Reduction of surface subsidence risk by fly ash exploitation as filling material in deep mining areas

The possibility of filling empty underground spaces, which exist owing to the extraction of mineral raw materials, with fly ash and cement fly ash mixes has been studied for the purpose of reducing the impact of deep mining on the surface. The method of physical modelling was used to study the behaviour of fly ash mixes deposited in extracted mine spaces. The models were constructed for two different geometries of underground extracted mine spaces: into cavities of the type of large slits created in the course of mining in steeply lode deposits without subsequently filling the empty space and in vertical shafts of rectangular or circular cross-section with horizontal side headings that have partly caved in due to mine shocks or other seismic events.     

Timing of Holocene sand accumulation along the coast of central and SE Vietnam

In Vietnam, the coastal sand barriers and dunes located in front of the steep slopes of the high rising Truong Son Mountains are sensitive to climate and environment change and give evidence for Holocene sea-level rise. The outer barrier sands were deposited shortly before or contemporaneous with the local sea-level high stand along the Van Phong Bay postdating the last glacial maximum (LGM). Optically stimulated luminescence (OSL) dating yielded deposition ages ranging from 8.3 ± 0.6 to 6.2 ± 0.3 ka for the stratigraphically oldest exposed barrier sands. Further periods of sand accumulation took place between 2.7 and 2.5 ka and between 0.7 and 0.5 ka. The youngest period of sand mobilisation was dated to 0.2 ± 0.01 ka and is most likely related to reworked sand from mining activities. At the Suoi Tien section in southern central Vietnam, the deposition of the inner barrier sands very likely correlate with an earlier sea-level high stand prior to the last glaciation. OSL age estimates range from 276 ± 17 to 139 ± 15 ka. OSL dating significantly improves our knowledge about the sedimentary dynamics along the coast of Vietnam during the Holocene.     

Re–Os age of non-mineralized black shale from the Kupferschiefer, Poland, and implications for metal enrichment

Six samples of non-mineralized black shale from a Kupferschiefer section in the northern part of the Polish Zechstein Basin (Zdrada IG-8 drill hole: 1026.16–1026.90 m) were studied for Re–Os isotopes and selected major and trace elements. These black shales, averaging 5.82 wt.% C_org and 1.69 wt.% S_tot, display very low base metal values (up to 106 ppb Cu, 792 ppb Pb, and 144 ppb Zn) and have abundances of 64–1376 ppb Re and 0.37–1.25 ppb Os, with a ¹⁸⁷Os/¹⁸⁸Os ratio of 6.95–22.5. The regression of all Re–Os data yields an age of 247 ± 20 Ma, which is within the range of uncertainties of previous Rb–Sr and K–Ar geochronological studies. The scatter in the Re–Os data can be explained in terms of fluctuations in sedimentary conditions, i.e., restricted basin with terrestrial influence.     

Thermal expansion and high-temperature P21/c–C2/c phase transition in clinopyroxene-type LiFeGe2O6 and comparison to NaFe(Si,Ge)2O6

