature. Rietveld analyses showed that both compounds crystallize in the monoclinic system and are isostructural to monazite LnPO₄ (Ln = La to Gd). The space group is P2₁/n (I.T. = 14) with Z = 2. The refined lattice parameters of CaTh(PO₄)₂ are a = 6.7085(8) Å, b = 6.9160(6) Å, c = 6.4152(6) Å, and β = 103.71(1)° with best fit parameters R _wp = 4.87%, R _p = 3.69% and R _B = 3.99%. For CaNp(PO₄)₂, we obtained a = 6.6509(5) Å, b = 6.8390(3) Å, c = 6.3537(8) Å, and β = 104.12(6)° and R _wp = 6.74%, R _p = 5.23%, and R _B = 6.05%. The results indicate significant distortions of bond length and angles of the PO₄ tetrahedra in CaTh(PO₄)₂ and to a lesser extent in CaNp(PO₄)₂. The structural distortions were confirmed by Raman spectroscopy of CaTh(PO₄)₂. A comparison with the isostructural compounds LnPO₄ (Ln = Ce and Sm) confirmed that the substitution of the large rare earth trivalent cations with Ca²⁺ and Th⁴⁺ introduces a distortion of the PO₄ tetrahedra.     

Environmental impact of the former Pb–Zn mining and smelting in East Belgium

In the mining district of Plombières-La Calamine (East Belgium), extensive Pb–Zn mining activities resulted in an important contamination of overbank sediments along the Geul river. Moreover, a huge amount of heavy metals is stored in a dredged mine pond tailing, which is located along the river. In the dredged mine pond tailing sediments, Pb–Zn minerals control the solubility of Zn, Pb and Cd. Although Pb, Zn and Cd display a lower solubility in overbank sediments compared to the mine tailing pond sediments, elevated concentrations of Pb, Zn and Cd are still found in the porewater of the overbank sediments. The considerable ‘actual’ and ‘potential’ mobility of Zn, Pb and Cd indicates that the mine pond tailing sediments and the overbank sediments downstream from the mine pond tailing represent a considerable threat for the environment. Besides the chemical remobilisation of metals from the sediments, the erosion of overbank sediments and the reworking of riverbed sediments act as a secondary source of pollution.     

Diagenesis and fracturing of Paleocene–Eocene carbonate turbidite systems in the Ionian Basin: The example of the Kelçyra area (Albania)

The Kelçyra area is emplaced in a foreland fold-and-thrust belt (FFTB), characterized by a westward thrusting with the Triassic evaporites as the major décollement level. Several secondary features related with this evolution, like backthrusting, folding, duplex structures, evaporite diapirism are present. During the FFTB evolution, the study area has been subjected to several fracturing events with associated stages of fluid migration. During the pre-deformational stage, complex textures such as crack-and-seal features most likely reflect expulsion of overpressured fluids. These fluids were dominantly host-rock buffered. Within the post-deformational stage, a meteoric fluid caused cementation and development of a karst network during a period of emergence after the thrust emplacement. Subsequently, Mg calcite reprecipitated in the more stable carbonate phase calcite and dolomite, which filled part of the karts network. The latter is finally dedolomitized and locally partially dissolved by a second meteoric fluid flow, which greatly increased the secondary porosity.     

Lower Eocene carbonate-cemented “chimney” structures (Varna, Bulgaria) — Control of seepage rates on their formation and stable isotopic signature

The genesis of Lower Eocene calcite-cemented columns, “pisoid”-covered structures and horizontal interbeds, clustered in dispersed outcrops in the Pobiti Kamani area (Varna, Bulgaria) is related to fossil processes of hydrocarbon migration. Field observations, petrography and stable isotope geochemistry of the cemented structures and associated early-diagenetic veins, revealed that varying seepage rates of a single, warm hydrocarbon-bearing fluid, probably ascending along active faults, controlled the type of structure formed and its geochemical signature. Slow seepage allowed methane to oxidize within the sediment under ambient seafloor conditions (δ¹⁸O = − 1 ± 0.5‰ V-PDB), explaining columns' depleted δ¹³C ratios of − 43‰. Increasing seepage rates caused methane to emanate into the water column (δ¹³C = − 8‰) and raised precipitation temperatures (δ¹⁸O = − 8‰). Calcite-cemented conduits formed and upward migrating fluids also affected interbed cementation. Even higher-energy fluid flow and temperatures likely controlled the formation of “pisoids”, whereby sediment was whirled up and cemented.     

