Development and morphometry of sinkholes in coastal plains of Apulia, southern Italy. Preliminary sinkhole susceptibility assessment

Evolution of coastlines in karst areas may be strongly controlled by dissolution processes which favour the development of surface and subsurface landforms. The generation of caves in these environments is commonly favoured by the mixing between fresh and brackish waters. The sinkholes resulting from the upward propagation of the caves may interfere with the anthropogenic environment and cause damage to human elements (property and activities). To highlight the often underestimated importance of karst phenomena in coastal areas, we have analyzed a coastal stretch of Apulia, in southern Italy. The study area, covering an extension of about 6 km², is situated in the Ionian coast, and presents several interesting karst landforms that are generally connected to caves. Tens of sinkholes were mapped through field surveys, multi-year aerial-photographs (dating back to the 1940s) and archival research. We have performed a morphometric analysis of the sinkholes. The analysis describes the main parameters of the sinkholes (area, length, width, and depth), and the control exerted by the main discontinuity systems in the area. The detrimental effects derived from interaction between human environment and these karst landforms is also under consideration. A sinkhole susceptibility map, which may provide useful information for planners, developers and the insurance industry has eventually been produced through application of a decision tree model.     

Variation of infiltration rate through karstic surfaces due to land use changes: A case study in Murgia (SE-Italy)

Groundwaters of the Murgia carbonate aquifer represent the main groundwater resource of the Apulia region (SE Italy). In the highlands (Alta Murgia) karst crops out in different forms and textures which have been preserved up to the 1970s: little evolved agriculture and sheep rearing produced only a marginal modification of the epikarst while a high degree of division into parcels by drystone walls helped in preserving soils from erosion. In the last years the original scenery of the Alta Murgia changed due to widespread transformations of surface karstic textures for agricultural purposes, with undeniable negative consequences on the hydrogeological balance, concerning both the infiltration and the runoff terms. Stone shattering led to flattening and deep alteration of a large part of the original karstic landscape and to demolition of drystone walls.In a study area of about 139 km² located in the Alta Murgia, the comparison of aerial photos related to the period 1950–2001 indicated that stone shattering had occurred for about 42% of the area.The hydrological behaviour of the first soil layer of experimental parcels representing both shattered stone and natural karstic surface textures was analysed by using the numerical model Hydrus-2D with the aim of estimating the variation on infiltration rate due to stone shattering. Intensive field and laboratory measurements concerned soil texture, soil water content, pressure head, saturated hydraulic conductivity, pan evaporation and meteorological parameters.     

A transdisciplinary analysis of water problems in the mountainous karst areas of Morocco

Water management and engineering in the karstic High Atlas of Morocco are difficult tasks under the prevailing geological, hydrogeological, geomorphological, vegetational and climatic conditions. It is important to be able to understand and predict the characteristics and availability of water for future water planning in the region under changing climatic and agricultural conditions. An interdisciplinary analysis of problems and adequate hydrological modelling tools developed by geologists, hydrologists and biologists are necessary. The karst areas of the High Atlas Mountains are characterised by impermeable triassic basalt underlying substantial subsurface reservoirs with high potential discharge rates. The karst groundwater aquifers are extensive but largely unknown in dimension, probably with a hierarchical network of groundwater flow paths. It is estimated that approximately 70% of the surface water is directly lost to groundwater. Steep landslide- and debris flow prone slopes exist next to coarse-grained, highly porous river beds. Infrequent, high intensity rainfall or snowmelt causes a particularly high flood risk to these karst areas. In addition, agriculture and land use changes have degraded the karst areas. The most important driving forces for degradation include permanent overgrazing even during droughts and the use of firewood by a continually growing population. Large scale degradation of vegetation has occurred in the oro-mediterranean (mountainous Mediterranean) zone, between 2600 and 3400 m which coincides with the most important zone for karstic groundwater creation. The combination of high amounts of groundwater flow and rapid surface flow due to sparse vegetation has increased the problems of flood flow.     

Shear strength characterization of municipal solid waste at the Suzhou landfill, China

