A first principles study of the distribution of iron in sphalerite

Quantum mechanical techniques, based on density functional theory, have been used to study the distribution of iron impurities in sphalerite (ZnS) at compositions ranging from 3.125 to 12.5 mol% FeS. Our results show that iron is most easily incorporated by direct substitution onto the zinc site and that energies for solution reactions involving FeS are exothermic when the system is zinc deficient. Furthermore, there appears to be a small driving force for the formation of bound Fe-Fe pairs at low iron concentrations, though there is no particular preference found for larger clusters of iron. The influence of iron on the sphalerite cell parameter is shown to be sensitive to the presence of Fe-Fe pairs and to the degree of sample non-stoichiometry.     

Coupled (H, M) substitutions in forsterite

Coupled substitutions involving hydrogen plus trivalent elements (Al, Eu, Fe, Ga, Gd, Lu, Mn, Nd, Pu, Sc, Y and Yb) in forsterite (Mg₂SiO₄) are studied using atomistic simulation methods. Incorporation of hydrogen is energetically favourable when included in the forsterite lattice as hydroxyl groups (OH⁻) at O3 sites while the trivalent cations replace either magnesium or silicon. Our calculations show a strong dependence on the ionic radius of the impurity species and some variation with pressure. There are also significant structural distortions around the impurity defects. At low pressure (0 GPa), the smaller trivalent cations, (e.g. Al, Fe, Mn and Ga) substitute into forsterite by replacing Si as: . The larger trivalent cations (e.g. Eu, Gd, Lu, Nd, Pu, Y and Yb) however, replace Mg at the M2 site coupled with an Mg1 vacancy as described by . At 12 GPa, the large cations are more stable at Mg1 relative to Mg2, but both are predicted to be less stable than configurations associated with Si vacancies. The trivalent ionic radius has a significant effect on the H incorporation mechanism, however, the high formation energy of Si vacancies suggests that the presence of H in forsterite could inhibit incorporation of these elements, particularly at high pressure.     

Geological controls and effects of floodplain asymmetry on river–groundwater interactions in the southeastern Coastal Plain, USA

Channel sediment and alluvial aquifer hydraulic properties exert a major control on river–groundwater interactions. Channels and floodplains are often asymmetrical, resulting in differences in sediment hydraulic properties across the river. Floodplain asymmetry is common along Coastal Plain rivers in South Carolina and North Carolina, USA. The Tar River, North Carolina, has an asymmetrical valley. The study objective was to characterize the effects of floodplain asymmetry and geological controls on river–groundwater interactions. Floodplain and river channel sediments adjacent to the river were characterized with split spoon cores and hand auger samples along a 22-km reach. Hydrogeology was characterized with 38 piezometers and water level recorders in and adjacent to the river. Ground penetrating radar was used to define the shallow stratigraphy. Channel sediments were significantly different between the north and south sides of the river. Hydraulic conductivity and groundwater inputs were greater on the side of the river (north) that contained more permeable fluvial deposits. Groundwater chemistry (δ¹⁸O, specific conductance) data also suggested greater exchange between surface water and groundwater on the north side of the river channel. A conceptual hydrogeological model illustrates that groundwater movement and contaminant transport to the river differs across the channel due to asymmetrical geology.     

Impacts of Oyster Reef Restoration on Primary Productivity and Nutrient Dynamics in Tidal Creeks of the North Central Gulf of Mexico

