Phenazine-1-Carboxylic Acid-Producing Bacteria Enhance the Reactivity of Iron Minerals in Dryland and Irrigated Wheat Rhizospheres.

Phenazine-1-carboxylic acid (PCA) is a broad-spectrum antibiotic produced by rhizobacteria in the dryland wheat fields of the Columbia Plateau. PCA and other phenazines reductively dissolve Fe and Mn oxyhydroxides in bacterial culture systems, but the impact of PCA upon Fe and Mn cycling in the rhizosphere is unknown. Here, concentrations of dithionite-extractable and poorly crystalline Fe were approximately 10% and 30-40% higher, respectively, in dryland and irrigated rhizospheres inoculated with the PCA-producing (PCA+) strain Pseudomonas synxantha 2-79 than in rhizospheres inoculated with a PCA-deficient mutant. However, rhizosphere concentrations of Fe(II) and Mn did not differ significantly, indicating that PCA-mediated redox transformations of Fe and Mn were transient or were masked by competing processes. Total Fe and Mn uptake into wheat biomass also did not differ significantly, but the PCA+ strain significantly altered Fe translocation into shoots. X-ray absorption near edge spectroscopy revealed an abundance of Fe-bearing oxyhydroxides and phyllosilicates in all rhizospheres. These results indicate that the PCA+ strain enhanced the reactivity and mobility of Fe derived from soil minerals without producing parallel changes in plant Fe uptake. This is the first report that directly links significant alterations of Fe-bearing minerals in the rhizosphere to a single bacterial trait.

Phenazine-1-carboxylic acid and soil moisture influence biofilm development and turnover of rhizobacterial biomass on wheat root surfaces.

Phenazine-1-carboxylic acid (PCA) is produced by rhizobacteria in dryland but not in irrigated wheat fields of the Pacific Northwest, USA. PCA promotes biofilm development in bacterial cultures and bacterial colonization of wheat rhizospheres. However, its impact upon biofilm development has not been demonstrated in the rhizosphere, where biofilms influence terrestrial carbon and nitrogen cycles with ramifications for crop and soil health. Furthermore, the relationships between soil moisture and the rates of PCA biosynthesis and degradation have not been established. In this study, expression of PCA biosynthesis genes was upregulated relative to background transcription, and persistence of PCA was slightly decreased in dryland relative to irrigated wheat rhizospheres. Biofilms in dryland rhizospheres inoculated with the PCA-producing (PCA+ ) strain Pseudomonas synxantha 2-79RN10 were more robust than those in rhizospheres inoculated with an isogenic PCA-deficient (PCA- ) mutant strain. This trend was reversed in irrigated rhizospheres. In dryland PCA+ rhizospheres, the turnover of 15 N-labelled rhizobacterial biomass was slower than in the PCA- and irrigated PCA+ treatments, and incorporation of bacterial 15 N into root cell walls was observed in multiple treatments. These results indicate that PCA promotes biofilm development in dryland rhizospheres, and likely influences crop nutrition and soil health in dryland wheat fields.

Quantitative Effects of Biochar Oxidation and Pyrolysis Temperature on the Transport of Pathogenic and Nonpathogenic Escherichia coli in Biochar-Amended Sand Columns.

The present study quantifies the transport of Escherichia coli pathogenic O157:H7 and nonpathogenic K12 strains in water-saturated Quincy sand (QS) columns amended with oxidized (OX) or unoxidized (UO) pine wood (PW) or pine bark (PB) biochar produced at either 350 or 600 °C. Our results showed that (1) the addition of oxidized biochar into QS columns enhanced the transport of E. coli O157:H7 by 3.1 fold compared to the unoxidized counterparts, likely because of an increase in the repulsive forces due to their higher negative charge densities. (2) The retention of E. coli O157:H7 was 3.3 fold higher than that of E. coli K12 in all biochar-amended sand columns. (3) Increased application rates of unoxidized PW600 biochar from 0 to 20 wt % led to a reduction in the transport of E. coli O157:H7 and K12 from 98 to 10% and from 95 to 70%, respectively. Our data showed that mixing sand with PW350-UO at a 20 wt % application rate almost completely retained the pathogenic E. coli in the subsurface, suggesting that utilizing sand mixed with biochar can act as a promising biofilter capable of protecting natural aquafers from pathogens.