The current practice of slope stability analysis for a municipal solid waste (MSW) landfill usually overlooks the dependence of waste properties on the fill age or embedment depth. Changes in shear strength of MSW as a function of fill age were investigated by performing field and laboratory studies on the Suzhou landfill in China. The field study included sampling from five boreholes advanced to the bottom of the landfill, cone penetration tests and monitoring of pore fluid pressures. Twenty-six borehole samples representative of different fill ages (0 to 13 years) were used to perform drained triaxial compression tests. The field and laboratory study showed that the waste body in the landfill can be sub-divided into several strata corresponding to different ranges of fill age. Each of the waste strata has individual composition and shear strength characteristics. The triaxial test results showed that the MSW samples exhibited a strain-hardening and contractive behavior. As the fill age of the waste increased from 1.7 years to 11 years, the cohesion mobilized at a strain level of 10% was found to decrease from 23.3 kPa to 0 kPa, and the mobilized friction angle at the same strain level increasing from 9.9° to 26°. For a confinement stress level greater than 50 kPa, the shear strength of the recently-placed MSW seemed to be lower than that of the older MSW. This behavior was consistent with the cone penetration test results. The field measurement of pore pressures revealed a perched leachate mound above an intermediate cover of soils and a substantial leachate mound near the bottom of the landfill. The measurements of shear strength properties and pore pressures were utilized to assess the slope stability of the Suzhou landfill.     

Assessing soil erosion in Mediterranean karst landscapes of Lebanon using remote sensing and GIS

Maps showing the potential for soil erosion at 1:100,000 scale are produced in a study area within Lebanon that can be used for evaluating erosion of Mediterranean karstic terrain with two different sets of impact factors built into an erosion model. The first set of factors is: soil erodibility, morphology, land cover/use and rainfall erosivity. The second is obtained by the first adding a fifth factor, rock infiltration. High infiltration can reflect high recharge, therefore decreasing the potential of surface runoff and hence the quantity of transported materials. Infiltration is derived as a function of lithology, lineament density, karstification and drainage density, all of which can be easily extracted from satellite imagery. The influence of these factors is assessed by a weight/rate approach sharing similarities between quantitative and qualitative methods and depending on pair-wise comparison matrix.The main outcome was the production of factorial maps and erosion susceptibility maps (scale 1:100,000). Spatial and attribute comparison of erosion maps indicates that the model that includes a measure of rock infiltration better represents erosion potential. Field investigation of rills and gullies shows 87.5% precision of the model with rock infiltration. This is 17.5% greater than the precision of the model without rock infiltration. These results indicate the necessity and importance of integrating information on infiltration of rock outcrops to assess soil erosion in Mediterranean karst landscapes.     

Oxygen isotopic compositions of Allende Type C CAIs: Evidence for isotopic exchange during nebular melting and asteroidal metamorphism

In situ oxygen isotopic measurements of primary and secondary minerals in Type C CAIs from the Allende CV3 chondrite reveal that the pattern of relative enrichments and depletions of ¹⁶O in the primary minerals within each individual CAI are similar to the patterns observed in Types A and B CAIs from the same meteorite. Spinel is consistently the most ¹⁶O-rich (Δ¹⁷O = −25‰ to −15‰), followed by Al,Ti-dioside (Δ¹⁷O = −20‰ to −5‰) and anorthite (Δ¹⁷O = −15‰ to 0‰). Melilite is the most ¹⁶O-depleted primary mineral (Δ¹⁷O = −5‰ to −3‰). We conclude that the original melting event that formed Type C CAIs occurred in a ¹⁶O-rich (Δ¹⁷O  −20‰) nebular gas and they subsequently experienced oxygen isotopic exchange in a ¹⁶O-poor reservoir. At least three of these (ABC, TS26F1 and 93) experienced remelting at the time and place where chondrules were forming, trapping and partially assimilating ¹⁶O-poor chondrule fragments. The observation that the pyroxene is ¹⁶O-rich relative to the feldspar, even though the feldspar preceded it in the igneous crystallization sequence, disproves the class of CAI isotopic exchange models in which partial melting of a ¹⁶O-rich solid in a ¹⁶O-poor gas is followed by slow crystallization in that gas. For the typical (not associated with chondrule materials) Type C CAIs as well for as the Types A and B CAIs, the exchange that produced internal isotopic heterogeneity within each CAI must have occurred largely in the solid state. The secondary phases grossular, monticellite and forsterite commonly have similar oxygen isotopic compositions to the melilite and anorthite they replace, but in one case (CAI 160) grossular is ¹⁶O-enriched (Δ¹⁷O = −10‰ to −6‰) relative to melilite (Δ¹⁷O = −5‰ to −3‰), meaning that the melilite and anorthite must have exchanged its oxygen subsequent to secondary alteration. This isotopic exchange in melilite and anorthite likely occurred on the CV parent asteroid, possibly during fluid-assisted thermal metamorphism.     