The ability of oysters to remove large quantities of particulates from the water column, thereby potentially improving water quality, has been cited as one of the reasons for oyster reef restoration. However, this ability has not yet been effectively demonstrated in the field. As part of the Alabama Oyster Reef Restoration Project, this study was designed to assess impacts of restored eastern oyster (Crassostrea virginica) reefs on primary production, nutrient dynamics, and water quality in shallow tidal creeks. Using a Before–After-Control–Impact (BACI) design, we monitored tidal creeks around Dauphin Island, AL, for changes induced by the introduction of oyster reefs. Reef placement resulted in increased ammonium (NH₄⁺) in two of the three experimental creeks. Interestingly, oyster reefs did not seem to reduce water column particulates or have an impact on phytoplankton or microphytobenthic biomass or productivity. We do not believe that our data discount the importance and/or usefulness of oysters in modifying the water column. Rather, we acknowledge that it is difficult to detect these impacts/environmental services in this type of system (i.e., a tidal creek system), because they seem to be very localized and short-lived (i.e., not ecologically relevant on a creek-wide scale). This study highlights the need to consider location and habitat in planning oyster restoration projects. Also, it demonstrates that the types, magnitudes, and spatial extent of changes in ecosystem services that should be expected after reef restoration might need to be re-evaluated.     

Geophysical prospection for late Holocene burials in coastal environments: Possibilities and problems from a pilot study in South Australia

Geophysical techniques have been widely employed for the noninvasive location of burial sites in archaeological and forensic investigations. This approach has met with varying degrees of success, depending on factors such as equipment choice, survey methodology, burial type, and geological setting. This paper reports the results of a multitechnique geophysical survey carried out immediately prior to the salvage excavation of two Indigenous burials from an eolian dune in coastal South Australia. Ground‐penetrating radar was not successful in defining the location of the burials owing to the disturbed nature of the local stratigraphy. Magnetic field intensity and apparent magnetic susceptibility surveys identified discrete anomalies that coincided with the location of skeletal material revealed during excavation, which we hypothesize to be due to burning or ochre use during funerary practices. Despite the spatial association of these features, subsequent laboratory analyses of the mineralogy and magnetic properties of sediments collected from the site failed to find a definite cause of the anomalies. Nevertheless, the association between them and the primary interment locations has implications for archaeological surveys carried out in the Australian coastal zone, as it highlights the potential of magnetic field intensity and apparent magnetic susceptibility geophysical techniques undertaken with a more refined survey methodology to afford a noninvasive, culturally appropriate means through which to detect Indigenous burials. This approach may prove particularly useful in areas with disturbed stratigraphy where ground‐penetrating radar is less effective. © 2010 Wiley Periodicals, Inc.     

Decay mechanism of indoor porous opuka stone: a case study from the main altar located in the St. Vitus Cathedral,Prague (Czech Republic)

A carving of the indoor main altar of St. Vitus Cathedral in Prague (Czech Republic) is made of the opuka stone—a clayey–calcareous silicite—which now exhibits the development of decay phenomena such as the formation of salt-laden case-hardened subsurface layer (approx. 150 mm thick), with detachment of the case-hardened layer manifested by blistering and/or flaking. Formation of this gypsum-rich layer is linked to the reaction of components (SO₂) from polluted air (both outdoor and indoor) and from the rock itself (calcium ion from calcite). Development of brittle damage in the subsurface layer and underlying stone is interpreted based on the results from previous environmental monitoring in the Cathedral’s interior, which indicated highly fluctuating temperature and humidity, resulting in a hygrothermal stress in the material described by the “double-layer sandwich” model. The sensitivity of the studied stone to the above-mentioned processes is evidenced by its microstructural properties, specifically parameters of the pore spaces which indicate an extremely high susceptibility to damage by the actions of freezing water and/or salt crystallisation.     

‘Acid rain’, dissolved aluminum and chemical weathering at the Hubbard Brook Experimental Forest,New Hampshire