The role of biochar porosity and surface functionality in augmenting hydrologic properties of a sandy soil.

This paper reports studies to elucidate the potential relationships between porosity and surface functionality of biochar and soil water retention characteristics. The biochars studied were produced from pine wood (PW), hybrid poplar wood (HP), and pine bark (PB) at temperatures of 350°C and 600°C. The resulting materials were then oxidized under air at 250°C to generate oxygenated functional groups on the surface. All biochar were thoroughly characterized (surface and bulk properties) and their hydrological properties measured in blends with Quincy sand. We prepared 39 microcosms for this study to examine the effect of biochar functionalities and porosity on the hydro-physical properties of Quincy sand. Each biochar was thoroughly mixed with the soil at 20gkg-1. The field capacity, wilting point, and total available soil moisture of the bio-char/Quincy sand mixtures were measured for both dry and wet ranges. The soil water potentials and soil water contents were fitted using the model of van Genuchten. Our results indicated that the amount of oxygenated functional groups on the surface of biochars clearly differentiated the biochars in terms of hydrophilicity, with the oxidized biochars being superior, followed by the low-temperature biochars, while the high temperature biochars possessed lowest hydrophilicity. As a result, oxidized biochars exhibited better wettability compared to unoxidized biochars, regardless their feedstock source. Significant correlation occurred between the total acidic functional groups on biochar surface and water contents at different matric potentials. Over a wide range of soil water potentials, oxidized biochar-soil mixtures held more water than the unoxidized biochar-soil mixtures except in the region between -0.1 and -5kPa of ψ, which is near saturation. Soil water contents at different matric potentials were significantly inter-correlated (P<0.01) and correlated with bulk densities of biochar-amended soil samples.

Competitive incorporation of perrhenate and nitrate into sodalite.

Nuclear waste storage tanks at the Hanford site in southeastern Washington have released highly alkaline solutions, containing radioactive and other contaminants, into subsurface sediments. When this waste reacts with subsurface sediments, feldspathoid minerals (sodalite, cancrinite) can form, sequestering pertechnetate (99TcO4-) and other ions. This study investigates the potential for incorporation of perrhenate (ReO4-), a chemical surrogate for 99TcO4-, into mixed perrhenate/nitrate (ReO4-/NO3-) sodalite. Mixed-anion sodalites were hydrothermally synthesized in the laboratory from zeolite A in sodium hydroxide, nitrate, and perrhenate solutions at 90 °C for 24 h. The resulting solids were characterized by bulk chemical analysis, X-ray diffraction, scanning electron microscopy, and X-ray absorption near edge structure spectroscopy (XANES) to determine the products' chemical composition, structure, morphology, and Re oxidation state. The XANES data indicated that nearly all rhenium (Re) was incorporated as Re(VII)O4-. The nonlinear increase of the unit cell parameter with ReO4-/NO3- ratios suggests formation of two separate sodalite phases in lieu of a mixed-anion sodalite. The results reveal that the sodalite cage is highly selective toward NO3- over ReO4-. Calculated enthalpy and Gibbs free energy of formation at 298 K for NO3- and ReO4-sodalite suggest that NO3- incorporation into the cage is favored over the incorporation of the larger ReO4-, due to the smaller ionic radius of NO3-. Based on these results, it is expected that NO3-, which is present at significantly higher concentrations in alkaline waste solutions than 99TcO4-, will be strongly preferred for incorporation into the sodalite cage.

Colloid mobilization and transport during capillary fringe fluctuations.

Capillary fringe fluctuations due to changing water tables lead to displacement of air-water interfaces in soils and sediments. These moving air-water interfaces can mobilize colloids. We visualized colloids interacting with moving air-water interfaces during capillary fringe fluctuations by confocal microscopy. We simulated capillary fringe fluctuations in a glass-bead-filled column. We studied four specific conditions: (1) colloids suspended in the aqueous phase, (2) colloids attached to the glass beads in an initially wet porous medium, (3) colloids attached to the glass beads in an initially dry porous medium, and (4) colloids suspended in the aqueous phase with the presence of a static air bubble. Confocal images confirmed that the capillary fringe fluctuations affect colloid transport behavior. Hydrophilic negatively charged colloids initially suspended in the aqueous phase were deposited at the solid-water interface after a drainage passage, but then were removed by subsequent capillary fringe fluctuations. The colloids that were initially attached to the wet or dry glass bead surface were detached by moving air-water interfaces in the capillary fringe. Hydrophilic negatively charged colloids did not attach to static air-bubbles, but hydrophobic negatively charged and hydrophilic positively charged colloids did. Our results demonstrate that capillary fringe fluctuations are an effective means for colloid mobilization.

