John C. Seaman

Ionic tracer movement through highly weathered sediments

A highly-weathered, sandy aquifer material from the Upper Coastal Plain region of the southeastern U.S.A. (Aiken, South Carolina) was used to determine the impact of ionic strength and solution composition on the determination of physical transport parameters using ionic tracers. The mineralogy of the clay fraction consisted primarily of kaolinite, goethite and mica. Repacked saturated columns (bulk density ∼ 1.5 g cm−3) were leached at a constant rate (∼ 0.25 cm min−1) with a given tracer solution. For comparison, tritium (∼ 200 pCi mL−1) was included in leachate of selected columns and several of the experiments were replicated in columns of acid-washed sand. Pore volume estimates based on tritium breakthrough were consistent with those calculated from the bulk density of the repacked matrix. In contrast, solute breakthrough for the sandy geologic material was dependent on concentration, as well as cation and anion type. At low ionic strenghts (0.0005–0.010 M) that are analogous to conditions that may be encountered ins field-scale transport experiments, neither the cation nor the anion acted conservatively, yielding systematically high estimates of column porosity or low estimates of flow velocity. At the higher ionic strengths (∼ 0.10 M), solute breakthrough was essentially conservative regardless of ionic composition. The impact of cation valence and concentration on Br− breakthrough was determined using MgBr2 and KBr solutions of varying concentrations (0.001–0.1 N). Bromide breakthrough was substantially delayed for concentrations below 0.10 M and was delayed to a greater extent in the presence of a divalent cation (Mg2+) than in the presence of a monovalent cation (K+). Failure to recognize these interactions in the field could lead to a false interpretation of Br displacement in terms of physical interactions, i.e. flow velocity, dispersivity, etc.

Kinetic and thermodynamic study of chlorophenol sorption in an allophanic soil.

The sorption of 2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol by a allophanic soil was studied in a series of batch experiments. Chlorophenol sorption behavior was evaluated as a function of reaction time (0-96h) and input concentration at a fixed ionic strength (0.1mol L(-1) KCl) at 25, 35, and 45 degrees C. Sorption results for the various reaction temperatures were used in calculating thermodynamic parameters. Chlorophenol sorption increased with temperature, suggesting an endothermic process. The Elovich equation was used to describe the kinetic data. Data from the isotherm experiments were described by the Triple-Layer Model in which monodentate outer- and inner-sphere complexes were formed between deprotonated organic molecules and active sites on the variable-charge soil. The calculated thermodynamic parameters suggest that chlorophenol sorption is a spontaneous (DeltaG<0), endothermic (DeltaH>0) and entropy-driven reaction (DeltaS>0).

Uranium immobilization in an iron-rich rhizosphere of a native wetland plant from the Savannah River Site under reducing conditions.

The hypothesis of this study was that iron plaques formed on the roots of wetland plants and their rhizospheres create environmental conditions favorable for iron reducing bacteria that promote the in situ immobilization of uranium. Greenhouse microcosm studies were conducted using native plants (Sparganium americanum) from a wetland located on the Savannah River Site, Aiken, SC. After iron plaques were established during a 73-day period by using an anoxic Fe(II)-rich nutrient solution, a U(VI) amended nutrient solution was added to the system for an additional two months. Compared to plant-free control microcosms, microcosms containing iron plaques successfully stimulated the growth of targeted iron reducing bacteria, Geobacter spp. Their population continuously increased after the introduction of the U(VI) nutrient solution. The reduction of some of the U(VI) to U(IV) by iron reducing bacteria was deduced based on the observations that the aqueous Fe(II) concentrations increased while the U(VI) concentrations decreased. The Fe(II) produced by the iron reducing bacteria was assumed to be reoxidized by the oxygen released from the roots. Advanced spectroscopic analyses revealed that a significant fraction of the U(VI) had been reduced to U(IV) and they were commonly deposited in association with phosphorus on the iron plaque.

Production of Coal Combustion Products and Their Potential Uses

Coal Combustion Products (CCPs) arise from the combustion of coal for energy, with fly ash (FA), bottom ash (BA) and flue-gas desulfurization residues (FGD) the most abundant. Our reliance on fossil fuel for energy is set to continue into the 21st century, and research into the environmental safety of beneficial re-use options, as well as novel re-use options, must continue. Since previous editions of collected CCP research1, significant changes have been made to both the New Source Review and the Clean Air Act that directly impact CCP production figures. New techniques such as x-ray absorption spectroscopy are increasingly being used to reveal micron-scale elemental characteristics of CCPs, and aid our understanding of the distribution and chemical form of the metallic constituents. This chapter summarizes production and use covering the period 2001–2003, new trends in reuse applications and discusses new research on the environmental safety of CCP re-use.

