Hydro-geochemical processes in an area with saline groundwater in lower Shire River valley, Malawi: An integrated application of hierarchical cluster and principal component analyses

Our ability to adapt to changes in groundwater quality, arising from a changing climate and/or local pressures, is dependent on comprehension of the governing controls of spatial variation in groundwater chemistry. This paper presents results of an assessment of dominant hydro-geochemical processes controlling groundwater chemical composition, using an integrated application of hierarchical cluster analysis (HCA) and principal component analysis (PCA) of a major ion dataset of groundwater from lower Shire River valley, Malawi. The area is in the southernmost part of the western section of the East African Rift System (EARS) and has localised occurrence of saline groundwater. HCA classified samples into three main clusters (C1-C3) according to their dominant chemical composition: C1 (dominant composition: Na-Cl; median TDS: 3436 mg L⁻¹), C2 (dominant composition: Na-HCO₃; median TDS: 966 mg L⁻¹) and C3 (dominant composition: alkali earths-HCO₃; median TDS: 528 mg L⁻¹). These clusters were in turn described by the principal components PC1, PC3 and PC2, respectively, resulting from the PCA. The results of the PCA and geochemical interpretation suggest that the spatial variation of groundwater quality in the area is influenced by the following processes: C3 samples result mainly from H₂CO₃ weathering of aluminosilicate minerals by percolating water supersaturated with CO₂. In addition to aluminosilicate weathering, C2 samples are influenced by the processes of cation exchange of Ca²⁺ and Mg²⁺ in the water for Na⁺ on clay minerals, and carbonate precipitation. The increase in ionic strength of C2 samples is attributed to mixing with high TDS groundwater in proximity with C2 samples. The saline/brackish C1 groundwater results from the processes of evaporation (for samples with high water table close to the Shire marshes) and dissolution of Cl⁻ and SO₄-evaporative salts followed by mineralised seep from sedimentary Karoo and Cretaceous Lupata sandstones.     

Neoproterozoic contaminated MORB of Wadi Ghadir ophiolite,NE Africa: Geochemical and Nd and Sr isotopic constraints

The ophiolitic metabasalts (pillowed and sheeted dikes) of Wadi Ghadir area, Eastern Desert, Egypt, were analyzed for their major, trace and rare earth elements, Nd and Sr isotopes and the chemistry of their plagioclase, amphibole and chlorite was also reported. Geochemically these rocks range from tholeiitic basalt to basaltic andesite. The generally low MgO, Cr and Ni and high Zr contents are consistent with derivation of these rocks from an evolved magma. The high TiO₂ contents (mostly between 1.76% and 2.23%) classify Wadi Ghadir ophiolitic metabasalts as MORB ophiolite. The chondrite-normalized REE patterns of most samples display small LREE-enrichment with (La/Yb)_n ranging from 1.44 to 2.56. The MORB-normalized spider diagram shows variable LILE abundances, which are either similar to or enriched relative to MORB, and most samples display small Nb depletion. The abundances of some LILE (Ba, Rb and K) as well as Na and Si were modified by post-magmatic seafloor hydrothermal alteration. Enrichment of the least mobile LILE (Th & U) indicates that Wadi Ghadir ophiolitic metabasalts are akin to C (contaminated)-MORB. These geochemical characteristics are similar to BABB modified by contamination.Wadi Ghadir metabasalts have low initial Sr ratios (0.7010–0.7034) which are similar to those of MORB, while their ε_Nd(t) values (+7.7–+4.5) are either more or less positive than the value of depleted mantle (DM). The more positive ε_Nd(t) values indicate DM source for these basalts, while the less positive ε_Nd(t) values reflect the involvement of slightly older component in Wadi Ghadir ophiolite. We suggest that the parent magma of metabasalts was contaminated by slightly older material, most probably oceanic-arc crustal rocks, which caused enrichment in LREE, and by analogy LILE, but did not significantly affect Nd isotopic systematics or modify Sr isotopes.Such contaminated MORB character also revealed by other ophiolitic metavolcanics in the Central Eastern Desert, contrasting the N-MORB character of the Gerf ophiolite in the South Eastern Desert. Moreover, the present work suggests the increase of the degree of contamination of the ophiolitic metabasalts from south to north in the Central Eastern Desert.     

A solution for the transition zone isosats in two-phase primary drainage in the presence of gravity

Primary drainage in a water-wet saturated medium in the absence of capillarity is typically a combination of shock (discontinuous) and rarefaction (continuous) waves. Using nonlinear relative permeability functions for the host fluid and the invading fluid leads to the existence of a shock wave front, and the degree of nonlinearity of the relative permeability functions has an inverse relationship with the size of the shock wave (i.e., difference of saturation between upstream and downstream of the shock wave), whereas for linear relative permeability functions, the shock wave size approaches 0. Injection of a lower-viscosity immiscible phase such as gas or solvent into a water-wet porous medium in the presence of large capillary pressure leads to development of an extended and growing saturation transition zone that follows the discontinuous shock wave front. In this article, a semianalytical solution for the position of equisaturation contours (isosats) in the transition zone in the presence of gravity is obtained for a set of linearized relative permeability functions. The capillary (diffusive) and buoyancy terms are neglected, and the generalized convective equation for mass conservation is obtained. The set of equations is then reduced to a one-dimensional steady-state differential equation through forcing the isosat formulation to obey mass conservation. This scheme allows the isosat distribution to be solved, and the case of injection into an axisymmetric geometry for a confined planar configuration is solved and presented. A finite element model was developed to demonstrate the reasonable agreement between analytical and numerical solutions.     