A synthetic clinopyroxene with composition LiFe³⁺Ge₂O₆, monoclinic s.g. P2₁/c, a = 9.8792(7), b = 8.8095(5), c = 5.3754(3) Å, β = 108.844(6)°, V = 442.75(16) ų, has been studied by in situ low- and high-temperature single-crystal X-ray diffraction. The variation of lattice parameters and the intensity of the b-type reflections (h + k = 2n + 1, only present in the P-symmetry) with increasing temperature showed a displacive phase transition from space group P2₁/c to C2/c at a transition temperature T _tr = 789 K, first order in character, with a sudden volume increase of 1.6% and a decrease of β by 1° at the transition. This spontaneous dilatation is reversible, shows a limited hysteresis of ±10°C, and corresponds to the vanishing of the b-type reflections, thus indicating a symmetry increase to space group C2/c. Below T _tr an expansion is observed for all the cell parameters, while the β angle remained almost constant; at T > T _tr the thermal volume expansion is due to dilatation of the structure in the $(\bar{1}\,0\,1) A synthetic clinopyroxene with composition LiFe³⁺Ge₂O₆, monoclinic s.g. P2₁/c, a = 9.8792(7), b = 8.8095(5), c = 5.3754(3) ?, β = 108.844(6)°, V = 442.75(16) ?³, has been studied by in situ low- and high-temperature single-crystal X-ray diffraction. The variation of lattice parameters and the intensity of the b-type reflections (h + k = 2n + 1, only present in the P-symmetry) with increasing temperature showed a displacive phase transition from space group P2₁/c to C2/c at a transition temperature T _tr = 789 K, first order in character, with a sudden volume increase of 1.6% and a decrease of β by 1° at the transition. This spontaneous dilatation is reversible, shows a limited hysteresis of ±10°C, and corresponds to the vanishing of the b-type reflections, thus indicating a symmetry increase to space group C2/c. Below T _tr an expansion is observed for all the cell parameters, while the β angle remained almost constant; at T > T _tr the thermal volume expansion is due to dilatation of the structure in the ([`1] 0 1)(\bar{1}\,0\,1) plane, mostly along [0 1 0], and pure shear in the (0 1 0) plane due to the decrease of β. From comparison with silicate analogues, the germanate clinopyroxenes are more expansible, while the P2₁/c expands more than the C2/c phase. The evolution of Q ² (calculated as the normalized intensity of b-type reflections) with T in the framework of the Landau theory has been done using a standard expression for a first order phase transition. We observe a jump of Q ₀² = 0.538(2) at T _tr, with T _c of 481(7) K, b/a = −2,290 K, and c/a = 3,192 K, and thus far from being tri-critical point. A closely related composition (LiFe³⁺Si₂O₆) shows an equivalent phase transition at 228 K, which is very close to the tri-critical point and 561 K cooler. This result indicates that a change in the composition of tetrahedral sites can have dramatic effects on the P2₁/c ↔ C2/c displacive phase transition in clinopyroxenes. The major changes observed in the evolution of the crystal structure with T are observed in the M2 polyhedron, with a volume decrease by ca. 13.3%, compared to ca. 1.3% observed in the M1 polyhedron. The tetrahedra behave as rigid units with neither a significant change of volume at T > T _tr (<1‰), nor a change of tilting of the basal plane. No change in coordination is observed at T > T _tr in the M2 polyhedron, which remains sixfold coordinated although a strong deformation of this polyhedron is observed. This deformation is related to a strong change by 51.4° at T _tr of the kinking angle (O3–O3–O3 angle) of the B-chain of tetrahedra, which switches from O-rotated to S-rotated [from 143.3(5)° to 194.7(6)°]. The A-chain is S-rotated at T < T _tr [206.8(5)° at 703 K] and extends by 12° at the transition.     

Nanoparticles in natural systems II: The natural oxide fraction at interaction with natural organic matter and phosphate

