Surface complexation effects on phosphate adsorption to ferric iron oxyhydroxides along pH and salinity gradients in estuaries and coastal aquifers

Non-conservative behavior of dissolved inorganic phosphate (DIP) in estuaries is generally ascribed to desorption from iron and aluminum (hydr)oxides with increasing salinity. Here, we assess this hypothesis by simulating the reversible adsorption of phosphate onto a model oxide (goethite) along physico-chemical gradients representative of surface and subsurface estuaries. The simulations are carried out using a surface complexation model (SCM), which represents the main aqueous speciation and adsorption reactions of DIP, plus the ionic strength-dependent coulombic interactions in solution and at the mineral-solution interface. According to the model calculations, variations in pH and salinity alone are unlikely to explain the often reported production of DIP in surface estuaries. In particular, increased aqueous complexation of phosphate by Mg²⁺ and Ca²⁺ ions with increasing salinity is offset by the formation of ternary Mg-phosphate surface complexes and the drop in electrical potential at the mineral-water interface. However, when taking into account the downstream decrease in the abundance of sorption sites, the model correctly simulates the observed release of DIP in the Scheldt estuary. The sharp increase in pH accompanying the admixing of seawater to fresh groundwater should also cause desorption of phosphate from iron oxyhydroxides during seawater intrusion in coastal aquifers. As for surface estuaries, the model calculations indicate that significant DIP release additionally requires a reduction in the phosphate sorption site density. In anoxic aquifers, this can result from the supply of seawater sulfate and the subsequent reductive dissolution of iron oxyhydroxides coupled to microbial sulfate reduction.     

Geochemical characterization of surface waters and groundwater resources in the Managua area (Nicaragua,Central America)

This paper reports new geochemical data on dissolved major and minor constituents in surface waters and ground waters collected in the Managua region (Nicaragua), and provides a preliminary characterization of the hydrogeochemical processes governing the natural water evolution in this area. The peculiar geological features of the study site, an active tectonic region (Nicaragua Depression) characterized by active volcanism and thermalism, combined with significant anthropogenic pressure, contribute to a complex evolution of water chemistry, which results from the simultaneous action of several geochemical processes such as evaporation, rock leaching, mixing with saline brines of natural or anthropogenic origin. The effect of active thermalism on both surface waters (e.g., saline volcanic lakes) and groundwaters, as a result of mixing with variable proportions of hyper-saline geothermal Na–Cl brines (e.g., Momotombo geothermal plant), accounts for the high salinities and high concentrations of many environmentally-relevant trace elements (As, B, Fe and Mn) in the waters. At the same time the active extensional tectonics of the Managua area favour the interaction with acidic, reduced thermal fluids, followed by extensive leaching of the host rock and the groundwater release of toxic metals (e.g., Ni, Cu). The significant pollution in the area, deriving principally from urban and industrial waste-water, probably also contributes to the aquatic cycling of many trace elements, which attain concentrations above the WHO recommended limits for the elements Ni (∼40 μg/l) and Cu (∼10 μg/l) limiting the potential utilisation of Lake Xolotlan for nearby Managua.     

Structural investigation of the synthetic CaAn(PO4)2 (An = Th and Np) cheralite-like phosphates

The crystallographic structures of the synthetic cheralite, CaTh(PO₄)₂, and its homolog CaNp(PO₄)₂ have been investigated by X-ray diffraction at room temperature. Rietveld analyses showed that both compounds crystallize in the monoclinic system and are isostructural to monazite LnPO₄ (Ln = La to Gd). The space group is P2₁/n (I.T. = 14) with Z = 2. The refined lattice parameters of CaTh(PO₄)₂ are a = 6.7085(8) Å, b = 6.9160(6) Å, c = 6.4152(6) Å, and β = 103.71(1)° with best fit parameters R _wp = 4.87%, R _p = 3.69% and R _B = 3.99%. For CaNp(PO₄)₂, we obtained a = 6.6509(5) Å, b = 6.8390(3) Å, c = 6.3537(8) Å, and β = 104.12(6)° and R _wp = 6.74%, R _p = 5.23%, and R _B = 6.05%. The results indicate significant distortions of bond length and angles of the PO₄ tetrahedra in CaTh(PO₄)₂ and to a lesser extent in CaNp(PO₄)₂. The structural distortions were confirmed by Raman spectroscopy of CaTh(PO₄)₂. A comparison with the isostructural compounds LnPO₄ (Ln = Ce and Sm) confirmed that the substitution of the large rare earth trivalent cations with Ca²⁺ and Th⁴⁺ introduces a distortion of the PO₄ tetrahedra.     

