Nikolla P. Qafoku

Variable Charge Soils: Their Mineralogy, Chemistry and Management

Soils in the Oxisols, Ultisols, Alfisols, Spodosols and Andisols orders that are rich in constituents with surface reactive groups with amphoteric properties are considered variable charge soils (VCS). They have developed under intensive weathering in subtropical and tropical regions or from volcanic ash parent material. The magnitude and sign of the surface charge of variable charge constituents depend on the chemistry of the contacting solution (pH and ionic strength). The mineralogical, physical and chemical characteristics of these soil systems are different from those observed in soil systems of temperate regions. In this chapter, the mineralogy, chemistry and management of VCS are reviewed and discussed, focusing on the chemistry of these systems.

Geochemical implications of gas leakage associated with geologic CO2 storage--a qualitative review.

Gas leakage from deep storage reservoirs is a major risk factor associated with geologic carbon sequestration (GCS). A systematic understanding of how such leakage would impact the geochemistry of potable aquifers and the vadose zone is crucial to the maintenance of environmental quality and the widespread acceptance of GCS. This paper reviews the current literature and discusses current knowledge gaps on how elevated CO(2) levels could influence geochemical processes (e.g., adsorption/desorption and dissolution/precipitation) in potable aquifers and the vadose zone. The review revealed that despite an increase in research and evidence for both beneficial and deleterious consequences of CO(2) migration into potable aquifers and the vadose zone, significant knowledge gaps still exist. Primary among these knowledge gaps is the role/influence of pertinent geochemical factors such as redox condition, CO(2) influx rate, gas stream composition, microbial activity, and mineralogy in CO(2)-induced reactions. Although these factors by no means represent an exhaustive list of knowledge gaps we believe that addressing them is pivotal in advancing current scientific knowledge on how leakage from GCS may impact the environment, improving predictions of CO(2)-induced geochemical changes in the subsurface, and facilitating science-based decision- and policy-making on risk associated with geologic carbon sequestration.

The biogeochemistry of technetium: A review of the behavior of an artificial element in the natural environment

Interest in the chemistry of technetium has only increased since its discovery in 1937, mainly because of the large and growing inventory of 99Tc generated during fission of 235U, its environmental mobility in oxidizing conditions, and its potential radiotoxicity. For every ton of enriched uranium fuel (3% 235U) that is consumed at a typical burn-up rate, nearly 1 kg of 99Tc is generated. Thus, the mass of 99Tc produced since 1993 has nearly quadrupled, and the pace of generation will likely increase if more emphasis is placed on nuclear power to slow the accumulation of atmospheric greenhouse gases. In order to gain a comprehensive understanding of the interaction of 99Tc and the natural environment, we review the sources of 99Tc in the nuclear fuel cycle and its biogeochemical behavior. We include an evaluation of the use of Re as a chemical analog of Tc, as well as a summary of the redox potential, sorption, colloidal behavior, and interaction of humic substances with Tc, and the potential for re-oxidation and remobilization of Tc(IV). What emerges is a more complicated picture of Tc behavior than that of an easily tractable transition of Tc(VII) to Tc(IV) with consequent immobilization. Reducing conditions (+200 to +100 mVEh) and the presence of Fe(II) sorbed onto Fe(III) (oxy)hydroxides will bring the mobile Tc(VII) species to a lower oxidation state and will form the relatively insoluble Tc(IV)O2 · nH2O, but even as a solid, equilibrium concentrations of aqueous Tc are nearly a factor of 20× above the EPA set drinking water standards. However, sequestration of Tc(IV) into Fe(III)-bearing phases, such as goethite, iron-bearing phyllosilicates and, perhaps, siderite, may ameliorate concerns over the mobility of Tc. A key factor, elucidated through experiment, in retarding the mobility of Tc in the environment is isolation from exposure to oxygen. One way to achieve isolation from oxygen occurs when Tc is locked in a crystallographic position in a solid phase.

Immobilization of 99-Technetium (VII) by Fe(II)-Goethite and Limited Reoxidation

During the nuclear waste vitrification process volatilized (99)Tc will be trapped by melter off-gas scrubbers and then washed out into caustic solutions, and plans are currently being contemplated for the disposal of such secondary waste. Solutions containing pertechnetate [(99)Tc(VII)O(4)(-)] were mixed with precipitating goethite and dissolved Fe(II) to determine if an iron (oxy)hydroxide-based waste form can reduce Tc(VII) and isolate Tc(IV) from oxygen. The results of these experiments demonstrate that Fe(II) with goethite efficiently catalyzes the reduction of technetium in deionized water and complex solutions that mimic the chemical composition of caustic waste scrubber media. Identification of the phases, goethite + magnetite, was performed using XRD, SEM and TEM methods. Analyses of the Tc-bearing solid products by XAFS indicate that all of the Tc(VII) was reduced to Tc(IV) and that the latter is incorporated into goethite or magnetite as octahedral Tc(IV). Batch dissolution experiments, conducted under ambient oxidizing conditions for more than 180 days, demonstrated a very limited release of Tc to solution (2-7 μg Tc/g solid). Incorporation of Tc(IV) into the goethite lattice thus provides significant advantages for limiting reoxidation and curtailing release of Tc disposed in nuclear waste repositories.