Lithogeochemical patterns around Pb-Zn mineralizations in Dinantian carbonate rocks of (eastern) Belgium

The lithogeochemical distribution patterns of Mg, Sr, Na, Zn, Pb, Fe, Mn, K, Corg (organic matter) and IR (insoluble residue) in the Dinantian limestones and dolomites from the eastern part of Belgium have been studied (Dinant and Verviers synclinorium). Comparison of geochemical data of non-mineralized strata revealed higher background values in the strata of the Verviers synclinorium where Pb-Zn mineralizations occur. In this area a relation may exist with the metallogenetic district (Herve-Vesdre-Theux district; proposed by Dejonghe 1985b). However, the higher background values also could relate to the more restricted sedimentation conditions in the Verviers synclinorium as opposed to the more open marine conditions in the Dinant synclinorium. The influence of mineralization on the geochemistry of limestones is limited and unpredictable. In dolomites, however, the effect can be important. In these rocks, the lithogeochemical distribution of Zn, Pb and Mn can be subdivided into three populations, i.e. a regional background, a local high background and a halo population. The higher trace element concentrations in the halo population is caused by the existence of disseminated sulfide minerals (sphalerite, galena and pyrite) and Zn-bearing goethite (mainly pseudomorphs after pyrite) and Mn-oxides. The sulfides relate to the ore emplacement. In the local high background only the Zn-bearing oxides occur. Their presence and thus the development of the local high background relates to weathering processes.     

Utilization of Shallow Geophysical Sensing at Two Abandoned Municipal/Industrial Waste Landfills on the Missouri River Floodplain

In the past 30 to 40 years, floodplain areas of large rivers, such as the Missouri River, have been extensively used for large industrial and municipal landfills. Many of these sites are now causing varying degrees of ground water contamination. Rapid geophysical characterization techniques have proven useful for delineation of anomalous areas indicative of potential contaminant plumes. These methods have also resulted in a cost effective approach to the location and number of monitoring wells.
An effective technique to initially characterize ground water contamination at such landfills along the Missouri River in northwestern Missouri involved a combination of electrical resistivity and electromagnetic conductivity methods. Resistivity was used to obtain soundings of the alluvium by using a modified Wenner array and to corroborate shallow electromagnetic conductivity measurements by using short Wenner array electrode spacings.
Upon confirmation of similar measurements of the upper soils for the two methods, numerous electromagnetic conductivity traverses were made at each landfill site. The data generated from these surveys were graphed and contoured to delineate anomalous areas. Based on the geophysical study, a ground water monitoring well network was then designed for each landfill.
As a result, a minimal number of wells were required to initially characterize the ground water quality at these two sites. In general, analysis of water samples from these wells displayed good correlation with the geophysical results.     

Geochemistry of overbank and high-order stream sediments in Belgium and Luxembourg: a way to assess environmental pollution

A geochemical survey of Belgium and Luxembourg was carried out as part of an international research project entitled ‘Regional geochemical mapping of Western Europe towards the year 2000'. The aim of this research was to map regional background geochemical patterns based on pristine or at least pre-industrial overbank samples and to deduce regional information on the degree of environmental pollution of floodplain and present-day river sediments. Over the entire study area (about 33,000 km²), 66 overbank sites have been sampled. Catchment areas range between 60 and 600 km². At each site an overbank profile has been dug out in the immediate vicinity of the river and described in detail. A first composite sample was taken 5–25 cm below the surface. This sample is supposed to represent deposition over the last centuries. Human interferences in this interval are often inferable based on changed sedimentary characteristics and the presence of anthropogenic particles such as charcoal, slags and brick fragments. A second composite sample was taken at depth, usually >1.5 m below the surface over an interval of about 20 cm. In most sites, the profile characteristics allowed to assume pre-industrial or even pristine conditions for this lower overbank sample. In some profiles this was confirmed by ¹⁴C-dating and/or by the absence of anthropogenic particles. Finally, a present-day stream sediment was sampled on the site to infer the actual pollution status. After drying at 80°C, disaggregation and sieving, the <125 μm fractions of the three sediment samples were analysed by XRF for major elements and several trace elements. Lower overbank samples generally show a direct link with the geological substrate and allow to assess natural background concentrations. Results from the mapping exercise as well as from the statistical analyses display a clear contrast between the northern part of Belgium where Cenozoic unconsolidated sandy and silty formations dominate which are especially vulnerable for erosion, and the southern part of Belgium and Luxembourg where Paleozoic and Mesozoic sandstones, carbonates, marls and shales are the prevalent lithologies. Here the shales are the most intensively eroded lithologies. This is especially reflected in the element patterns of Al₂O₃, MgO, K₂O, Ga, Ni, Rb, Sc and V which negatively correlate with SiO₂. Despite the human related pollution, the geological contrast between north and south Belgium is still recognisable in the geochemical pattern of the upper overbank and present-day stream sediment samples for the above-mentioned elements. Furthermore there is a clear increase in heavy metal contents (Zn, Cd, Pb, Cu), As and in certain locations in Ba from the lower to the upper overbank sediment, as well as to the present-day stream sediment. The relative increase in element content allows to assess the degree of pollution and helps to define those drainage areas where more detailed research is needed.     

