Chrome-spinels in serpentinites and talc carbonates of the El Ideid-El Sodmein District, central Eastern Desert, Egypt: their metamorphism and petrogenetic implications

Serpentinites and talc-carbonate rocks of El Ideid-El Sodmein District (ISD), central Eastern Desert, Egypt, contain variably altered chrome-spinels. Back-scattered electron images and electron microprobe analyses of chrome-spinels and associated silicates are made to evaluate their textural and compositional variations with metamorphism. In most cases the chrome-spinel crystals are concentrically zoned with unaltered cores through transitional zone of ferritchromit to Cr-magnetite toward the rims. In talc-carbonate rocks chrome-spinels are extensively altered to Cr-magnetite. Compared to cores, the metamorphic rims are enriched in Cr# (0.83–1.0 vs. 0.58–0.63 for rims and cores, respectively) and impoverished in Mg# (0.05–0.29 vs. 0.57–0.63), due to Mg–Fe and Al(Cr)–Fe³⁺ exchange with the surrounding silicates during regional metamorphism rather than serpentinization process. Textural and compositional features of the chrome-spinels suggest transitional greenschist-amphibolite up to lower amphibolite facies metamorphism (at 500–600 °C), which is isofacial with the country rocks. The common preservation of unaltered chrome-spinel cores in the serpentinites, contrary to talc-carbonate rocks, implies that full equilibration has not been attained due to small metamorphic fluid–rock ratio. Microprobe analyses profile across a concentrically zoned grain confirms the presence of two compositional (miscibility?) gaps; one between chrome-spinel core and ferritchromit zone; and another one between ferritchromit zone and Cr-magnetite outer rim.Chrome-spinel cores do not appear to have re-equilibrated completely with the metamorphic spinel rims and surrounding silicates, indicating relic magmatic composition not affected by metamorphism. Core compositions suggest an ophiolitic origin and derivation by high degrees of melting of reduced, depleted harzburgite to dunite mantle peridotites in an oceanic supra-subduction zone (marginal-basin) tectonic environment.     

Application of precise 142Nd/144Nd analysis of small samples to inclusions in diamonds (Finsch,South Africa) and Hadean Zircons (Jack Hills,Western Australia)

¹⁴⁶Sm–¹⁴²Nd and ¹⁴⁷Sm–¹⁴³Nd systematics were investigated in garnet inclusions in diamonds from Finsch (S. Africa) and Hadean zircons from Jack Hills (W. Australia) to assess the potential of these systems as recorders of early Earth evolution. The study of Finsch inclusions was conducted on a composite sample of 50 peridotitic pyropes with a Nd model age of 3.3 Ga. Analysis of the Jack Hills zircons was performed on 790 grains with ion microprobe ²⁰⁷Pb/²⁰⁶Pb spot ages from 3.95 to 4.19 Ga. Finsch pyropes yield 100 × ?¹⁴²Nd = ? 6 ± 12 ppm, ?¹⁴³Nd = ? 32.5, and ¹⁴⁷Sm/¹⁴⁴Nd = 0.1150. These results do not confirm previous claims for a 30 ppm ¹⁴²Nd excess in South African cratonic mantle. The lack of a ¹⁴²Nd anomaly in these inclusions suggests that isotopic heterogeneities created by early mantle differentiation were remixed at a very fine scale prior to isolation of the South African lithosphere. Alternatively, this result may indicate that only a fraction of the mantle experienced depletion during the first 400 Myr of its history. Analysis of the Jack Hills zircon composite yielded 100 × ?¹⁴²Nd = 8 ± 10 ppm, ?¹⁴³Nd = 45 ± 1, and ¹⁴⁷Sm/¹⁴⁴Nd = 0.5891. Back-calculation of this present-day ?¹⁴³Nd yields an unrealistic estimate for the initial ?¹⁴³Nd of ? 160 ?-units, clearly indicating post-crystallization disturbance of the ¹⁴⁷Sm–¹⁴³Nd system. Examination of ^146,147Sm–^142,143Nd data reveals that the Nd budget of the Jack Hills sample is dominated by non-radiogenic Nd, possibly contained in recrystallized zircon rims or secondary subsurface minerals. This secondary material is characterized by highly discordant U–Pb ages. Although the mass fraction of altered zircon is unlikely to exceed 5–10% of total sample, its high LREE content precludes a reliable evaluation of ¹⁴⁶Sm–¹⁴²Nd systematics in Jack Hills zircons.     