Does water content or flow rate control colloid transport in unsaturated porous media?

Mobile colloids can play an important role in contaminant transport in soils: many contaminants exist in colloidal form, and colloids can facilitate transport of otherwise immobile contaminants. In unsaturated soils, colloid transport is, among other factors, affected by water content and flow rate. Our objective was to determine whether water content or flow rate is more important for colloid transport. We passed negatively charged polystyrene colloids (220 nm diameter) through unsaturated sand-filled columns under steady-state flow at different water contents (effective water saturations Se ranging from 0.1 to 1.0, with Se = (θ - θr)/(θs - θr)) and flow rates (pore water velocities v of 5 and 10 cm/min). Water content was the dominant factor in our experiments. Colloid transport decreased with decreasing water content, and below a critical water content (Se < 0.1), colloid transport was inhibited, and colloids were strained in water films. Pendular ring and water film thickness calculations indicated that colloids can move only when pendular rings are interconnected. The flow rate affected retention of colloids in the secondary energy minimum, with less colloids being trapped when the flow rate increased. These results confirm the importance of both water content and flow rate for colloid transport in unsaturated porous media and highlight the dominant role of water content.

Does colloid shape affect detachment of colloids by a moving air-water interface?

Air-water interfaces interact strongly with colloidal particles by capillary forces. The magnitude of the interaction force depends on, among other things, the particle shape. Here, we investigate the effects of particle shape on colloid detachment by a moving air-water interface. We used hydrophilic polystyrene colloids with four different shapes (spheres, barrels, rods, and oblong disks), but otherwise identical surface properties. The nonspherical shapes were created by stretching spherical microspheres on a film of polyvinyl alcohol (PVA). The colloids were then deposited onto the inner surface of a glass channel. An air bubble was introduced into the channel and passed through, thereby generating a receding followed by an advancing air-water interface. The detachment of colloids by the air-water interfaces was visualized with a confocal microscope, quantified by image analysis, and analyzed statistically to determine significant differences. For all colloid shapes, the advancing air-water interface caused pronounced colloid detachment (>63%), whereas the receding interface was ineffective in colloid detachment (<1.5%). Among the different colloid shapes, the barrels were most readily removed (94%) by the advancing interface, followed by the spheres and oblong disks (80%) and the rods (63%). Colloid detachment was significantly affected by colloid shape. The presence of an edge, as it occurs in a barrel-shaped colloid, promoted colloid detachment because the air-water interface is being pinned at the edge of the colloid. This suggests that the magnitude of colloid mobilization and transport in porous media is underestimated for edged particles and overestimated for rodlike particles when a sphere is used as a model colloid.

Transport of europium colloids in vadose zone lysimeters at the semiarid Hanford site.

The objective of this study was to quantify transport of Eu colloids in the vadose zone at the semiarid Hanford site. Eu-hydroxy-carbonate colloids, Eu(OH)(CO3), were applied to the surface of field lysimeters, and migration of the colloids through the sediments was monitored using wick samplers. The lysimeters were exposed to natural precipitation (145-231 mm/year) or artificial irrigation (124-348 mm/year). Wick outflow was analyzed for Eu concentrations, supplemented by electron microscopy and energy-dispersive X-ray analysis. Small amounts of Eu colloids (<1%) were detected in the deepest wick sampler (2.14 m depth) 2.5 months after application and cumulative precipitation of only 20 mm. We observed rapid transport of Eu colloids under both natural precipitation and artificial irrigation; that is, the leading edge of the Eu colloids moved at a velocity of 3 cm/day within the first 2 months after application. Episodic infiltration (e.g., Chinook snowmelt events) caused peaks of Eu in the wick outflow. While a fraction of Eu moved consistent with long-term recharge estimates at the site, the main mass of Eu remained in the top 30 cm of the sediments. This study illustrates that, under field conditions, near-surface colloid mobilization and transport occurred in Hanford sediments.

Diffusive release of uranium from contaminated sediments into capillary fringe pore water.

Despite remediation efforts at the former nuclear weapons facility, leaching of uranium (U) from contaminated sediments to the ground water persists at the Hanford site 300 Area. Flooding of contaminated capillary fringe sediments due to seasonal changes in the Columbia River stage has been identified as a source for U supply to ground water. We investigated U release from Hanford capillary fringe sediments by packing sediments into reservoirs of centrifugal filter devices and saturating them with Columbia River water for 3 to 84days at varying solution-to-solid ratios. After specified times, samples were centrifuged. Within the first three days, there was an initial rapid release of 6-9% of total U, independent of the solution-to-solid ratio. After 14days of reaction, however, the experiments with the narrowest solution-to-solid ratios showed a decline in dissolved U concentrations. The removal of U from the solution phase was accompanied by removal of Ca and HCO(3)(-). Geochemical modeling indicated that calcite could precipitate in the narrowest solution-to-solid ratio experiment. After the rapid initial release in the first three days for the wide solution-to-solid ratio experiments, there was sustained release of U into the pore water. This sustained release of U from the sediments had diffusion-limited kinetics.

Links among nitrification, nitrifier communities, and edaphic properties in contrasting soils receiving dairy slurry.

Soil biotic and abiotic factors strongly influence nitrogen (N) availability and increases in nitrification rates associated with the application of manure. In this study, we examine the effects of edaphic properties and a dairy (Bos taurus) slurry amendment on N availability, nitrification rates and nitrifier communities. Soils of variable texture and clay mineralogy were collected from six USDA-ARS research sites and incubated for 28 d with and without dairy slurry applied at a rate of ~300 kg N ha(-1). Periodically, subsamples were removed for analyses of 2 M KCl extractable N and nitrification potential, as well as gene copy numbers of ammonia-oxidizing bacteria (AOB) and archaea (AOA). Spearman coefficients for nitrification potentials and AOB copy number were positively correlated with total soil C, total soil N, cation exchange capacity, and clay mineralogy in treatments with and without slurry application. Our data show that the quantity and type of clay minerals present in a soil affect nitrifier populations, nitrification rates, and the release of inorganic N. Nitrogen mineralization, nitrification potentials, and edaphic properties were positively correlated with AOB gene copy numbers. On average, AOA gene copy numbers were an order of magnitude lower than those of AOB across the six soils and did not increase with slurry application. Our research suggests that the two nitrifier communities overlap but have different optimum environmental conditions for growth and activity that are partly determined by the interaction of manure-derived ammonium with soil properties.

Adsorption and desorption of chlorpyrifos to soils and sediments.

