Groundwater control of mangrove surface elevation: Shrink and swell varies with soil depth

We measured monthly soil surface elevation change and determined its relationship to groundwater changes at a mangrove forest site along Shark River, Everglades National Park, Florida. We combined the use of an original design, surface elevation table with new rod-surface elevation tables to separately track changes in the mid zone (0–4 m), the shallow root zone (0–0.35 m), and the full sediment profile (0–6 m) in response to site hydrology (daily river stage and daily groundwater piezometric pressure). We calculated expansion and contraction for each of the four constituent soil zones (surface [accretion and erosion; above 0 m], shallow zone [0–0.35 m], middle zone [0.35–4 m], and bottom zone [4–6]) that comprise the entire soil column. Changes in groundwater pressure correlated strongly, with changes in soil elevation for the entire profile (Adjusted R² = 0.90); this relationship was not proportional to the depth of the soil profile sampled. The change in thickness of the bottom soil zone accounted for the majority (R² = 0.63) of the entire soil profile expansion and contraction. The influence of hydrology on specific soil zones and absolute elevation change must be considered when evaluating the effect of disturbances, sea level rise, and water management decisions on coastal wetland systems.     

Web-cam’s potential for collaborative activities in the Earth sciences

We report here our experiences from using easily acquired web-cam components for collaborative ventures in the Earth sciences. We have used a variety of hardware and different software. We demonstrate from various locations in the U.S.A. the feasibility of using web-cam in multitudinous activities, relevant for conducting research and knowledge dissemination. We summarize the quality of the connections from the various combinations of communicating parties. Today, web-cams can be utilized as an economical and viable means of point-to-point communication in the Earth science community. Greater bandwidth is sorely needed for activities such as multi-party conferencing on the present internet network. We propose that web-cam can be readily deployed as a web-service for facilitating collaborative research over the GRID infrastructure, using the middleware Narada-Brokering. Web-cam will play an important role in the emerging field of geoinformatics.     

The “suevite” conundrum,Part 1: The Ries suevite and Sudbury Onaping Formation compared

The term “suevite” has been applied to various impact melt‐bearing breccias found in different stratigraphic settings within terrestrial impact craters. Suevite was coined initially for impact glass‐bearing breccias from the Ries impact structure, Germany, which is the type locality. Various working hypotheses have been proposed to account for the formation of the Ries suevite deposits over the past several decades, with the most recent being molten‐fuel‐coolant interaction (MFCI) between an impact melt pool and water. This mechanism is also the working hypothesis for the origin of the bulk of the Onaping Formation at the Sudbury impact structure, Canada. In this study, the key characteristics of the Ries suevite, the Onaping Formation and MFCI deposits from phreatomagmatic volcanic eruptions are compared. The conclusion is that there are clear and significant lithological, stratigraphic, and petrographic observational differences between the Onaping Formation and the Ries suevite. The Onaping Formation, however, shares many key similarities with MFCI deposits, including the presence of layering, their well‐sorted and fine‐grained nature, and the predominance of vitric particles with similar shapes and lacking included mineral and lithic clasts. These differences argue against the viability of MFCI as a working hypothesis for genesis of the Ries suevite and for a required alternative mechanism for its formation.     

Metal binding capacity of selected maine surface waters

Concentrations of Ca, Cd, Cu, Fe, and Pb and binding capacities for Cd, Cu, and Pb were determined for water samples collected from 12 lakes in southwestern Maine using atomic absorption and ion-selective electrodes, respectively. Surface waters in this area are soft and characterized by low pH. Some lakes were highly colored with refractory organics, whereas others had very low organic carbon concentrations. Both Cu and Pb concentrations were positively correlated with organic carbon content. Copper and Pb binding capacities were significantly correlated with organic carbon content, whereas Cd binding capacity was positively correlated with pH, but not with organic carbon. Surface water binding capacity for Pb was greater than that for Cu or Cd. More than 99% of the Ca from all waters studied was removed onto cationic exchange resins. Less than 1% of the total Cu existed as cationic species in highly humic waters, whereas as much as 65% existed as cationic species in less huic waters. Conversely, more than 99% of the Cd present in humic waters existed as cationic species, whereas as little as 50% existed as cationic species in less humic, more alkaline waters. These correlative studies indicate that binding by organic carbon is important for both Cu and Pb in this area and must be considered in models of trace metal speciation. However, Cd binding in the same waters is not correlated with organic carbon, which does not need to be considered in speciation models for Cd.     