Information on the particle size and reactive surface area of natural samples and its interaction with natural organic matter (NOM) is essential for the understanding bioavailability, toxicity, and transport of elements in the natural environment. In part I of this series (Hiemstra et al., 2010), a method is presented that allows the determination of the effective reactive surface area (A, m²/g soil) of the oxide particles of natural samples which uses a native probe ion (phosphate) and a model oxide (goethite) as proxy. In soils, the natural oxide particles are generally embedded in a matrix of natural organic matter (NOM) and this will affect the ion binding properties of the oxide fraction. A remarkably high variation in the natural phosphate loading of the oxide surfaces (Γ, μmol/m²) is observed in our soils and the present paper shows that it is due to surface complexation of NOM, acting as a competitor via site competition and electrostatic interaction. The competitive interaction of NOM can be described with the charge distribution (CD) model by defining a ≡NOM surface species. The interfacial charge distribution of this ≡NOM surface species can be rationalized based on calculations done with an evolved surface complexation model, known as the ligand and charge distribution (LCD) model. An adequate choice is the presence of a charge of −1 v.u. at the 1-plane and −0.5 v.u. at the 2-plane of the electrical double layer used (Extended Stern layer model).The effective interfacial NOM adsorption can be quantified by comparing the experimental phosphate concentration, measured under standardized field conditions (e.g. 0.01 M CaCl₂), with a prediction that uses the experimentally derived surface area (A) and the reversibly bound phosphate loading (Γ, μmol/m²) of the sample (part I) as input in the CD model. Ignoring the competitive action of adsorbed NOM leads to a severe under-prediction of the phosphate concentration by a factor ∼10 to 1000. The calculated effective loading of NOM is low at a high phosphate loading (Γ) and vice versa, showing the mutual competition of both constituents. Both constituents in combination usually dominate the surface loading of natural oxide fraction of samples and form the backbone in modeling the fate of other (minor) ions in the natural environment.Empirically, the effective NOM adsorption is found to correlate well to the organic carbon content (OC) of the samples. The effective NOM adsorption can also be linked to DOC. For this, a Non-Ideal Competitive adsorption (NICA) model is used. DOC is found to be a major explaining factor for the interfacial loading of NOM as well as phosphate. The empirical NOM-OC relation or the parameterized NICA model can be used as an alternative for estimating the effective NOM adsorption to be implemented in the CD model for calculation of the surface complexation of field samples. The biogeochemical impact of the NOM-PO₄ interaction is discussed.     

Decoupling of As and Fe release to Bangladesh groundwater under reducing conditions. Part I: Evidence from sediment profiles

This study reexamines the notion that extensive As mobilization in anoxic groundwater of Bangladesh is intimately linked to the dissolution of Fe oxyhydroxides on the basis of analyses performed on a suite of freshly collected samples of aquifer material. Detailed sediment profiles extending to 40 to 70 m depth below the surface were obtained at six sites where local groundwater As concentrations were known to span a wide range. The sediment properties that were measured include (1) the proportion of Fe(II) in the Fe fraction leached in hot 1.2 N HCl, (2) diffuse spectral reflectance, and (3) magnetic susceptibility.In parallel with local concentrations of dissolved As ranging from <5 to 600 μg/L, Fe(II)/Fe ratios in shallow (gray) Holocene sands tended to gradually increase with depth from values of 0.3 to 0.5 to up to 0.9. In deeper (orange) aquifers of presumed Pleistocene age that were separated from shallow sands by a clay layer and contained <5 μg/L dissolved As, leachable Fe(II)/Fe ratios averaged ∼0.2. There was no consistent relation between sediment Fe(II)/Fe and dissolved Fe concentrations in groundwater in nearby wells. The reflectance measurements indicate a systematic linear relation (R² of 0.66; n = 151) between the first derivative transform of the reflectance at 520 nm and Fe(II)/Fe. The magnetic susceptibility of the shallow aquifer sands ranged from 200 to 3600 (x 10⁻⁹ m³/kg SI) and was linearly related (R² of 0.75; n = 29) to the concentrations of minerals that could be magnetically separated (0.03 to 0.79% dry weight). No systematic depth trends in magnetic susceptibility were observed within the shallow sands, although the susceptibility of deeper low-As aquifers was low (up to ∼200 × 10⁻⁹ m³/kg SI).This set of observations, complemented by incubation results described in a companion paper by van Geen et al. (this volume), suggests that the release of As is linked to the transformation of predominantly Fe (III) oxyhydroxide coatings on sand particles to Fe(II) or mixed Fe(II/III) solid phases with a flatter reflectance spectrum such as siderite, vivianite, or magnetite, without necessarily resulting in the release of Fe to groundwater. The very low As/Fe ratio of magnetically separated minerals compared to the As/Fe of bulk acid leachate (2 vs. 40 10⁻⁶, respectively) suggests that such a transformation could be accompanied by a significant redistribution of As to a mobilizable phase on the surface of aquifer particles.     