Grain-size trends, basin subsidence and sediment supply in the Campanian Castlegate Sandstone and equivalent conglomerates of central Utah

Reconstructions of grain-size trends in alluvial deposits can be used to understand the dominant controls on stratal architecture in a foreland basin. Different initial values of sediment supply, tectonic subsidence and base-level rise are investigated to constrain their influence on stratal geometry using the observed grain-size trends as a proxy of the goodness of fit of the numerical results to the observed data. Detailed measurements of grain-size trends, palaeocurrent indicators, facies and thickness trends, channel geometries and palynological analyses were compiled for the middle Campanian Castlegate Sandstone of the Book Cliffs and its conglomerate units in the Gunnison and Wasatch plateaus of central Utah. They define the initial conditions for a numerical study of the interactions between large-scale foreland basin and small-scale sediment transport processes. From previous studies, the proximal foreland deposits are interpreted as recording a middle Campanian thrusting event along the Sevier orogenic belt, while the stratal architecture in the Book Cliffs region is interpreted to be controlled by eustatic fluctuation with local tectonic influence. Model results of stratal geometry, using a subsidence curve with a maximum rate of ≈45 m Myr^?1 for the northern Wasatch Plateau region predict the observed grain-size trends through the northern Book Cliffs. A subsidence curve with a maximum rate of ≈30 m Myr^?1 in the Gunnison–Wasatch Plateaus best reproduces the observed grain-size trends in the southern transect through the southern Wasatch Plateau. Eustasy is commonly cited as controlling Castlegate deposition east of the Book Cliffs region. A eustatic rise of 45 m Myr^?1 produces grain-size patterns that are similar to the observed, but a rate of eustatic rise based on Haq et al. (1988) will not produce the observed stratal architecture or grain-size trends. Tectonic subsidence alone, or a combined rate of tectonic subsidence and a Haq et al. (1988) eustatic rise, can explain the stratal and grain-size variations in the proximal and downstream regions.     

Crustal thickening and crustal extension as controls on the evolution of the drainage network of the central Swiss Alps between 30 Ma and the present: constraints from the stratigraphy of the North Alpine Foreland Basin and the structural evolution of the Alps

The combined information about sedimentary petrography from the North Alpine Foreland Basin and structural geology from the Alps allows a qualitative reconstruction of the drainage network of the central Swiss Alps between 30 Ma and the present. This study suggests that crustal thickening and crustal thinning significantly controlled the location of the drainage divide. It also reveals the possible controls of crustal thickening/thinning on the change of the orientation of the drainage network from across-strike between 30 and 14 Ma to along-strike thereafter. Initial crustal thickening in the rear of the wedge is considered to have formed the drainage divide between north and south at 30 Ma. Because the location of crustal thickening shifted from east to west between ≈30–20 Ma, the catchment areas of the eastern dispersal systems reached further south than those of the western Alpine palaeorivers for the same time slice. Similarly, the same crustal dynamics appear to have controlled two phases of denudation that are reflected in the Molasse Basin by petrographic trends. Uplift in the rear of the wedge caused the Alpine palaeorivers to expand further southward. This is reflected in the foreland basin by increasing admixture of detritus from structurally higher units. However, tectonic quiescence in the rear of the wedge allowed the Alpine palaeorivers to cut down into the Alpine edifice, resulting in an increase of detritus from structurally lower units. Whereas uplift in the rear of the wedge was responsible for initiation of the Alpine drainage systems, underplating of the external massifs some 50 km further north is thought to have caused along-strike deviation of the major Alpine palaeorivers. Besides crustal thickening, extension in the rear of the wedge appears to have significantly controlled the evolution of the drainage network of the western Swiss Alps. Slip along the Simplon detachment fault exposed the core of the Lepontine dome, and caused a 50-km-northward shift of the drainage divide.