Structure energies of the alkali feldspars

Structural energetics of the alkali feldspars have been studied using a “lattice” or structure energy model. Electrostatic energies, U _e,for 20 well-refined, non-intergrown alkali feldspars were calculated using Bertaut's (1952) summation procedure and average about ?13,400 kcal/mol; the repulsive energies of the alkali site in each structure (～15 kcal/mol) were calculated using repulsive parameters for K-O and Na-O interactions estimated from bulk modulus data for NaF and KF and the exponential form of the repulsive potential. Using a procedure in which the position of the alkali cation was varied while the oxygen cage was kept fixed, structure energy gradients for the alkali sites of high albite and a hypersolvus Ab₄₂Or₅₈ structure were computed. In both cases, a broad structure energy well, elongated approximately parallel to c and subparallel to the observed split Na positions, was found. In both structures there is a single energy minimum corresponding closely with the observed single alkali positions. Comparison of U _e values for the alkali feldspars with different K/Na ratios shows that intermediate compositions are predicted to be less “stable” than either endmember and that the potassic end-member is predicted to be less “stable” than the sodic one, assuming that all other factors contributiong to the free energies of each phase are approximately the same. Comparison of U _e values for the high albite and low sanidine structures with different Al/Si distributions and a fixed tetrahedral framework indicates that the ordered charge distributions are 63.0 and 54.8 kcal/mol, respectively, more “stable” than the disordered distributions. Smaller, more realistic energy differences were obtained by using U _evalues averaged from four separate calculations with a +3 charge on a different T site in each and with +4 charges on the other T sites. If, in addition, the charges on cations and oxygen are reduced to half their nominal formal charges, in agreement with Pauling's electroneutrality principle and the results of recent molecular orbital calculations on silicates, the predicted electrostatic energy differences are reduced to 3.6 and 1.6 kcal/mol, respectively. These calculations also indicate that the T₁O site in the high albite structure energetically favors Al and that the Al/Si distribution determines the Na position within the alkali site.     

Analysis and Simulation of Propagule Dispersal and Salinity Intrusion from Storm Surge on the Movement of a Marsh–Mangrove Ecotone in South Florida

Coastal mangrove–freshwater marsh ecotones of the Everglades represent transitions between marine salt-tolerant halophytic and freshwater salt-intolerant glycophytic communities. It is hypothesized here that a self-reinforcing feedback, termed a “vegetation switch,” between vegetation and soil salinity, helps maintain the sharp mangrove–marsh ecotone. A general theoretical implication of the switch mechanism is that the ecotone will be stable to small disturbances but vulnerable to rapid regime shifts from large disturbances, such as storm surges, which could cause large spatial displacements of the ecotone. We develop a simulation model to describe the vegetation switch mechanism. The model couples vegetation dynamics and hydrologic processes. The key factors in the model are the amount of salt-water intrusion into the freshwater wetland and the passive transport of mangrove (e.g., Rhizophora mangle) viviparous seeds or propagules. Results from the model simulations indicate that a regime shift from freshwater marsh to mangroves is sensitive to the duration of soil salinization through storm surge overwash and to the density of mangrove propagules or seedlings transported into the marsh. We parameterized our model with empirical hydrologic data collected from the period 2000–2010 at one mangrove–marsh ecotone location in southwestern Florida to forecast possible long-term effects of Hurricane Wilma (24 October 2005). The model indicated that the effects of that storm surge were too weak to trigger a regime shift at the sites we studied, 50 km south of the Hurricane Wilma eyewall, but simulations with more severe artificial disturbances were capable of causing substantial regime shifts.     

Uranyl adsorption onto montmorillonite: Evaluation of binding sites and carbonate complexation

The fate and transport of uranium in contaminated soils and sediments may be affected by adsorption onto the surface of minerals such as montmorillonite. Extended X-ray absorption fine structure (EXAFS) spectroscopy has been used to investigate the adsorption of uranyl (UO₂²⁺) onto Wyoming montmorillonite. At low pH (∼4) and low ionic strength (10⁻³ M), uranyl has an EXAFS spectrum indistinguishable from the aqueous uranyl cation, indicating binding via cation exchange. At near-neutral pH (∼7) and high ionic strength (1 M), the equatorial oxygen shell of uranyl is split, indicating inner-sphere binding to edge sites. Linear-combination fitting of the spectra of samples reacted under conditions where both types of binding are possible reveals that cation exchange at low ionic strengths on SWy-2 may be more important than predicted by past surface complexation models of U(VI) adsorption on related montmorillonites. Analysis of the binding site on the edges of montmorillonite suggests that U(VI) sorbs preferentially to [Fe(O,OH)₆] octahedral sites over [Al(O,OH)₆] sites. When bound to edge sites, U(VI) occurs as uranyl-carbonato ternary surface complexes in systems equilibrated with atmospheric CO₂. Polymeric surface complexes were not observed under any of the conditions studied. Current surface complexation models of uranyl sorption on clay minerals may need to be reevaluated to account for the possible increased importance of cation exchange reactions at low ionic strengths, the presence of reactive octahedral iron surface sites, and the formation of uranyl-carbonato ternary surface complexes. Considering the adsorption mechanisms observed in this study, future studies of U(VI) transport in the environment should consider how uranium retardation will be affected by changes in key solution parameters, such as pH, ionic strength, exchangeable cation composition, and the presence or absence of CO₂.     

