Assessment of the likely sensitivity to climate change for the key marine species in the southern Benguela system

Climate change is altering many environmental parameters of coastal waters and open oceans, leading to substantial present-day and projected changes in the distribution, abundance and phenology of marine species. Attempts to assess how each species might respond to climate change can be data-, resource- and time-intensive. Moreover, in many regions of the world, including South Africa, species may be of vital socioeconomic or ecological importance though critical gaps may exist in our basic biological or ecological knowledge of the species. Here, we adapt and apply a trait-based sensitivity assessment for the key marine species in the southern Benguela system to estimate their potential relative sensitivity to the impacts of climate change. For our analysis, 40 priority species were selected based on their socioeconomic, ecological and/or recreational importance in the system. An extensive literature review and consultation with experts was undertaken concerning each species to gather information on their life history, habitat use and potential stressors. Fourteen attributes were used to estimate the selected species’ sensitivity and capacity to respond to climate change. A score ranging from low to high sensitivity was given for each attribute, based on the available information. Similarly, a score was assigned to the type and quality of information used to score each particular attribute, allowing an assessment of data-quality inputs for each species. The analysis identified the white steenbras Lithognathus lithognathus, soupfin shark Galeorhinus galeus, St Joseph Callorhinchus capensis and abalone Haliotis midae as potentially the most sensitive species to climate-change impacts in the southern Benguela system. There were data gaps for larval dispersal and settlement and metamorphosis cues for most of the evaluated species. Our results can be used by resource managers to determine the type of monitoring, intervention and planning that may be required to best respond to climate change, given the limited resources and significant knowledge gaps in many cases.     

Cation sorption on the muscovite (0 0 1) surface in chloride solutions using high-resolution X-ray reflectivity

The structure and mechanism of cation sorption at the (0 0 1) muscovite-water interface were investigated in 0.01 and 0.5 m KCl, CsCl, and CaCl₂ and 0.01 m BaCl₂ solutions at slightly acidic pH by high-resolution X-ray reflectivity. Structural relaxations of atom positions in the 2M₁ muscovite were small (?0.07 Å) and occurred over a distance of 30 to 40 Å perpendicular to the interface. Cations in all solutions were sorbed dominantly in the first and second solution layers adjacent to the mineral surface. The derived heights of the first solution layer in KCl and CsCl solutions, 1.67(6)-1.77(7) and 2.15(9)-2.16(2) Å, respectively, differ in magnitude by the approximate difference in crystallographic radii between K and Cs, and correspond closely to the interlayer cation positions in bulk K- and Cs-mica structures. The first solution layer heights in CaCl₂ and BaCl₂ solutions, 2.46(5)-2.56(11) and 2.02(5) Å, respectively, differ in a sense opposite to that expected based on crystallographic or hydrated radii of the divalent cations. The derived ion heights in all solutions imply that there is no intercalated water layer between the first solution layer and the muscovite surface. Molecular compositions were assigned to the first two solution layers in the electron density profiles using models that constrain the number density of sorbed cations, water molecules, and anions by considering the permanent negative charge of the muscovite and average solution density. The models result in partial charge balance (at least 50%) by cations sorbed in the first two layers in the 0.01 m solutions and approximately full charge balance in the 0.5 m solutions. Damped oscillations of model water density away from the first two solution layers agree with previous X-ray reflectivity results on the muscovite (0 0 1) surface in pure water.     

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.     

Structure of hydrated Zn at the rutile TiO2 (110)-aqueous solution interface: Comparison of X-ray standing wave, X-ray absorption spectroscopy, and density functional theory results

Adsorption of Zn²⁺ at the rutile TiO₂ (110)-aqueous interface was studied with Bragg-reflection X-ray standing waves (XSW), polarization-dependent surface extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) calculations to understand the interrelated issues of adsorption site, its occupancy, ion-oxygen coordination and hydrolysis. At pH 8, Zn²⁺ was found to adsorb as an inner-sphere complex at two different sites, i.e., monodentate above the bridging O site and bidentate between two neighboring terminal O sites. EXAFS results directly revealed a four or fivefold first shell coordination environment for adsorbed Zn²⁺ instead of the sixfold coordination found for aqueous species at this pH. DFT calculations confirmed the energetic stability of a lower coordination environment for the adsorbed species and revealed that the change to this coordination environment is correlated with the hydrolysis of adsorbed Zn²⁺. In addition, the derived adsorption locations and the occupancy factors of both sites from three methods agree well, with some quantitative discrepancies in the minor site location among the XSW, EXAFS, and DFT methods. Additional XSW measurements showed that the adsorption sites of Zn²⁺ were unchanged at pH 6. However, the Zn²⁺ partitioning between the two sites changed substantially, with an almost equal distribution between the two types of sites at pH 6 compared to predominantly monodentate occupation at pH 8.     