Mineral inclusions in diamonds from the Kelsey Lake Mine, Colorado, USA: Depleted Archean mantle beneath the Proterozoic Yavapai province

Thirty-four silicate and oxide inclusions large enough for in situ WDS electron microprobe analysis were exposed by grinding/polishing of 19 diamonds from the Kelsey Lake Mine in the Colorado-Wyoming State Line Kimberlite district. Eighteen olivines, seven Cr-pyropes, four Mg-chromites, and one orthopyroxene in 15 stones belong to the peridotite (P) suite and three garnets and one omphacite in three stones belong to the eclogite (E) suite. The fact that this suite is dominated by the peridotite population is in stark contrast to the other diamond suites studied in the State Line district (Sloan, George Creek), which are overwhelmingly eclogitic. Kelsey Lake olivine inclusions are magnesian (17 of 18 grains in 9 stones are in the range Fo 92.7-93.1), typical of harzburgitic P-suite stones worldwide, but unlike the more Fe-rich (lherzolitic) Sloan olivine suite. Mg-chromites (wt% MgO = 12.8-13.8; wt% Cr₂O₃ = 61.4-66.6) are in the lower MgO range of diamond inclusion chromites worldwide. Seven harzburgitic Cr-pyropes in five stones have moderately low calcium contents (wt% CaO = 3.3-4.3) but are very Cr-rich (wt% Cr₂O₃ = 9.7-16.7). A few stones have been analyzed by SIMS for carbon isotope composition and nitrogen abundance. One peridotitic stone is apparently homogeneous in carbon isotope composition (δ¹³C_PDB = −6.2‰) but with variable nitrogen abundance (1296-2550 ppm). Carbon isotopes in eclogitic stones range from “normal” for the upper mantle (δ¹³C_PDB = −5.5‰) to somewhat low (δ¹³C_PDB = −10.2‰), with little internal variation in individual stones (maximum difference is 3.6‰). Nitrogen contents (2-779 ppm) are lower than in the peridotitic stone, and are lower in cores than in rims. As, worldwide, harzburgite-suite diamonds have been shown to have formed in Archean time, we suggest that the Kelsey Lake diamond population was derived from a block of Archean lithosphere that, at the time of kimberlite eruption, existed beneath the Proterozoic Yavapai province. The mixed diamond inclusion populations from the State Line kimberlites appear to support models in which volumes of Wyoming Craton Archean mantle survive buried beneath Proterozoic continental crust. Such material may be mixed with eclogitic/lherzolitic regimes emplaced beneath or intermingled with the Archean rocks by Proterozoic subduction.     

Iron isotopes constrain biologic and abiologic processes in banded iron formation genesis

The voluminous 2.5 Ga banded iron formations (BIFs) from the Hamersley Basin (Australia) and Transvaal Craton (South Africa) record an extensive period of Fe redox cycling. The major Fe-bearing minerals in the Hamersley-Transvaal BIFs, magnetite and siderite, did not form in Fe isotope equilibrium, but instead reflect distinct formation pathways. The near-zero average δ⁵⁶Fe values for magnetite record a strong inheritance from Fe³⁺ oxide/hydroxide precursors that formed in the upper water column through complete or near-complete oxidation. Transformation of the Fe³⁺ oxide/hydroxide precursors to magnetite occurred through several diagenetic processes that produced a range of δ⁵⁶Fe values: (1) addition of marine hydrothermal , (2) complete reduction by bacterial dissimilatory iron reduction (DIR), and (3) interaction with excess that had low δ⁵⁶Fe values and was produced by DIR. Most siderite has slightly negative δ⁵⁶Fe values of ∼ −0.5‰ that indicate equilibrium with Late Archean seawater, although some very negative δ⁵⁶Fe values may record DIR. Support for an important role of DIR in siderite formation in BIFs comes from previously published C isotope data on siderite, which may be explained as a mixture of C from bacterial and seawater sources.Several factors likely contributed to the important role that DIR played in BIF formation, including high rates of ferric oxide/hydroxide formation in the upper water column, delivery of organic carbon produced by photosynthesis, and low clastic input. We infer that DIR-driven Fe redox cycling was much more important at this time than in modern marine systems. The low pyrite contents of magnetite- and siderite-facies BIFs suggests that bacterial sulfate reduction was minor, at least in the environments of BIF formation, and the absence of sulfide was important in preserving magnetite and siderite in the BIFs, minerals that are poorly preserved in the modern marine record. The paucity of negative δ⁵⁶Fe values in older (Early Archean) and younger (Early Proterozoic) BIFs suggests that the extensive 2.5 Ga Hamersley-Transvaal BIFs may record a period of maximum expansion of DIR in Earth’s history.     

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.     

Core formation and the oxidation state of the Earth: Additional constraints from Nb, V and Cr partitioning

We have combined metal-silicate partitioning data from the literature with new experimental results at 1.5-8 GPa and 1480-2000 °C to parameterize the effects of pressure, temperature and composition on the partitioning of V, Cr and Nb between liquid Fe metal (with low S and C content) and silicate melt.Using information from the steelmaking literature to correct for interactions in the metal phase, we find that, for peridotitic silicate melts, metal-silicate partition coefficients are given by: