The heptahydrate of sodium sulfate: Does it have a role in terrestrial and planetary geochemistry?

Sodium sulfate readily forms a metastable heptahydrate from concentrated aqueous solutions on cooling to around 10 °C. It crystallises much more easily than the well recognised and less soluble decahydrate (mirabilite), although the existence of the heptahydrate is almost entirely ignored in the geochemical literature on sodium sulfate. There is strong evidence that the heptahydrate is stable below a triple point temperature of −9.5 °C at low water vapour pressures, conditions which are found in cold dry environments such as the surface of Mars and the icy moons of Jupiter.     

Tidal currents and wind waves controlling sediment distribution in a subtidal point bar of the Venice Lagoon (Italy)

The present study aims to improve current understanding of the sedimentation of subtidal point bars, analyzing interaction between tidal currents and waves in shaping a submerged meander bend of the microtidal Venice Lagoon (Italy), and it is based on coupling of sedimentological studies, geophysical analyses and numerical modelling. The Venice Lagoon is characterized by an average depth of about 1·5 m over subtidal platforms and a mean tidal range of about 1·0 m. The morphodynamic evolution of the lagoon is strongly affected by intense seasonal windstorms, which promote the formation of wind waves triggering sediment resuspension and bottom erosion. The study channel is 70 to 100 m wide, it has a radius of curvature of about 260 m and cuts through a permanently submerged subtidal platform. Water depth ranges from 1·0 to 5·0 m below mean sea level on the subtidal platform and channel thalweg, respectively. Different from classical architectural models, the study point‐bar beds do not show sigmoidal geometries, but consist of horizontally‐bedded deposits abruptly overlying clinostratified beds. Sedimentation in the study bar is hypothesized to stem from the interaction between the in‐channel secondary helical flow, as for most meander bends, and wave winnowing of the subaqueous overbank areas. Laterally accreting point‐bar deposits point out that the curvature‐induced helical flow redistributed sediment from the channel thalweg to the bar top and contributed to the development of the ‘classical’ fining‐upward grain size trend. The marked truncation surface, separating clinostratified bar deposits from overlying horizontally‐bedded platform sediments is interpreted here as due to bar top wave‐winnowing, which also possibly promoted bank collapses. In the proposed model, sediments remobilized from bar top and subaqueous overbank areas were transported into the channel, forming peculiar ‘apron‐like’ accumulations, where sand accumulated through avalanching processes and mud settled down from suspension.     

Sericitic alteration at the La Crocetta deposit (Elba Island,Italy): interplay between magmatism,tectonics and hydrothermal activity

The La Crocetta mine near Porto Azzurro (Elba Island, Tuscany, Italy) is an important producer of raw material for the ceramic industry. Exploitation focuses on a pervasively sericitized porphyritic aplite of the Tuscan Magmatic Province, locally known as "eurite", which underwent significant potassium enrichment during sericitic alteration. Eurites are located along the hanging wall of the Elba Centrale Fault, a low-angle extensional lineament of regional significance. A later carbonatization stage, apparently associated with high-angle extensional tectonics, locally overprinted the sericitized facies. It is expressed by carbonate ± pyrite ± quartz veins, with adverse effects on ore quality. Sericitization was accompanied by addition of potassium, and loss of Na (± Ca, Fe). Rubidium was not enriched along with potassium during sericitization, contrary to what would be expected for interaction with late-magmatic fluids. New ⁴⁰Ar–³⁹Ar data from eurites provide an isochron age of about 6.7 Ma for the sericitization, whereas the age of the unaltered protolith is ca. 8.8 Ma. Field evidence indicates the Elba Centrale Fault to be the main channel for the hydrothermal fluids. On the other hand, the involvement of heat and/or fluids contributed by the Porto Azzurro pluton, which crops out in the La Crocetta area, is ruled out by field, geochemical and geochronological data (⁴⁰Ar–³⁹Ar age of Porto Azzurro =5.9 Ma, i.e. significantly younger than the sericitization event). Fluid inclusion studies suggest that sericitization was associated with a low-temperature (<250 °C) hydrothermal system. Fluids were locally boiling, of variable salinity (4–17 wt% NaCl equiv.), and contained some CO₂ (XCO₂≤0.027). Their ultimate source is not unequivocally constrained; meteoric and/or magmatic contributions may be possible. Low-salinity (≤2.6 wt% NaCl equiv.), low-temperature (<250 °C) fluids are associated with the late carbonate veining. They are considered to be of dominantly meteoric nature because of their low salinity. In summary, sericitization at La Crocetta is regarded as the product of a detachment fault-related, low temperature hydrothermal system, resulting from the structurally controlled focusing of meteoric and possibly magmatic fluids. Hence, potential targets for exploration for similar resources are represented by aplitic bodies located in the hanging wall of Elba Centrale Fault. Electronic supplementary material to this paper can be obtained by using the Springer LINK server located at http://dx.doi.org/10.1007/s00126-002-0279-2.     