CHARACTERIZING CLAY MINERAL SUSPENSIONS USING ACOUSTIC AND ELECTROACOUSTIC SPECTROSCOPY – A REVIEW

Recently, significant advances have been made in the theory and application of acoustic and electroacoustic spectroscopies for measuring the particle-size distribution (PSD) and zeta potential (ζ potential) of colloidal suspensions, respectively. These techniques extend or replace other techniques, such as light-scattering methods, particularly in concentrated suspensions. In this review, we summarize acoustic and electroacoustic theory and published results on clay mineral suspensions, detail theoretical constraints, and indicate potential applications for the study of environmentally significant clay mineral suspensions. Using commercially available instrumentation and suspension concentrations up to 45 vol.%, acoustic spectroscopy can characterize particle sizes from 10 nm to 10 µm, or greater. Electroacoustic spectroscopy can determine the ζ potential of a suspension with a precision and accuracy in the mV range. Despite the clear potential for their use in environmental settings, to date, acoustic methods have been used mainly on clay mineral colloids with industrial application, typically combined with similar measurements such as isoelectric point (IEP) determined from shear yield stress or ζ potential from electrophoretic mobility measurements. Potential applications in environmentally relevant suspension concentrations are significant, as PSD and ζ potential are important factors influencing the transport of mineral colloids and associated contaminants through porous media. Applications include determining the effects of suspension concentration, surfactants, electrolyte strength, pH and solution composition on soil clay properties and colloidal interactions, and determining changes in PSD, aggregation and ζ potential due to adsorption or variations in the clay mineralogy.

Functionalized magnetic mesoporous silica nanoparticles for U removal from low and high pH groundwater

U(VI) species display limited adsorption onto sediment minerals and synthetic sorbents in pH <4 or pH >8 groundwater. In this work, magnetic mesoporous silica nanoparticles (MMSNs) with magnetite nanoparticle cores were functionalized with various organic molecules using post-synthetic methods. The functionalized MMSNs were characterized using N2 adsorption-desorption isotherms, thermogravimetric analysis (TGA), transmission electron microscopy (TEM), (13)C cross polarization and magic angle spinning (CPMAS) nuclear magnetic resonance (NMR) spectroscopy, and powder X-ray diffraction (XRD), which indicated that mesoporous silica (MCM-41) particles of 100-200nm formed around a core of magnetic iron oxide, and the functional groups were primarily grafted into the mesopores of ∼3.0nm in size. The functionalized MMSNs were effective for U removal from pH 3.5 and 9.6 artificial groundwater (AGW). Functionalized MMSNs removed U from the pH 3.5 AGW by as much as 6 orders of magnitude more than unfunctionalized nanoparticles or silica and had adsorption capacities as high as 38mg/g. They removed U from the pH 9.6 AGW as much as 4 orders of magnitude greater than silica and 2 orders of magnitude greater than the unfunctionalized nanoparticles with adsorption capacities as high as 133mg/g. These results provide an applied solution for treating U contamination that occurs at extreme pH environments and a scientific foundation for solving critical industrial issues related to environmental stewardship and nuclear power production.

Spectroscopic Evidence of Uranium Immobilization in Acidic Wetlands by Natural Organic Matter and Plant Roots

Biogeochemistry of uranium in wetlands plays important roles in U immobilization in storage ponds of U mining and processing facilities but has not been well understood. The objective of this work was to study molecular mechanisms responsible for high U retention by Savannah River Site (SRS) wetland sediments under varying redox and acidic (pH = 2.6-5.8) conditions using U L3-edge X-ray absorption spectroscopy. Uranium in the SRS wetland sediments existed primarily as U(VI) bonded as a bidentate to carboxylic sites (U-C bond distance at ∼2.88 Å), rather than phenolic or other sites of natural organic matter (NOM). In microcosms simulating the SRS wetland processes, U immobilization on roots was 2 orders of magnitude higher than on the adjacent brown or more distant white sands in which U was U(VI). Uranium on the roots were both U(IV) and U(VI), which were bonded as a bidentate to carbon, but the U(VI) may also form a U phosphate mineral. After 140 days of air exposure, all U(IV) was reoxidized to U(VI) but remained as a bidentate bonding to carbon. This study demonstrated NOM and plant roots can highly immobilize U(VI) in the SRS acidic sediments, which has significant implication for the long-term stewardship of U-contaminated wetlands.