Evolution of the Axial Geometry of the Southwest Indian Ocean Ridge between the Melville Fracture Zone and the Indian Ocean Triple Junction – Implications for Segmentation on Very Slow-Spreading Ridges

Geophysical data from 900 km of the Southwest Indian Ridge are used todescribe the pattern of evolution of the plate boundary between 61° Eand 70° E over the past 20 million years. The SWIR is anobliquely-opening, ultra slow-spreading axis, and east of61° E comprises a series of ridge sections, each about 100–120 kmin length. The orientation of these sections varies fromsub-orthogonal to oblique to the approximately N–S spreadingdirection. In general, the suborthogonal sections are shallower, commonlysubdivided into an array of discrete axial segments, and carry recognisablecentral magnetic anomalies. The majority of the oblique sections are single,continuous rifts without continuous axial magnetic signatures.Morphotectonics of the Southwest Indian Ridge crust have not previously beenwell constrained off-axis, and we here present sidescan sonar andswath bathymetric data up to 100 km from the ridge to demonstrate the complexities of its spatial and temporal evolution.A model is proposed that the segmentation style correlates with analong-axis variation between: (a) relatively thick crustal sections which overlie mantle sections with higher magmatic supply created in orthogonally-spreading segments and (b) those oblique sections associated with cooler, magmatically-starved mantle and thinner crust. These latter sections are formed at broad offset zones in theplate boundary, more precisely defined on faster-spreading ridges asnontransform discontinuities. The nonsystematic pattern of crustalconstruction, extensional basin formation and the absence of extension-parallel traces of discontinuities off-axis suggest that the oblique spreading sections are not fixed in space or time.     

Preliminary attempt to characterize the rotation of seafloor in the Pito Deep area of the Easter Microplate using a submersible magnetometer

Several mechanisms have been proposed to account for the rotation of the nearly north-south abyssal hill fabric formed on the East Pacific Rise north of the Easter Microplate to the nearly east-west trends in the northern microplate interior. Proposed mechanisms include rigid microplate rotation, transform fault – parallel shear, and bookshelf faulting during the transfer of lithosphere from the Nazca Plate to the microplate. We used a submersible magnetometer on a NAUTILE dive program to measure the magnetic vector rotation of a pillow basalt and dike spur near Pito Deep, the present location of the tip of the propagating rift system that created the microplate. Our results, although too limited to draw strong conclusions from, suggest clockwise rotations of the seafloor magnetic vectors inconsistent with the transform-parallel shear model, and larger than can be explained solely by rigid microplate rotation.     

Active spreading and hydrothermalism in North Fiji Basin (SW Pacific). Results of Japanese French Cruise Kaiyo 87

The aim of the Japanese-French Kaiyo 87 cruise was the study of the spreading axis in the North Fiji Basin (SW Pacific). A Seabeam and geophysical survey allowed us to define the detailed structure of the active NS spreading axis between 16° and 22° S and its relationships with the left lateral motion of the North Fiji Fracture Zone. Between 21° S and 18°10′ S, the spreading axis trends NS. From 18°10 S to 16°40 S the orientation of the spreading axis changes from NS to 015°. North of 16°40′ S the spreading axis trends 160°. These two 015° and 160° branches converge with the left lateral North Fiji fracture zone around 16°40′ S to define an RRFZ triple junction. Water sampling, dredging and photo TV deep towing give new information concerning the hydrothermal activity along the spreading axis. The discovery of hydrothermal deposits associated with living communities confirms this activity.     

Distribution and transfer of trace elements in the Western Mediterranean

Results concerning the concentration of cadmium and lead in Mediterranean waters collected during the 2nd PHYCEMED cruise (Oct. 1983) are discussed. Sampling has been performed at seven stations in the Western Mediterranean Basin, two in the Strait of Gibraltar and the near Atlantic, two in the Sicily Strait and the Eastern Basin.In the Western Basin the observations are in fair agreement with those of PHYCEMED 1. Cadmium has a fairly homogeneous distribution vertically as well as from one station to another, with an average concentration of 8 ng l⁻¹; while lead shows a slight but continuous decrease in concentrations with depth (from at least 50 ng l⁻¹ in surface waters to 20 or 25 ng l⁻¹ at depth). On the other hand, at the basin boundaries, where waters from different origins are present, vertical distributions appear very different. On the basis of calculated water budgets it can be estimated that the Mediterranean Sea discharges about 200 t y⁻¹ of cadmium and about 250 t y⁻¹ of lead into the Atlantic Ocean while 1000 t y⁻¹ of lead are transferred from the Western to the Eastern Basin.