Contemporary ‘acid rain’ in the Hubbard Brook ecosystem has induced a series of geochemical responses. Neutralization is accomplished in essentially a 2-step process. Initially, hydrogen ion acidity is neutralized by the dissolution of reactive alumina primarilly found in the soil zone. In the Hubbard Brook area this reactive alumina has solution properties much like natural gibbsite. Aluminum-rich surface waters with a pH of 4.7 5.2 are typical of this neutralization stage. In a second step, both hydrogen ion acidity and aluminum acidity are neutralized by the chemical weathering of primary silicate minerals, i.e. by the alkali and alkaline earths contained in the bedrock and glacial till of the watershed. The chemical weathering reaction is much slower than the alumina dissolution reaction, so that the aluminum acidity stage (pH 4.7 5.2) may persist for substantial periods. Typically, however, in the Hubbard Brook area the aluminum acidity has been neutralized and a pH > 5.2 is obtained before surface waters reach a third-over stream channel. Because of the relatively low pH's throughout the soil zone and in the streamwater, carbonic acid reactions are essentially absent at the present time in the Hubbard Brook system. Water pathlength (or residence time) in the soil zone is the crucial factor in the state of acid rain neutralization, aluminum chemistry and chemical weathering. As measured by the losses of alkali and alkaline earths from the ecosystem, chemical weathering rate in the Hubhard Brook area at the present time is not especially high relative to other areas.     

The role of reaction affinity and secondary minerals in regulating chemical weathering rates at the Santa Cruz Soil Chronosequence, California

In order to explore the reasons for the apparent discrepancy between laboratory and field weathering rates and to determine the extent to which weathering rates are controlled by the approach to thermodynamic equilibrium, secondary mineral precipitation, and flow rates, a multicomponent reactive transport model (CrunchFlow) was used to interpret soil profile development and mineral precipitation and dissolution rates at the 226 ka Marine Terrace Chronosequence near Santa Cruz, CA. Aqueous compositions, fluid chemistry, transport, and mineral abundances are well characterized [White A. F., Schulz M. S., Vivit D. V., Blum A., Stonestrom D. A. and Anderson S. P. (2008) Chemical weathering of a Marine Terrace Chronosequence, Santa Cruz, California. I: interpreting the long-term controls on chemical weathering based on spatial and temporal element and mineral distributions. Geochim. Cosmochim. Acta72 (1), 36-68] and were used to constrain the reaction rates for the weathering and precipitating minerals in the reactive transport modeling. When primary mineral weathering rates are calculated with either of two experimentally determined rate constants, the nonlinear, parallel rate law formulation of Hellmann and Tisserand [Hellmann R. and Tisserand D. (2006) Dissolution kinetics as a function of the Gibbs free energy of reaction: An experimental study based on albite feldspar. Geochim. Cosmochim. Acta70 (2), 364-383] or the aluminum inhibition model proposed by Oelkers et al. [Oelkers E. H., Schott J. and Devidal J. L. (1994) The effect of aluminum, pH, and chemical affinity on the rates of aluminosilicate dissolution reactions. Geochim. Cosmochim. Acta58 (9), 2011-2024], modeling results are consistent with field-scale observations when independently constrained clay precipitation rates are accounted for. Experimental and field rates, therefore, can be reconciled at the Santa Cruz site.Additionally, observed maximum clay abundances in the argillic horizons occur at the depth and time where the reaction fronts of the primary minerals overlap. The modeling indicates that the argillic horizon at Santa Cruz can be explained almost entirely by weathering of primary minerals and in situ clay precipitation accompanied by undersaturation of kaolinite at the top of the profile. The rate constant for kaolinite precipitation was also determined based on model simulations of mineral abundances and dissolved Al, SiO₂(aq) and pH in pore waters. Changes in the rate of kaolinite precipitation or the flow rate do not affect the gradient of the primary mineral weathering profiles, but instead control the rate of propagation of the primary mineral weathering fronts and thus total mass removed from the weathering profile. Our analysis suggests that secondary clay precipitation is as important as aqueous transport in governing the amount of dissolution that occurs within a profile because clay minerals exert a strong control over the reaction affinity of the dissolving primary minerals. The modeling also indicates that the weathering advance rate and the total mass of mineral dissolved is controlled by the thermodynamic saturation of the primary dissolving phases plagioclase and K-feldspar, as is evident from the difference in propagation rates of the reaction fronts for the two minerals despite their very similar kinetic rate laws.