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.     

Structures of quartz (100)- and (101)-water interfaces determined by x-ray reflectivity and atomic force microscopy of natural growth surfaces

The structures of prismatic (100) and pyramidal (101) growth faces of natural quartz crystals, and their modification upon annealing at T ≤ 400°C were investigated ex situ by atomic force microscopy (AFM) and in water by high-resolution X-ray reflectivity. AFM images revealed the presence of ∼ 0.1 to 1 μm-wide flat terraces delimited by steps of one to several unit cells in height. These steps follow approximately directions given by the intersection of growth faces. Modeling of X-ray reflectivity data indicates that surface silica groups on flat terraces have only one free Si-O bond each (presumably hydroxylated), except for some having two free Si-O bonds observed on a single (100) surface. Vertical relaxation of atomic positions (< 0.4 Å for terminal oxygens and < 0.2 Å for silicon and oxygen atoms fully coordinated to structural tetrahedra) is limited to a depth of 14 Å. Electron density profiles for all measured interfaces are consistent with a single layer of adsorbed water, with no evidence for additional organization of water molecules into distinct layers extending into the bulk solution. Similar interfacial structures were observed for natural and annealed surfaces of identical crystallographic orientation, indicating that extensive reconstruction of the silica network at the quartz surface did not occur under the annealing conditions.     

The hydrothermal system of Volcan Puracé, Colombia

This paper presents chemical and isotopic data for thermal waters, gases and S deposits from Volcan Puracé (summit elevation 4600 m) in SW Colombia. Hot gas discharges from fumaroles in and around the summit crater, and thermal waters discharge from three areas on its flanks. The waters from all areas have D values of-75±1, indicating a single recharge area at high elevation on the volcano. Aircorrected values of³He/⁴He in thermal waters range from 3.8 to 6.7 R_A, and approach those for crater fumarole gas (6.1–7.1 R_A), indicating widespread addition of magmatic volatiles. An economic S deposit (El Vinagre) is being mined in the Rio Vinagre fault zone at 3600 m elevation. Sulfur isotopic data are consistent with a magmatic origin for S species in thermal waters and gases, and for the S ore deposit. Isotopic equilibration between S species may have occurred at 220±40°C, which overlaps possible equilibration temperatures (170±40°C) determined by a variety of other geothermometers for neutral thermal waters. Apparent CH₄–CO₂ equilibration temperatures for gases from thermal springs (400±50°C) and crater fumaroles (520±60°C) reflect higher temperatures deeper in the system. Hot magmatic gas ascending through the Rio Vinagre fault zone is though to have precipitated S and generated thermal waters by interaction with descending meteoric waters.     

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.     

Origin of low-18O metamorphic rocks from a Late Proterozoic shear zone in the Eastern Desert of Egypt

Anomalously low and variable ¹⁸O/¹⁶O ratios (whole rock ¹⁸O_SMOW=–1.9 to +6.0) have been measured in several Late Proterozoic metamorphic units associated with a large scale low-angle ductile shear zone at Meatiq Dome in the central Eastern Desert of Egypt. The low-¹⁸O units consist of granite gneiss, quartzofeldspathic mylonite, and quartz phyllonite. These are intruded by syntectonic diorite-tonalite-granodiorite and post-tectonic granite, both having normal ¹⁸O. No evidence for other low-¹⁸O country rock units has been found. Oxygen isotope fractionation between quartz and magnetite in the granite gneiss ( _QZ-MT=8.0 to 9.3) is consistent with equilibration at amphibolite grade temperatures, suggesting that ¹⁸O depletion occurred prior to metamorphism. Whole rock geochemical analyses indicate that the low-¹⁸O units were derived from two granitic protoliths, one of which apparently underwent local sericitic alteration prior to metamorphism; it is proposed that ¹⁸O depletion and sericitic alteration occurred simultaneously in a high-temperature meteorichydrothermal system associated with emplacement of these granitic protoliths. The relatively high ductility of the sericitically altered rock may have been an important factor in the subsequent localization of the shear zone.