Contents of Volume 30

Volume Contents

Contents of Volume 30     

A quantum chemical investigation of the oxidation and dissolution mechanisms of Galena

The oxidation and dissolution mechanisms of galena (PbS) remain uncertain with a wide variety of possible mechanisms having been proposed in the literature. In this study, the thermodynamic viability of some possible mechanisms has been tested using semi-empirical quantum chemical calculations applied to a perfect (001) galena surface.The adsorption of O₂ and H₂O has been examined in both the gaseous and aqueous environments. In agreement with previous ab initio quantum chemical calculations, the surface induced dissociation of H₂O in either environment was found to be energetically unfavourable. However, the dissociative adsorption of O₂ was found to be possible and resulted in two O atoms bonded to diagonally adjacent S atoms with the O atoms oriented along the diagonal.The adsorption of H⁺ and possible subsequent dissolution mechanisms have been examined in the aqueous environment. An anaerobic mechanism leading to the dissolution of hydroxylated Pb²⁺ was identified. The mechanism involves the protonation of 3 surface S atoms surrounding a central surface Pb atom followed by substitution of this Pb by a further H⁺. The activation energy of this mechanism was estimated to be ≈100 kJ mol⁻¹. Pb²⁺ dissolution could only occur with vacancy stabilisation by a H⁺. The analogous mechanisms for systems comprising H⁺ adsorbed on either 2 or 4 of the S atoms surrounding a central surface Pb were not found to be energetically viable. Subsequent dissolution of one of the protonated S atoms to form H₂S_(g) was not found to be possible thus indicating the likely formation of a Pb-deficient S-rich surface under acidic anaerobic conditions.Acidic aerobic dissolution has also been examined. Congruent dissolution to form H₂SO₄ and Pb²⁺•6H₂O is energetically viable. The dissolution of one of the protonated S atoms neighbouring the Pb²⁺ vacancy, resulting from the anaerobic dissolution, to form H₂SO₄, is also possible.     

Studies of equilibrium, structure, and dynamics in the aqueous Al(iii)-oxalate-fluoride system by potentiometry, C and F NMR spectroscopy

The AlOx_1-3 (Ox = oxalate) species were identified in 0.6 M aqueous NaCl by ¹³C nuclear magnetic resonance (NMR). Rate constants and activation parameters for intramolecular cis/trans isomerization of the Werner-type AlOx₂⁻ complex (k(298 K) = 5 s⁻¹, ΔH^# = 67 ± 5 kJ mol⁻¹, ΔS^# = −6 ± 6 J mol⁻¹ K⁻¹, the rate determining step could be the breaking of the Al-O(C=O) bond) and a very slow intermolecular ligand exchange reaction of AlOx₃³⁻ complex and the free ligand (k₃₀(298 K) = 6.6 · 10⁻⁵ s⁻¹, ΔH^# = 164 ± 17 kJ mol⁻¹, ΔS^# = 225 ± 51 J mol⁻¹ K⁻¹, D/I_d mechanism) were determined by dynamic 1D and 2D ¹³C NMR measurements. Mixed complexes, AlFOx, AlFOx₂^2-, AlF₂Ox⁻, and AlF₂Ox₂^3-, with overall stability (logβ) of 11.53 ± 0.03, 15.67 ± 0.03, 15.74 ± 0.02, and 19.10 ± 0.04 were measured by potentiometry using pH- and fluoride-selective electrodes and confirmed by ¹³C and¹⁹F NMR. The role of these complexes in gibbsite dissolution was modeled. The mixed Al(III)-Ox^2--F⁻ complexes have to be considered as the chemical speciation of Al(III) in natural waters is discussed.     

Seismotectonic re-evaluation of the 1976 Friuli, Italy, seismic sequence

The 1976 Friuli seismic sequence is known for itscomplexity, with several unusually large aftershocksoccurring in the epicentral area. The source region, where the northeastern part of the Alpine chain meetsthe northern Dinaric chain, is characterized by a complexcompressional tectonic regime. Previous studies have not clearly identified which of the two main tectonic systems was activated, in part due to the limited precision of derived earthquake parameters, such as hypocentral coordinates and focal mechanisms. We review the locations for the 10 largest events of the sequence, including theSeptember 16, 1977 and April 18, 1979 earthquakes andwe compute their centroid moment tensors. Source parameters are calculated using intermediate period surfacewaves and the modification of the Harvard centroid-moment tensoralgorithm proposed by Arvidsson and Ekström (1998). A summary of all available geological, geodetic and seismological data show that most of the earthquakes may be associated with the Periadriatic overthrust and other related thrust faults. Based on their locations and focal mechanisms only two ofthe early aftershocks (May 7, 1976 and May 9, 1976) appear instead to have occurred on Dinaric structures.     

Reconstructing lake and drainage basin history using terrestrial sediment layers: analysis of cores from a post-glacial lake in New England, USA

Four sediment cores and twenty-five ¹⁴C ages from Ritterbush Pond in northern Vermont provide a detailed and continuous temporal record of Holocene lake and watershed dynamics. Using visual logs, carbon content, magnetic susceptibility, stable isotope signatures, and X-radiography, all measured at 1-cm scale, we identify and date discrete layers of terrestrially-derived sediment in the organic-rich, lacustrine gyttja. These inorganic layers range in thickness from <1 mm to >10 cm and range in grain size and sorting from homogeneous silt to graded sand. AMS radiocarbon ages both from macrofossils within the thickest layers, and gyttja bracketing these layers, provide the basis for correlation among the cores, the dating of 52 basin-wide sedimentation events, and the development of a detailed sedimentation chronology for the Holocene.Physical, chemical, and isotopic analyses suggest the inorganic layers are terrestrially derived and result from hydrologic events large enough to erode and transport sediment from the watershed into the pond. The temporal and spatial distribution of the inorganic layers suggests changing basin-wide sedimentation and thus erosion dynamics since deglaciation over 12,000 years ago. Specifically, for intervals lasting 400 to 1000 years, during the early (>8600 cal yBP), middle (6400 to 6800 cal yBP) and late Holocene (1800 to 2600 cal yBP), the Ritterbush Pond watershed eroded more rapidly than at other times and terrestrially derived material poured into the pond. Analysis of Ritterbush Pond sediments demonstrates the potential for North American lakes to preserve a record of drainage basin dynamics.