Paleoclimate record in the Nubian Sandstone Aquifer,Sinai Peninsula,Egypt

Sixteen groundwater samples collected from production wells tapping Lower Cretaceous Nubian Sandstone and fractured basement aquifers in Sinai were analyzed for their stable isotopic compositions, dissolved noble gas concentrations (recharge temperatures), tritium activities, and ¹⁴C abundances. Results define two groups of samples: Group I has older ages, lower recharge temperatures, and depleted isotopic compositions (adjusted ¹⁴C model age: 24,000–31,000 yr BP; δ¹⁸O: − 9.59‰ to − 6.53‰; δ²H: − 72.9‰ to − 42.9‰; < 1 TU; and recharge T: 17.5–22.0°C) compared to Group II (adjusted ¹⁴C model age: 700–4700 yr BP; δ¹⁸O: − 5.89‰ to − 4.84‰; δ²H: − 34.5‰ to − 24.1‰; < 1 to 2.78 TU; and recharge T: 20.6–26.2°C). Group II samples have isotopic compositions similar to those of average modern rainfall, with larger d-excess values than Group I waters, and locally measurable tritium activity (up to 2.8 TU). These observations are consistent with (1) the Nubian Aquifer being largely recharged prior to and/or during the Last Glacial Maximum (represented by Group I), possibly through the intensification of paleowesterlies; and (2) continued sporadic recharge during the relatively dry and warmer interglacial period (represented by Group II) under conditions similar to those of the present.     

The origin of small-scale geochemical and mineralogic variations in a granite intrusion

A post-tectonic unzoned granite intrusion in the Meatiq Dome, a Late Proterozoic metamorphic complex in the Central Eastern Desert of Egypt, shows significant chemical and mineralogic heterogeneity on the scale of sampling (5 kg). Whole rock analyses of 21 samples indicate small variations in SiO₂, Al₂O₃, Na₂O and K₂O, and larger systematic variations in the less abundant major elements such as FeO, TiO₂, CaO, MnO and MgO, and trace elements such as Sc, Cr, Co, Rb, Sr, Zr, La, Ce, Nd, Sm, Tb, Yb, Lu, Ta, Th and U. These variations cannot be accounted for by processes such as marginal accretion, assimilation, alteration by late stage fluids, or multiple intrusion. Instead, we proposed a model involving 35 percent solidification of the granite magma followed by partial solid-liquid segregation during emplacement, resulting in rocks containing 7–71 volume percent early-formed solids. Such randomly distributed local segregation could have been caused by filter pressing, flow differentiation, and possibly gravity segregation, either singly or in combination. Thus, each sample is interpreted as a mixture of two end-members with nearly constant compositions: an early-formed solid assemblage of crystals and a complementary residual liquid. Early formed solids are enriched in TiO₂, FeO, CaO, P₂O₅, Sc, Co, Cr, Sr, La, Ce and depleted in SiO₂, Rb, Yb, Lu, Ta, Th, and U, while the residual liquid has complementary enrichments and depletions. This simple mixing model is consistent with field and petrographic observations, experimental studies pertaining to the crystallization sequence in the system Ab-Or-Qtz-H₂O at 1 Kb, and physical properties of silicic magmas. Furthermore, it is quantitatively supported by trace-element data for minerals, computed endmember compositions at 35% crystallization using mineral analyses and reasonable Kd values, and internal consistency in the percent solid for each sample computed from each of 17 elements in the inferred end-members. We suggest that this model might also apply to other small epizonal granite intrusions that show small-scale chemical heterogeneities.     

Structure of the orthoclase (001)- and (010)-water interfaces by high-resolution X-ray reflectivity

High-resolution in situ X-ray specular reflectivity was used to measure the structures of orthoclase (001) and (010) cleavage surfaces in contact with deionized water at 25°C. X-ray reflectivity data demonstrate a high degree of structural similarity between these two orthoclase-water interfaces. Both interfacial structures include cleavage along the plane of minimal bond breakage resulting in surfaces terminated by non-bridging oxygens; structured water within 5 Å of the orthoclase surface (consisting of adsorbed species at the surface and layered water above the surface), with a featureless water profile beyond 5 Å; substitution of outermost K⁺ ions by an oxygen containing species (presumably H₃O⁺); and small structural displacements of the near surface atoms. The interfacial water structure, in comparison with recent results for other mineral-water interfaces, is intermediate between the minimal structure found at calcite-, barite-, and quartz-water interfaces and the more extensive structure found at the muscovite-water interface.     

Structure and reactivity of the dolomite (104)-water interface: New insights into the dolomite problem

The structure and reactivity of the dolomite (104)-water interface was probed in situ with high resolution X-ray reflectivity and surface force microscopy at room temperature. Measurements in stoichiometric solutions alternating between saturated and supersaturated (log IAP/K = 2.3) conditions show that the dolomite surface termination readily changes in response to solution composition, but these changes are self-limiting and partially irreversible. The freshly cleaved dolomite (104) surface in contact with the saturated solution has a stoichiometric termination, a distinct surface hydration layer and small surface structural displacements, similar to those observed previously at the calcite-water interface. After reaction with supersaturated solutions dolomite is terminated by a two-layer thick Ca-rich film with substantial structural displacements of the cations. With subsequent exposure to a saturated solution this surface was transformed to an interfacial structure different from the freshly cleaved surface, having a reduced density of the outermost surface layer and a Ca-rich second layer. These results provide new insight into the lack of dolomite growth in modern carbonate environments (i.e., the “dolomite problem”), suggesting that this behavior is associated with a combination of thermodynamic and kinetic factors, including (1) growth of compositionally modified epitaxial Ca_XMg_2−X(CO₃)₂ layers having thicknesses limited by lattice strain, (2) slow incorporation of Mg during layer growth, and (3) partial irreversibility of surface reactions.     

