Dissolution and carbonation of a serpentinite: Inferences from acid attack and high P-T experiments performed in aqueous solutions at variable salinity

Dissolution experiments on a serpentinite were performed at 70 °C, 0.1 MPa, in H₂SO₄ solution, in open and closed systems, in order to evaluate the overall dissolution rate of mineral components over different times (4, 9 and 24 h). In addition, the serpentinite powder was reacted with a NaCl-bearing aqueous solution and supercritical CO₂ for 24 h at higher pressures (9-30 MPa) and temperatures (250-300 °C) either in a stirred reactor or in an externally-heated pressure vessel to assess both the dissolution rate of serpentinite minerals and the progress of the carbonation reaction. Results show that, at 0.1 MPa, MgO extraction from serpentinite ranges from 82% to 98% and dissolution rate varies from 8.5 × 10⁻¹⁰ mole m⁻² s⁻¹ to 4.2 × 10⁻⁹ mole m⁻² s⁻¹. Attempts to obtain carbonates from the Mg-rich solutions by increasing their pH failed since Mg- and NH₄- bearing sulfates promptly precipitated. On the other hand, at higher pressures, significant crystallization (5.0-10.4 wt%) of Ca- and Fe-bearing magnesite was accomplished at 30 MPa and 300 °C using 100 g L⁻¹ NaCl aqueous solutions. The corresponding amount of CO₂ sequestered by crystallization of carbonates is 9.4-15.9 mole%. Dissolution rate (from 6.3 × 10⁻¹¹ mole m⁻² s⁻¹ to 1.3 × 10⁻¹⁰ mole m⁻² s⁻¹) is lower than that obtained at 0.1 MPa and 70 °C but it is related to pH values much higher (3.3-4.4) than that (−0.65) calculated for the H₂SO₄ solution.Through a thorough review of previous experimental investigations on the dissolution kinetics of serpentine minerals the authors propose adopting: (i) the log rate [mole m⁻² s⁻¹] value of −12.08 ± 0.16 (1σ), as representative of the neutral dissolution mechanism at 25 °C and (ii) the following relationship for the acidic dissolution mechanism at 25 °C:

log rate=-0.45(±0.09)×pH-10.01(±0.30).     

Lagrangian model of zooplankton dispersion: numerical schemes comparisons and parameter sensitivity tests

This paper presents two comparisons or tests for a Lagrangian model of zooplankton dispersion:numerical schemes and time steps.Firstly,we compared three numerical schemes using idealized circulations.Results show that the precisions of the advanced Adams-Bashfold-Moulton(ABM) method and the Runge-Kutta(RK) method were in the same order and both were much higher than that of the Euler method.Furthermore,the advanced ABM method is more efficient than the RK method in computational memory requirements and time consumption.We therefore chose the advanced ABM method as the Lagrangian particle-tracking algorithm.Secondly,we performed a sensitivity test for time steps,using outputs of the hydrodynamic model,Symphonie.Results show that the time step choices depend on the fluid response time that is related to the spatial resolution of velocity fields.The method introduced by Oliveira et al.in 2002 is suitable for choosing time steps of Lagrangian particle-tracking models,at least when only considering advection.     

Spatial pattern of coastal fish assemblages in different habitats in North‐western Mediterranean

Variability of fish assemblages across habitat structures can depend on spatial scales. A hierarchical sampling design was used to assess the spatial variability of temperate fish assemblages in different habitats and at multiple scales. Underwater visual censuses were carried out along the coasts of Elba Island (NW Mediterranean) on Posidonia oceanica beds, rocky algal reefs and sandy habitat at three spatial scales, namely tens of metres (individual replicates), hundreds of metres (sites) and tens of kilometres (locations). At the assemblage level, there was a clear relationship between fish and habitat type and the observed habitat‐related differences were largely dependent on species identity. Fish assemblages on P. oceanica beds and rocky reefs shared a high number of species, whereas overlap with sandy assemblages was negligible. Multivariate analyses revealed significant differences in fish assemblages among habitats, although there was also a significant habitat × site interaction. These differences relied mainly upon assemblage composition and species richness. Assemblages on rocky reefs and P. oceanica meadows usually harboured a higher number of species and individuals compared with sandy assemblages. Nevertheless, the patterns of habitat‐related differences in species richness and, especially, in the total number of fish, changed significantly from site to site. Eight species showed significant differences over habitats, but they were not consistent due to the interaction of habitat with site. Predictability of fish at both assemblage and population levels decreased with the scale of observation, and the spatial pattern of fish observed at the smallest scale was likely dependent on factors other than habitat type.     

Deglaciation of the western margin of the Barents Sea Ice Sheet — A swath bathymetric and sub-bottom seismic study from the Kveithola Trough

Kveithola Trough, an E–W trending glacial trough in the NW Barents Sea, was surveyed for the first time during the EGLACOM cruise of R/V OGS-Explora in summer 2008. Swath bathymetry shows that the seafloor is characterized by E–W trending mega-scale glacial lineations (MSGL) that record a fast flowing ice stream draining the Svalbard/Barents Sea Ice Sheet (SBIS) during the Last Glacial Maximum (LGM). MSGL are overprinted by transverse sediment ridges about 15 km apart which give rise to a staircase axial profile of the trough. Such transverse ridges are interpreted to be grounding-zone wedges (GZWs) formed by deposition of subglacial till during episodic ice stream retreat. Sub-bottom (CHIRP) and multi-channel reflection seismic data show that the present-day morphology is largely inherited from the palaeo-seafloor topography at the time of deposition of the transverse ridges, overlain by a draping glaciomarine unit which in places is over 15 m thick. Our data allow the reconstruction of depositional processes which accompanied deglaciation of the Spitsbergen Bank area. The sedimentary drape deposited on top of the GZWs is suggested to have accumulated at a very high rate, (on average in the order of 1–1.5 m ka^?1) and therefore may potentially preserve a high-resolution palaeoclimatic record of deglaciation and post-glacial conditions in this sector of the Barents Sea.     

Sources,seasonal variability,and trajectories of atmospheric aerosols over central Siberian forest ecosystems

The possibility to obtain reliable data on the chemical and physical characteristics of aerosols and the regularities in the processes of their formation and transportation under the background natural-climatic conditions is a necessary requirement for verification of existing climate models [1, 2].     

Use of sedimentary pigments to infer past phosphorus concentration in lakes

We propose a palaeolimnological method for inferring past total phosphorus (TP) concentrations in lake water from spectrophotometrically-measured sedimentary pigments, particularly total carotenoids (TC). Our approach is based on a highly significant statistical correlation (P < 0.0001) between pigment concentrations (total carotenoids) in the surface sediment of 28 Italian lakes (subalpine, large, deep, shallow, volcanic) and TP concentrations measured in these lakes at overturn when the core was collected. A transfer function was developed from this “training” set, and used to estimate past TP concentrations from pigment concentrations in sediment cores. The results generally agreed with TP values as measured by long-term water quality monitoring programs. Contrasting results were obtained by a comparison with diatom-inferred TP. While the diatom model showed a tendency to overestimate TP values higher than 100 μg l⁻¹, the pigment model correctly estimated TP in lakes when TP was <100 μg l⁻¹, but not when lakes were rich in macrophytes. In fact, lakes with extensive populations of aquatic submersed macrophytes and epiphytes are outliers in terms of the TC versus TP relationship. The root mean square error of prediction of the pigment model is lower than those derived from certain diatom—based inference models. The predicted and residual values are not related to the estimated values and their average is not statistically different from zero. Errors were estimated via a ‘leave-one-out’ re-sampling technique. The proposed method permits rapid and relatively inexpensive determination of reference trophic conditions.     

Sensitivity of LAGEOS to changes in Earth's (2, 2) gravity coefficients

In recent years it has become of geophysical interest to detect a possible time variation of the low-degree coefficients of the Earth's gravity field, in particular the (2, 2) tesseral harmonic. We investigate the possibility of detecting such a phenomenon via analysis of the tracking data from LAGEOS, the passive geodynamics satellite tracked by laser stations on the ground. For this purpose the main problems are caused: (i) for short orbital arcs, by the irregular distribution in time of the tracking data, and by the dynamical effects of oceanic tides, which cannot be easily separated from the effects of geopotential changes; (ii) for long orbital arcs, by the difficulty of reliably predicting the variable drag-like force that is causing a slow semimajor axis decay. We estimate that a relative accuracy of the order of 10^–4 in the (2, 2) coefficients can be reached provided that a larger number of higher technology laser stations is available, and that better modelling is possible of the drag-like force. Both these conditions seem quite unrealistic at present. If a relative accuracy better than 10^–4 has to be reached, an effective separation of the tidal perturbations is also needed, since they give rise to perturbations with a similar signature.     

Evolution of mass-transfer during progressive oblique under-thrusting of the Variscan foreland: eastern Bohemian Massif

Abstract

Four ductile shear zones were sampled in the autochthonous Thaya basement and the Upper Bíte? nappe (Moravian unit) at the Eastern margin of the Bohemian massif. In both studied units, the tectono-metamorphic evolution and the chemical mass transfer are different. Two deformational events are recognised: the first deformation stage under amphibolite facies conditions is overprinted by a second event under greenschist facies conditions.

The first deformation affected the western margin of the Thaya basement and the whole Bíte? nappe: microstructures are characterised by dynamic recrystallisation of feldspars and quartz, and occurrence of myrmekites and grain-boundary migration of quartz. None or weak chemical mass transfer is related to this medium to high temperature deformation. This deformation corresponds to the thrusting of Moldanubdian units on the Brunovistulian units (Moravian nappes and autochthonous Thaya basement).

The second deformation generated shear zones in the until then preserved Thaya basement and reactivated both shear zones of the western margin of the Thaya basement and those of the Bíte? nappe. This deformation is retrograde and mainly associated with chemical mass transfer: a decrease of CaO, FeO, FeO/Fe₂O₃ and an increase of MgO, K₂O and H₂O. These chemical changes are related to greenschist metamorphic reactions leading to the destabilisation of feldspars and the crystallisation of white micas and Ca-silicates. The large chemical mass transfer is associated with the circulation of a large volume of fluids. A model of progressive fluid circulation correlated with Variscan prograde and retrograde metamorphism during the collision of Moldanubian and Brunovistulian units is proposed.     

Nickel-rich metasomatism of the lithospheric mantle by pre-kimberlitic alkali-S–Cl-rich C–O–H fluids

Metasomatism of the lithospheric mantle sometimes produces unusual assemblages containing native metals and alloys, which provide important insight into metasomatic processes in the mantle. In this study, we describe the metasomatic enrichment of a refractory harzburgite xenolith in Ni, Fe and, to a lesser extent, Cu, Co, As and Sb. The xenolith (XM1/422) derives from the Bultfontein kimberlite (Kimberley, South Africa) and hosts Ni mineralisation that includes native nickel (Ni_84.5-98.0), heazlewoodite (Ni₃S₂) and Ni-rich silicates (e.g. up to 37.5 wt % NiO in olivine, and 22.4 wt % NiO in phlogopite). The presence of several mineral phases enriched in alkali and volatile species (e.g. phlogopite, phosphates, carbonates, chlorides, djerfisherite) indicates that the transition metal cations were likely introduced during metasomatism by alkali-rich C–O–H fluids or alkali-carbonate melts. It is postulated that sulphide breakdown and fluid reaction with refractory mantle rocks contributed to the fluid’s enrichment in Ni and other metallic cations. The Ni-rich assemblages of xenolith XM1/422 show local chemical disequilibrium, and modelling of the Ni diffusion profiles adjacent to olivine-native nickel and olivine-heazlewoodite grain boundaries, suggests a close temporal relationship between Ni-rich metasomatism and subsequent entrainment by the kimberlite magma. However, metal-rich metasomatism has also been observed in other lithospheric mantle domains, including orogenic peridotitic massifs and the suboceanic mantle; regions unaffected by kimberlite magmatsim. As micro-scale occurrences of metallic phases are easily overlooked, it is possible that metal-rich metasomatism is more widespread in the Earth’s mantle than previously recognised.