Uranium in Framboidal Pyrite from a Naturally Bioreduced Alluvial Sediment

Samples of a naturally bioreduced, U-contaminated alluvial sediment were characterized with various microscopic and spectroscopic techniques and wet chemical extraction methods. The objective was to investigate U association and interaction with minerals of the sediment. Bioreduced sediment comprises approximately 10% of an alluvial aquifer adjacent to the Colorado River, in Rifle, CO, that was the site of a former U milling operation. Past and ongoing research has demonstrated that bioreduced sediment is elevated in solid-associated U, total organic carbon, and acid-volatile sulfide, and depleted in bioavailable Fe(III) confirming that sulfate and Fe(III) reduction have occurred naturally in the sediment. SEM/EDS analyses demonstrated that framboidal pyrites (FeS(2)) of different sizes ( approximately 10-20 microm in diameter), and of various microcrystal morphology, degree of surface weathering, and internal porosity were abundant in the <53 microm fraction (silt + clay) of the sediment and absent in adjacent sediments that were not bioreduced. SEM-EMPA, XRF, EXAFS, and XANES measurements showed elevated U was present in framboidal pyrite as both U(VI) and U(IV). This result indicates that U may be sequestered in situ under conditions of microbially driven sulfate reduction and pyrite formation. Conversely, such pyrites in alluvial sediments provide a long-term source of U under conditions of slow oxidation, contributing to the persistence of U of some U plumes. These results may also help in developing remedial measures for U-contaminated aquifers.

Abiotic reductive immobilization of U(VI) by biogenic mackinawite.

During subsurface bioremediation of uranium-contaminated sites, indigenous metal and sulfate-reducing bacteria may utilize a variety of electron acceptors, including ferric iron and sulfate that could lead to the formation of various biogenic minerals in situ. Sulfides, as well as structural and adsorbed Fe(II) associated with biogenic Fe(II)-sulfide phases, can potentially catalyze abiotic U(VI) reduction via direct electron transfer processes. In the present work, the propensity of biogenic mackinawite (Fe 1+x S, x = 0 to 0.11) to reduce U(VI) abiotically was investigated. The biogenic mackinawite produced by Shewanella putrefaciens strain CN32 was characterized by employing a suite of analytical techniques including TEM, SEM, XAS, and Mössbauer analyses. Nanoscale and bulk analyses (microscopic and spectroscopic techniques, respectively) of biogenic mackinawite after exposure to U(VI) indicate the formation of nanoparticulate UO2. This study suggests the relevance of sulfide-bearing biogenic minerals in mediating abiotic U(VI) reduction, an alternative pathway in addition to direct enzymatic U(VI) reduction.

RETENTION AND TRANSPORT OF CALCIUM NITRATE IN VARIABLE CHARGE SUBSOILS

Salt retention has been observed in many variable charge soils. However, studies on the extent of the nitrate salt retention in tropical and subtropical soils are not documented in the literature. No attempts have been made to relate the extent of nitrate salt retention with soil mineralogy and the parameters of the soil chemistry, such as cation and anion exchange capacities (CEC and AEC) and soil solution pH and ionic strength (IS). Our objective was to provide evidence of the retention of Ca(NO3)2 in variable charge subsoils with extremely diverse mineralogical and chemical characteristics and to estimate the change in the extent of salt retention as a function of pH and IS. Laboratory leaching experiments were conducted with disturbed subsoil materials collected from the southeastern United States and other areas. Four lime treatments and four Ca(NO3)2 solutions of different concentrations were used to test the effect of pH and IS on nitrate salt retention. The results show that the transport of Ca(NO3)2 is affected by soil mineralogy and chemistry. The magnitude of salt retention was higher in subsoils with appreciable AEC and equivalent amounts of CEC, where both kaolinite and Al/Fe oxides dominate the clay fraction. In the subsoils with the highest magnitude, the electrical conductivity breakthrough curves (EC BTC) have an extended plateau of low EC values, and the first pore volumes of leachate contain virtually no salt. The cation and anion of the leaching electrolyte (Ca++ and NO3−) are adsorbed with no net release of other ions from exchange sites. Both pH and IS of the subsoil solution affect ion transport and alter the extent of Ca(NO3)2 retention. This study leads to the conclusion that mineralogy, surface charge, pH, and IS affect the magnitude of salt retention in variable charge subsoils, and their effects should be considered when predicting ion mobility and transport in these subsoils.