Bioaccumulation of gold by sulfate-reducing bacteria cultured in the presence of gold(I)-thiosulfate complex

A sulfate-reducing bacterial (SRB) enrichment, from the Driefontein Consolidated Gold Mine, Witwatersrand Basin, Republic of South Africa, was able to destabilize gold(I)-thiosulfate complex and precipitate elemental gold. The precipitation of gold was observed in the presence of active (live) SRB due to the formation and release of hydrogen sulfide as an end-product of metabolism, and occurred by three possible mechanisms involving iron sulfide, localized reducing conditions, and metabolism. The presence of biogenic iron sulfide caused significant removal of gold from solutions by adsorption and reduction processes on the iron sulfide surfaces. The presence of gold nanoparticles within and immediately surrounding the bacterial cell envelope highlights the presence of localized reducing conditions produced by the bacterial electron transport chain via energy generating reactions within the cell. Specifically, the decrease in redox conditions caused by the release of hydrogen sulfide from the bacterial cells destabilized the solutions. The presence of gold as nanoparticles (<10 nm) inside a sub-population of SRB suggests that the reduction of gold was a part of metabolic process. In late stationary phase or death phase, gold nanoparticles that were initially precipitated inside the bacterial cells, were released from the cells and deposited in the bulk solution as addition of gold nanoparticles that already precipitated in the solution. Ultimately, the formation of micrometer-scale sub-octahedral and octahedral gold and spherical aggregates containing octahedral gold was observed.     

Hydrocarbons generated by hydropyrolysis of suspended marine particulate organic matter: Relationship to the oceanography of the Black Sea and the Rhodes Gyre

The suspended particulate organic matter, SPOM, in the autumnal Black Sea has been characterised using catalytic hydropyrolysis (HyPy) of the total (bound plus free) lipid material. The technique, which generates maximum yields of volatile products from sediments, kerogens and phytoplankton, was followed using gas chromatography and gas chromatography/mass spectrometry. The generated alkanes were dominated by n-C₁₈, hypothesised to arise predominantly from unsaturated C₁₈ fatty acids. Steranes were generated from reductive conversion of free and bound sterols. The generation of branched alkanes and especially of hopanes provided formal evidence for the participation of bacteria in the mineralisation of the SPOM. Whereas similar distributions of n-alkanes were generated from SPOM sampled from different depths of the comparatively well-stirred Rhodes Gyre (eastern Mediterranean), mineralisation of the SPOM at each depth of the central Black Sea produced characteristic changes in the composition and concentration of the HyPy products. Depth profiles of the n-alkanes generated from SPOM in the region of the Rim Current were affected by the local hydrography. Polynuclear aromatic hydrocarbons (PAHs) of anthropogenic origin were present in the surface waters of the central Black Sea. Some methyl benzenes, thiophenes and pyrroles were also generated.     

Soft X-ray spectroscopic studies of the reaction of fractured pyrite surfaces with Cr(VI)-containing aqueous solutions

We have used synchrotron-based soft X-ray core-level photoemission and adsorption spectroscopies to study the reaction of aqueous sodium chromate solutions with freshly fractured pyrite surfaces. Pyrite surfaces were reacted with 50 μM sodium chromate solution at pH 7 for reaction times between 1 min and 37 hr. Additional experiments were performed at pH 2 and pH 4 with 50 μM sodium chromate solutions and at pH 7 with 5 mM solutions. At chromate concentrations of 50 μM, all chromium present on the pyrite surface was in the form of Cr(III), while at 5 mM, both Cr(III) and Cr(VI) were present at the pyrite surface. Minor quantities of oxidized sulfur species (sulfate, sulfite, and zero-valent sulfur) were identified as reaction products on the pyrite surface. The amount of oxidized sulfur species observed on the surface was greater when pyrite was reacted with 5 mM Cr(VI) solutions because the rate of chromium deposition exceeded the rate of dissolution of pyrite oxidation products, effectively trapping Cr(VI) and oxidized sulfur species in an overlayer of iron(III)-containing Cr(III)-hydroxide. This work shows that pyrite, an extremely cheap and readily available waste material, may be suitable for the removal of hexavalent chromium from acidic to circumneutral waste streams. The reduced chromium ultimately forms a coating on the pyrite surface, which passivates the pyrite surface towards further oxidation.