Controls on porphyroblast size along a regional metamorphic field gradient

Garnet-bearing schists from the Waterville Formation of south-central Maine provide an opportunity to examine the factors governing porphyroblast size over a range of metamorphic grade. Three-dimensional sizes and locations for all garnet porphyroblasts were determined for three samples along the metamorphic field gradient spanning lowest garnet through sillimanite grade, using high-resolution X-ray computed tomography. Comparison of crystal size distributions to previous data sets obtained by stereological methods for the same samples reveals significant differences in mode, mean, and shape of the distributions. Quantitative textural analysis shows that the garnets in each rock crystallized in a diffusion-controlled nucleation and growth regime. In contrast to the typical observation of a correlation between porphyroblast size and position along a metamorphic field gradient, porphyroblast size of the lowest-grade specimen is intermediate between the high- and middle-grade specimens’ sizes. Mean porphyroblast size does not correlate with peak temperatures from garnet-biotite Fe-Mg exchange thermometry, nor is post-crystallization annealing (Ostwald Ripening) required to produce the observed textures, as was previously proposed for these rocks. Robust pseudosection calculations fail to reproduce the observed garnet core compositions for two specimens, suggesting that these calc-pelites experienced metasomatism. For each of these two specimens, Monte Carlo calculations suggest potential pre-metasomatism bulk compositions that replicate garnet core compositions. Pseudosection analyses allow the estimation of the critical temperatures for garnet growth: ∼481, ∼477, and ∼485°C for the lowest-garnet-zone, middle-garnet-zone, and sillimanite-zone specimens, respectively. Porphyroblast size appears to be determined in this case by a combination of the heating rate during garnet crystallization, the critical temperature for the garnet-forming reaction and the kinetics of nucleation. Numerical simulations of thermally accelerated, diffusion-controlled nucleation, and growth for the three samples closely match measured crystal size distributions. These observations and simulations suggest that previous hypotheses linking the garnet size primarily to the temperature at the onset of porphyroblast nucleation can only partially explain the observed textures. Also important in determining porphyroblast size are the heating rate and the distribution of favorable nucleation sites.     

Geomorphological hazards related to deep dissolution phenomena in the Western Italian Alps: Distribution, assessment and interaction with human activities

Deep dissolution affects great part of soluble rocks (e.g. gypsum and anhydrite) of the Western Italian Alps. The related superficial phenomena (sinkholes, gravity-induced processes and a local worsening of geomechanical rock properties) are not limited to typical karsts landscape and cause slope instability also affecting populated sites and infrastructures. The paper aims to describe general characteristic of dissolution phenomena, to interpret their conditioning factors and evolutionary stages and to assess possible hazards due to their superficial effects.The search for evidences of deep dissolution leads to the selection of representative sites in the central part of the Western Italian Alps (Piemonte and Valle d'Aosta Region). Detailed geological and geomorphological studies have been used to classify the selected sites by type, size and variable state of activity. Very different evolutionary stages of dissolution phenomena have been interpreted by comparison of case-studies: some are early “embryonic”; others are more evolved, up to typical sinkholes, or even remodelled by other phenomena. Some cases show an extreme complexity in the interactions between corrosion phenomena and other geomorphic processes: slope deformations, from one side, and karst, fluvial and glacial phenomena, to the other. A wide range of movement rates on slope instabilities induced by deep dissolution have been estimated by topographic and geomorphic data. Geochemical data on removed rocks by dissolution indicate 0.4 mm/year values for local subsidence. Historical and technical data indicate low frequency of major dissolution-induced collapses, but highlight widespread damages to tunnels, roads and buildings, especially along slopes.     

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.     

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.     

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.     

Seasonal patterns of carbon chemistry and isotopes in tufa depositing groundwaters of southwestern Japan

Annually laminated carbonates, known as tufas, commonly develop in limestone areas and typically record seasonal patterns of oxygen- and carbon-isotope compositions. δ¹⁸O values are principally controlled by seasonal changes of water temperature, whereas δ¹³C values are the result of complex reactions among the gaseous, liquid, and solid sources of carbon in the system. We examined the processes that cause the seasonal patterns of δ¹³C in groundwater systems at three tufa-depositing sites in southwestern Japan by applying model calculations to geochemical data. Underground inorganic carbon species are exchanged with gaseous CO₂, which is mainly introduced to the underground hydrological system by natural atmospheric ventilation and by diffusion of soil air. These processes control the seasonal pattern of δ¹³C, which is low in summer and high in winter. Among the three sites we investigated, we identified two extreme cases of the degree of carbon exchange between liquid and gaseous phases. For the case with high radiocarbon composition (Δ¹⁴C) and low pCO₂, there was substantial carbon exchange because of a large contribution of atmospheric CO₂ and a small water mass. For the other extreme case, which was characterized by low Δ¹⁴C and high pCO₂, the contribution of atmospheric CO₂ was small and the water mass was relatively large. Our results suggest that at two of the three sites water residence time within the soil profile was longer than 1 year. Our results also suggested a short residence time (less than 1 year) of water in the soil profile at the site with the smallest water mass, which is consistent with large seasonal amplitude of the springwater temperature variations. The Δ¹⁴C value of tufas is closely related to the hydrological conditions in which they are deposited. If the initial Δ¹⁴C value of a tufa-depositing system is stable, ¹⁴C-chronology can be used to date paleo-tufas.