Chapter Two - terrestrial nanoparticles and their controls on soil-/geo-processes and reactions.

Abstract This review provides insights on some unique properties of nanoparticles (NPs) that are present in soils. In addition, this review discusses the role of NPs in controlling or influencing single and/or coupled chemical, biological, and hydrological soil- and/or geo-processes, which directly or indirectly affect the mobility or may determine the ultimate fate of aqueous and sorbed (adsorbed or precipitated) chemical species of nutrients and contaminants in terrestrial ecosystems. The chapter is composed of five review sections, followed by another section on future research directions, the acknowledgments, and the list of the references. A brief introduction to nanotechnology, nanoscience and environmental soil nanoscience, and definitions of relevant terms and chapter objectives are provided in the first section. A discussion on size-dependent properties and controls, focusing initially on the differences in nanoscale versus bulk scale properties, and later on the properties that change within the nanoscale, is presented in the second section. The important topic of NP origin (natural or manufactured) and occurrence in soils is presented in the third section. The behavior of NPs in soils is discussed in the fourth section. Two subsections are included. In the first one, processes that may affect NPs behavior in soils, such as growth, stability, solid phase transformation, aggregation, and aging are discussed. In the second one, processes that may be affected by the presence of NPs in soils, such as contaminant and/or nutrient sorption, redox reactions, and their advective or diffusive mobility, are discussed. A brief discussion on NPs toxicity is presented in the fifth and last review section of this chapter.

Cr(OH) 3 (s) Oxidation Induced by Surface Catalyzed Mn(II) Oxidation

We examined the feasibility of Cr(OH)3(s) oxidation mediated by surface catalyzed Mn(II) oxidation under common groundwater pH conditions as a potential pathway of natural Cr(VI) contaminations. Dissolved Mn(II) (50 μM) was reacted with or without synthesized Cr(OH)3(s) (1.0 g/L) at pH 7.0-9.0 under oxic or anoxic conditions. Homogeneous Mn(II) oxidation by dissolved O2 was not observed at pH ≤ 8.0 for 50 days. At pH 9.0, by contrast, dissolved Mn(II) was completely removed within 8 days and precipitated as hausmannite. When Cr(OH)3(s) was present, this solid was oxidized and released substantial amounts of Cr(VI) as dissolved Mn(II) was added into the suspension at pH ≥ 8.0 under oxic conditions. Production of Cr(VI) was attributed to Cr(OH)3(s) oxidation by a newly formed Mn oxide via Mn(II) oxidation catalyzed on Cr(OH)3(s) surface. XANES results indicated that this surface-catalyzed Mn(II) oxidation produced a mixed valence Mn(III/IV) solid phase. Our results suggest that toxic Cr(VI) can be naturally produced via Cr(OH)3(s) oxidation coupled with the oxidation of dissolved Mn(II). In addition, this study evokes the potential environmental hazard of sparingly soluble Cr(OH)3(s), which has been considered the most common and a stable remediation product of Cr(VI) contamination.

Influence of acidic and alkaline waste solution properties on uranium migration in subsurface sediments

This study shows that acidic and alkaline wastes co-disposed with uranium into subsurface sediments have significant impact on changes in uranium retardation, concentration, and mass during downward migration. For uranium co-disposal with acidic wastes, significant rapid (i.e., hours) carbonate and slow (i.e., 100 s of hours) clay dissolution resulted, releasing significant sediment-associated uranium, but the extent of uranium release and mobility change was controlled by the acid mass added relative to the sediment proton adsorption capacity. Mineral dissolution in acidic solutions (pH2) resulted in a rapid (<10 h) increase in aqueous carbonate (with Ca(2+), Mg(2+)) and phosphate and a slow (100 s of hours) increase in silica, Al(3+), and K(+), likely from 2:1 clay dissolution. Infiltration of uranium with a strong acid resulted in significant shallow uranium mineral dissolution and deeper uranium precipitation (likely as phosphates and carbonates) with downward uranium migration of three times greater mass at a faster velocity relative to uranium infiltration in pH neutral groundwater. In contrast, mineral dissolution in an alkaline environment (pH13) resulted in a rapid (<10h) increase in carbonate, followed by a slow (10 s to 100 s of hours) increase in silica concentration, likely from montmorillonite, muscovite, and kaolinite dissolution. Infiltration of uranium with a strong base resulted in not only uranium-silicate precipitation (presumed Na-boltwoodite) but also desorption of natural uranium on the sediment due to the high ionic strength solution, or 60% greater mass with greater retardation compared with groundwater. Overall, these results show that acidic or alkaline co-contaminant disposal with uranium can result in complex depth- and time-dependent changes in uranium dissolution/precipitation reactions and uranium sorption, which alter the uranium migration mass, concentration, and velocity.