Extremely slow slope movements influencing the stability of Spis Castle,UNESCO site

Spis Castle, a monument included in the UNESCO World Heritage Site list (Eastern Slovakia) is built on a travertine mound overlying soft Paleogene rocks. Lateral spreading resulting from the subsidence of strong upper travertine into soft claystone strata has fractured and separated the castle rock into several cliffs. The differential movement of individual cliff faces is the primary influence on the stability of the monument. In order to monitor and quantify the movement, two techniques were adopted: a mechanical-optical TM-71 crack gauge and a demec gauge (demountable mechanical—SOMET type crack gauge). This paper presents the results and interpretation of medium and short-term monitoring at the site.     

Alternative water management options to reduce vulnerability for climate change in the Netherlands

Urbanization, land subsidence and sea level rise will increase vulnerability of the urbanized low-lying areas in the western part of the Netherlands. In this article possibilities are explored to reduce vulnerability of these areas by implementing alternative water management options. Two main water management fields are distinguished, water supply and flood control. A four-component vulnerability framework is presented that includes threshold capacity, coping capacity, recovery capacity, and adaptive capacity. By using the vulnerability framework it is shown that current water supply and flood control strategies in the Netherlands focus on increasing threshold capacity by constructing higher and stronger dikes, improved water storage and delivery infrastructure. A complete vulnerability decreasing strategy requires measures that include all four capacities. Flood damage reduction, backup water supply systems and emergency plans are measures that can contribute to increasing coping capacity. Recovery capacity can be increased by multi-source water supply, insurance, or establishing disaster funds. Adaptive capacity can be developed by starting experiments with new modes of water supply and urbanization. Including all four components of the vulnerability framework enables better understanding of water and climate related vulnerability of urban areas and enables developing more complete water management strategies to reduce vulnerability.     

The presolar grain inventory of fine‐grained chondrule rims in the Mighei‐type (CM) chondrites

We investigated the inventory of presolar silicate, oxide, and silicon carbide (SiC) grains of fine‐grained chondrule rims in six Mighei‐type (CM) carbonaceous chondrites (Banten, Jbilet Winselwan, Maribo, Murchison, Murray and Yamato 791198), and the CM‐related carbonaceous chondrite Sutter's Mill. Sixteen O‐anomalous grains (nine silicates, six oxides) were detected, corresponding to a combined matrix‐normalized abundance of ~18 ppm, together with 21 presolar SiC grains (~42 ppm). Twelve of the O‐rich grains are enriched in ¹⁷O, and could originate from low‐mass asymptotic giant branch stars. One grain is enriched in ¹⁷O and significantly depleted in ¹⁸O, indicative of additional cool bottom processing or hot bottom burning in its stellar parent, and three grains are of likely core‐collapse supernova origin showing enhanced ¹⁸O/¹⁶O ratios relative to the solar system ratio. We find a presolar silicate/oxide ratio of 1.5, significantly lower than the ratios typically observed for chondritic meteorites. This may indicate a higher degree of aqueous alteration in the studied meteorites, or hint at a heterogeneous distribution of presolar silicates and oxides in the solar nebula. Nevertheless, the low O‐anomalous grain abundance is consistent with aqueous alteration occurring in the protosolar nebula and/or on the respective parent bodies. Six O‐rich presolar grains were studied by Auger Electron Spectroscopy, revealing two Fe‐rich silicates, one forsterite‐like Mg‐rich silicate, two Al‐oxides with spinel‐like compositions, and one Fe‐(Mg‐)oxide. Scanning electron and transmission electron microscopic investigation of a relatively large silicate grain (490 nm × 735 nm) revealed that it was crystalline åkermanite (Ca₂Mg[Si₂O₇]) or a an åkermanite‐diopside (MgCaSi₂O₆) intergrowth.