Orthoclase dissolution kinetics probed by in situ X-ray reflectivity: effects of temperature, pH, and crystal orientation

Initial dissolution kinetics at orthoclase (001) and (010) cleavage surfaces were measured for ∼2 to 7 monolayers as a function of temperature using in situ X-ray reflectivity. The sensitivity of X-ray reflectivity to probe mineral dissolution is discussed, including the applicability of this approach for different dissolution processes and the range of dissolution rates (∼10⁻¹² to 10⁻⁶ mol/m²/sec) that can be measured. Measurements were performed at pH 12.9 for the (001) surface and at pH 1.1 for the (001) and (010) surfaces at temperatures between 46 and 83°C. Dissolution at pH 12.9 showed a temperature-invariant process with an apparent activation energy of 65 ± 7 kJ/mol for the (001) cleavage surface consistent with previous powder dissolution results. Dissolution at pH 1.1 of the (001) and (010) surfaces revealed a similar process for both surfaces, with apparent activation energies of 87 ± 7 and 41 ± 7 kJ/mol, respectively, but with systematic differences in the dissolution process as a function of temperature. Longer-term measurements (five monolayers) show that the initial rates reported here at acidic pH are greater than steady-state rates by a factor of 2. Apparent activation energies at acidic pH differ substantially from powder dissolution results for K-feldspar; the present results bracket the value derived from powder dissolution measurements. The difference in apparent activation energies for the (001) and (010) faces at pH 1.1 reveals an anisotropy in dissolution kinetics that depends strongly on temperature. Our results imply a projected ∼25-fold change in the ratio of dissolution rates for the (001) and (010) surfaces between 25 and 90°C. The dissolution rate of the (001) surface is higher than that of the (010) surface above 51°C and is projected to be lower below this temperature. These results indicate clearly that the kinetics and energetics of orthoclase dissolution at acidic pH depend on crystal orientation. This dependence may reflect the different manifestation of the Al-Si ordering between the T1 and T2 tetrahedral sites at these two crystal faces and can be rationalized in terms of recent theoretical models of mineral dissolution.     

Groundwater-derived contaminant fluxes along a channelized Coastal Plain stream

Recent studies in various settings across eastern North America have examined the movement of volatile organic compound (VOC) plumes from groundwater to streams, but few studies have addressed focused discharge of such plumes in unlithified sediments. From 1999 through 2002, we monitored concentrations of trichloroethene (TCE) and the non-volatile co-contaminant technetium-99 (⁹⁹Tc) along Little Bayou Creek, a first-order perennial stream in the Coastal Plain of western Kentucky. Spring flow contributed TCE and ⁹⁹Tc to the creek, and TCE concentrations tended to vary with ⁹⁹Tc in springs. Contaminant concentrations in stream water fluctuated seasonally, but not always synchronously with stream flow. However, contaminant influxes varied seasonally with stream flow and were dominated by a few springs. Concentrations of O₂, , and , values of δ³⁷Cl_DOCl in groundwater, and the lack of less-chlorinated ethenes in groundwater and stream water indicated that anaerobic biodegradation of TCE was unlikely. Losses of TCE along Little Bayou Creek resulted mainly from volatilization, in contrast to streams receiving diffuse contaminated discharge, where intrinsic bioremediation of VOCs appears to be prevalent.     

Metabolic activity throughout early development of dusky kob Argyrosomus japonicus (Sciaenidae)

The physiology of fishes in the early stages of development remains poorly assessed despite the importance of identifying energy bottlenecks in organisms faced with changing environmental conditions. This study describes the metabolic activity of dusky kob Argyrosomus japonicus throughout its early development, from hatchling to settlement stage. Standard, routine and active metabolic rates (SMR, RMR and AMR, respectively) were assessed to determine the species’ metabolic scope and identify how metabolism changes with growth and development. Distinct metabolic changes occurred in association with developmental changes during the early life stages, with flexion-stage larvae showing significantly reduced metabolic scope (approx. 0.30 µmol O₂ ind.^–1 h^–1), representing an energy bottleneck. Based on these findings, it is likely that larvae of A. japonicus are most susceptible to environmental perturbations during flexion. The variability of metabolic rates during the diel cycle was also assessed and revealed that the early-stage larvae showed no preference for daylight, although settlement-stage juveniles were more active during daylight hours (RMR = 12.78 µmol O₂ ind.^–1 h^–1) than at night (RMR = 5.87 µmol O₂ ind.^–1 h^–1). These results suggest that metabolic measurements of the SMR of A. japonicus larvae can be taken at any time of the diel cycle until the settlement phase, when readings should take place at night.