Expression of the Early Toarcian negative carbon-isotope excursion in separated carbonate microfractions (Jurassic,Paris Basin)

The causes of the pronounced negative excursion in carbon-isotope values that was recorded during the Early Toarcian Oceanic Anoxic Event (T-OAE) are still under debate, particularly with regard to the local versus global pattern of the excursion, and the extent to which recorded signals are under a diagenetic control. In this study we employ a novel microseparation technique in order to investigate the isotopic and mineralogical characteristics of different size fractions of the carbonate content from a Toarcian section recovered from the Sancerre–Couy borehole, southern Paris Basin. Beyond the recognition of a ? 6‰ δ¹³C excursion in the bulk carbonate content, our data also demonstrate that biogenic particles (such as coccoliths) and inorganic grains precipitated as early diagenetic phases (including dolomite) both record the excursion with the same magnitude. Although several black shales occur through the Paris Basin Toarcian section, it is only that associated with the onset of the OAE that coincides with a large negative carbon-isotope excursion. Taken together these observations indicate that during this event, the entire water column was characterized by homogeneous carbon-isotope values; such a pattern is incompatible with the idea that the negative excursion was generated simply through the upwelling of bottom waters enriched in re-mineralized organic carbon (cf. “the Küspert model”), since this would have required a strong vertical gradient in the water column. Additionally, the Paris Basin data show that the decrease in carbonate δ¹³C values during the OAE occurred in several discrete steps (each of some ? 2‰), as has previously been found for organic carbon substrates in other European sections. The stepped nature of the isotopic profile, which is part of a stratigraphic signature previously ascribed to Milankovitch forcing, is compatible with regular pulsed input of light carbon into the whole atmosphere–ocean system from a climatically sensitive source such as gas hydrate, or from thermal methanogenesis of organic-rich sediments in the Karoo–Ferrar large igneous province. Contrasts in the amplitude of the negative carbon-isotope excursion on a regional scale remain an important unexplained aspect of the Toarcian record.     

Inclusion of ice cover in a storm surge model for the Beaufort Sea

Storm surges in the Beaufort Sea present a severe problem for navigation as well as for offshore oil drilling activities. Influence of ice cover on storm surges in the Beaufort Sea is examined making use of a numerical model as well as a set of observations.The automated shallow-water model of Henry has been modified to incorporate ice cover and is adapted to the Beaufort Sea. The leading edge of the permanent ice is calculated from the loci of identifiable points. Generalized similarity theory is employed to compute wind stresses. Simulations are made using model-predicted ice concentrations and observed ice concentrations. Ice motion is relatively small in units of model grid distance (approximately 18 km) during surges. Spherical effects are important and should be included in future adaptations of the model. Comparison of the computed surges with observed surges for eight different events showed reasonable agreement.     

A new approach to simulating disorder in crystals

The technique of calculating lattice dissociation energies using static, minimum lattice energy, ionic models has been extended to allow for multiple occupancy of the ionic sites. A particular lattice site can have a fraction x of an ionic species A and a fraction y of an ionic species B, where the position of each can be relaxed separately along with the unit cell dimensions until an equilibrium is reached. Various degrees of long and short range order can be modelled. This technique has been applied to the mineral sillimanite, Al₂SiO₅, to calculate the effect on the lattice energy of (Al, Si) ordering over the tetrahedral sites. It is found using this method that (Al, Si) ordering with space group Pbmn stabilizes the material by 29.25 kcal/mol (Al^iv-O-Al^iv), with respect to the completely disordered material.     

A review of dimethylsulfoxide in aquatic environments

Abstract

Dimethylsulfoxide (DMSO) is an ubiquitous, albeit poorly understood, component of the marine sulfur cycle. Conventionally, the accepted formation pathways are the photochemical and microbial oxidation of dimethylsulfide (DMS). The principal loss mechanism is thought to be via microbial transformation, either consumption or reduction to DMS. The interactions between DMSO and DMS are likely to be important in controlling sea surface concentrations of DMS, and thus DMSO could influence the role played by DMS in global climate regulation. This review examines current knowledge of the distribution of DMSO in aquatic environments and the possible link between DMSO, DMS and global climate control. Mechanisms for the formation and loss of DMSO are also considered in addition to some of the factors influencing these processes. The review also considers that DMSO may be biosynthesized by phytoplankton, representing a non‐DMS source for DMSO, and that DMSO can undergo photochemical oxidation, a potential loss mechanism for DMSO in the marine environment.     