The Production and Use of Coal Combustion Products

Coal combustion byproducts (CCBs) arising from energy generation are the most abundant waste streams worldwide. Legislation aimed at reducing environmental pollution associated with coal combustion will continue to add to this waste stream into the future, increasing the need to develop pertinent and safe end uses for these materials. While production of CCBs continues to rise so also do the costs associated with their disposal and landfilling. This chapter presents updated information about the production of the main categories of CCB in the U.S., outlining their individual characteristics and describing their various end uses. Further, it introduces the reader to current research on potential novel end uses of CCBs, and their effect on the environment.

Contaminant mobility in soils amended with fly ash and flue-gas gypsum: Intact soil cores and repacked columns

The impact of the land application of coal combustion by-products, fly ash (FA) and flue-gas desulfurization gypsum(FDG), to coarse-textured soils of the southeastern U.S.A. wasinvestigated using batch and dynamic column techniques. Two FAsamples, one an alkaline FA (Alk-FA) and the other an acidic FA(Acid-FA), were evaluated alone and in combination with FDG assoil amendments to an Appling loamy sand (Typic Hapludults). Theeffects of these waste products on clay dispersion, soilhydraulic conductivity (Ksat) and the migration ofcontaminants such as Arsenic (As) and Boron (B) were studiedusing intact soil cores and repacked soil columns. FA or combinationsof FA + FDG were applied to the surface of intact soil cores (10 Mg ha-1) and repacked soil columns or incorporated withinrepacked soil columns. The columns were saturated and thenleached for a prescribed number of pore volumes to simulateleaching conditions in the field. Effluent pH, electricalconductivity (EC), and turbidity were monitored and leachatefractions were collected for B, As, Ca, Mg, K and Na analysis.Both FA materials were ineffective at decreasing the inherentdispersibility of clay from the Ap horizon in batch tests.In fact, high application rates of the Alk-FA induced some claydispersion in the well-flocculated Bt soil materials, andcolumn results suggest that incorporating the Alk-FA within thesurface soil may actually reduce Ksat. In contrast,treatments with FDG were highly effective at inducing rapid clayflocculation in batch tests and eliminating effluent turbidityfor intact and repacked soil columns. Boron was readily mobilefrom both intact and repacked soil columns, a majority of whichleached from the columns within the first three pore volumes.Boron leaching was greater for combined treatments (FA + FDG),possibly indicative of enhanced solubilization in the presenceof FDG or sulfate (SO42-) competition for sorptionsites. Arsenic levels present in the leachates from FA and FDGcolumns were generally lower than control columns and roughlycorrelated with effluent turbidity. Combined treatments (FA +FDG) enhanced Mg and K leaching due to the added competition ofCa for cation exchange sites. Following leaching, the intactsoil cores were sectioned at 5 cm intervals and the pH and EC ofthe soil, as well as the vertical distribution of As and B, weredetermined. Levels of residual As were only slightly higher in the upper section of the FA-amended columns, showing little downward movement, but no clear trend in residual B was observed due to its greater mobility.

ACOUSTIC AND ELECTROACOUSTIC CHARACTERIZATION OF VARIABLE-CHARGE MINERAL SUSPENSIONS

Acoustic and electroacoustic measurements of particle-size distribution (PSD) and zeta potential (ζ potential), respectively, were used to obtain in situ measures of the effects of suspension concentration and pH on interactions between mixed-charge clays and clay minerals from a highly weathered sediment. Measurements were obtained in concentrated suspensions as a function of weight fraction and as a function of pH during titrations. Standard dispersion and centrifugation methods were used to obtain a comparative measure of PSD. Thermogravimetric analysis and X-ray diffraction patterns were used to obtain semi-quantitative and descriptive analyses, respectively, of the sediment, which is composed of Fe oxide minerals, kaolinite, gibbsite, quartz, crandallite, chlorite and traces of other clay minerals. Acoustic measurements showed that the PSD of the clay fraction varied with suspension concentration, and electroacoustic measurements showed the ‘bulk’ ζ potential increased in absolute value as the suspension concentration decreased. Titration results were also sensitive to suspension concentration. Acoustic measurements indicated that the suspensions became unstable at ∼pH 7.5–8.0, as the attenuation spectra changed character near this pH and the calculated PSD shifted to a larger particle size. This pH value is near the points of zero charge of goethite and gibbsite, as verified by titrations on mineral standards. The results confirm the central role oxide minerals play in regulating clay mineral interactions in highly weathered sediments, and indicate that the average ζ potential of a suspension may be a poor indicator of controls on suspension stability.