A note on the effects of virtual temperature: Research note

Abstract

The effects of virtual temperature on parcel buoyancy are investigated and the following results obtained. For descent or unsaturated ascent, the buoyancy acceleration is enhanced if the mixing ratio increases with pressure. However, for saturated ascent, the buoyancy acceleration is inhibited unless the lapse rate of mixing ratio exceeds a value slightly greater than that along a moist adiabat. This criterion is evaluated for several mean soundings. For the case of Oklahoma supercells, the mixing ratio lapse rate is clearly large enough. However, for other cases it often is not. Horizontal gradients in water vapour and condensed water can have a significant influence on the thermal wind.     

Simplified analytical solution for point load acting behind a cantilever wall

The analysis of earth pressure resulting from an applied point load behind a retaining wall is to be carried out in three dimensions as the earth pressure distribution varies both in vertical and horizontal directions. In this research, the semi‐empirical expressions developed by Terzaghi [Trans. ASCE 1954; 119 ] for earth pressure due to point load are integrated and a correction factor is introduced to develop equivalent equations for two‐dimensional analyses. A new parameter referred to as the design width, which is the horizontal distance retained by the individual vertical retaining element is introduced. The used procedure and the resulted equations are tested and verified by adopting different design width values covering the practical range. The resulted equations together with the semi‐empirical expressions of earth pressure due to line load developed by Terzaghi [Trans. ASCE 1954; 119 ] can be easily used for two‐dimensional analysis of the effect of point load. Copyright © 2011 John Wiley & Sons, Ltd.     

Enriched crustal and mantle components and the role of the lithosphere in generating Paleoproterozoic dyke swarms of the Ungava Peninsula,Canada

Paleoproterozoic mafic dyke swarms (2.5–2.0 Ga) of the Ungava Peninsula can be divided in three chemical groups. The main group has a wide range of Fe (10–18 wt.% Fe₂O₃) and Ti (0.8–2.0 wt.% TiO₂) contents, and the most magnesian samples have compositions consistent with melting of a fertile lherzolitic mantle at ~ 1.5 GPa. Dykes of a low-LREE (light rare earth element) subgroup (La/Yb ≤ 4) display decreasing Zr/Nb with increasing La/Yb ratios and positive εNd_2.0 Ga values (+ 3.9 to + 0.2) that trend from primitive mantle towards the composition of Paleoproterozoic alkaline rocks. In contrast, dykes of a high-LREE subgroup (La/Yb ≥4) display increasing Zr/Nb ratios and negative εNd_2.0 Ga values (? 2.3 to ? 6.4) that trend towards the composition of Archean crust. A low Fe–Ti group has low Fe (< 11 wt.% Fe₂O₃), Ti (< 0.8 wt.% TiO₂), high field strength elements (HFSE; < 6 ppm Nb) and heavy rare earth elements (HREE; < 2 ppm Yb) contents, but are enriched in large ion lithophile elements (LILE; K/Ti = 0.7–3) and LREE (La/Yb > 4). These dykes are interpreted as melts of a depleted harzburgitic mantle that has experienced metasomatic enrichment. A positive correlation of Zr/Nb ratio and La/Yb ratio, negative εNd_2.0 Ga values (? 14 to ? 6), and the presence of inherited Archean zircons further suggest the incorporation of a crustal component. A high Fe–Ti group has high Fe (> 14 wt.% Fe₂O₃) and Ti (> 1.4 wt.% TiO₂) contents, along with higher Na contents relative to the main group dykes. Dykes of a high-Al subgroup (> 12 wt.% Al₂O₃) share Fe contents, εNd_2.0 Ga values (? 2.3 to ? 3.4), La/Yb and Th/Nb ratios with Archean ferropicrites, and may represent evolved ferropicrite melts. A low-Al subgroup (< 12 wt.% Al₂O₃) has relatively lower Yb contents (< 2 ppm) and fractionated HREE patterns that indicate the presence of garnet in their melting residue. A comparison with ~ 5 GPa experimentally-derived melts suggests that these dykes may be derived from garnet-bearing pyroxenite or peridotite. The εNd_2.0 Ga values (? 0.3 to ? 2.0) of these dykes lie between the compositions of Archean granitoids and Paleoproterozoic alkaline rocks, signifying their petrogenesis involved both crustal and mantle components.Paleoproterozoic dykes containing a crustal component occur within, or close to, an isotopically enriched Archean terrane (T_DM 4.3–3.1 Ga), whereas dykes without this component occur in an isotopically juvenile terrane (T_DM < 3.1 Ga). The lack of a crustal component and the positive εNd_2.0 Ga values of dykes intruding the latter suggest that the crust they intruded was either too cold to be assimilated, or that its lower crust and/or lithosphere were Paleoproterozoic in age. In contrast, the ubiquitous presence of a crustal component and the diversity of mantle sources for dykes intruding the enriched terrane (lherzolite, harzburgite, pyroxenite) suggest a warmer crust with underlying heterogeneous lithospheric mantle.