Chlorpyrifos, one of the most widely used insecticides, has been detected in air, rain, marine sediments, surface waters, drinking water wells, and solid and liquid dietary samples collected from urban and rural areas. Its metabolite, TCP, has also been widely detected in urinary samples collected from people of various age groups. With a goal of elucidating the factors that control the environmental contamination, impact, persistence, and ecotoxicity of chlorpyrifos, we examine, in this review, the peer-reviewed literature relating to chlorpyrifos adsorption and desorption behavior in various solid-phase matrices. Adsorption tends to reduce chlorpyrifos mobility, but adsorption to erodible particulates, dissolved organic matter, or mobile inorganic colloids enhances its mobility. Adsorption to suspended sediments and particulates constitutes a major off-site migration route for chlorpyrifos to surface waters, wherein it poses a potential danger to aquatic organisms. Adsorption increases the persistence of chlorpyrifos in the environment by reducing its avail- ability to a wide range of dissipative and degradative forces, whereas the effect of adsorption on its ecotoxicity is dependent upon the route of exposure. Chlorpyrifos adsorbs to soils, aquatic sediments, organic matter, and clay minerals to differing degrees. Its adsorption strongly correlates with organic carbon con- tent of the soils and sediments. A comprehensive review of studies that relied on the batch equilibrium technique yields mean and median Kd values for chlorpyrifos of 271 and 116 L/kg for soils, and 385 and 403 L/kg for aquatic sediments. Chlorpyrifos adsorption coefficients spanned two orders of magnitude in soils. Normalizing the partition coefficient to organic content failed to substantially reduce variability to commonly acceptable level of variation. Mean and median values for chlorpyrifos partition coefficients normalized to organic carbon, K, were 8,163 and 7,227 L/kg for soils and 13,439 and 15,500 L/kg for sediipents. This variation may result from several factors, including various experimental artifacts, variation in quality of soil organic matter, and inconsistencies in experimental methodologies. Based on this review, there appears to be no definitive quantification of chlorpyrifos adsorption or desorption characteristics. Thus, it is difficult to predict its adsorptive behavior with certainty, without resorting to experimental methods specific to the soil or sediment of interest. This limitation should be recognized in the context of current efforts to predict the risk, fate, and transport of chlorpyrifos based upon published partition coefficients. Based on a comprehensive review of the peer-reviewed literature related to adsorption and desorption of chlorpyrifos, we propose the following key areas for future research. From this review, it becomes increasingly evident that pesticide partitioning cannot be fully accounted for by the fraction of soil or solid-matrix organic matter or carbon content. Therefore, research that probes the variation in the nature and quality of soil organic matter on pesticide adsorption is highly desirable. Pesticide persistence and bioavailability depend on insights into desorption capacity. Therefore, understanding the fate and environmental impact of hydrophobic pesticides is incomplete without new research being performed to improve insights into pesticide desorption from soils and sediments. There is also a need for greater attention and consistency in developing experimental methods aimed at estimating partition coefficients. Moreover, in such testing, choosing initial concentrations and liquid-solid ratios that are more representative of environmental conditions could improve usefulness and interpretation of data that are obtained. Future monitoring efforts should include the sampling and analysis of suspended particulates to account for suspended solid-phase CPF, a commonly underestimated fraction in surface water quality monitoring programs. Finally, management practices related to the reduction of off-site migration of CPF should be further evaluated, including alternative agricultural practices leading to reduction in soil erosion and structural best management practices, such as sedimentation ponds, treatment wetlands, and vegetated edge-of-field strips.

Nonsingular adsorption/desorption of chlorpyrifos in soils and sediments: experimental results and modeling.

At environmentally relevant concentrations in soils and sediments, chlorpyrifos, a hydrophobic organic insecticide, showed strong adsorption that correlated significantly with organic matter content. Chlorpyrifos desorption followed a nonsingular falling desorption isotherm that was estimated using a memory-dependent mathematical model. Desorption of chlorpyrifos was biphasic in nature, with a labile and nonlabile component. The labile component comprised 18-28% of the original solid-phase concentration, and the residue was predicted to slowly partition to the aqueous phase, implying long-term desorption from contaminated soils or sediments. The newly proposed mechanism to explain sorption/desorption hysteresis and biphasic desorption is the unfavorable thermodynamic energy landscape arising from limitation of diffusivity of water molecules through the strongly hydrophobic domain of soils and sediments. Modeling results suggest that contaminated soils and sediments could be secondary long-term sources of pollution. Long-term desorption may explain the detection of chlorpyrifos and other hydrophobic organic compounds in aquatic systems far from application sites, an observation that contradicts conventional transport predictions.

Detachment of deposited colloids by advancing and receding air-water interfaces.

Moving air-water interfaces can detach colloidal particles from stationary surfaces. The objective of this study was to quantify the effects of advancing and receding air-water interfaces on colloid detachment as a function of interface velocity. We deposited fluorescent, negatively charged, carboxylate-modified polystyrene colloids (diameter of 1 µm) into a cylindrical glass channel. The colloids were hydrophilic with an advancing air-water contact angle of 60° and a receding contact angle of 40°. After colloid deposition, two air bubbles were sequentially introduced into the glass channel and passed through the channel at different velocities (0.5, 7.7, 72, 982, and 10,800 cm/h). The passage of the bubbles represented a sequence of receding and advancing air-water interfaces. Colloids remaining in the glass channel after each interface passage were visualized with confocal microscopy and quantified by image analysis. The advancing air-water interface was significantly more effective in detaching colloids from the glass surface than the receding interface. Most of the colloids were detached during the first passage of the advancing air-water interface, while the subsequent interface passages did not remove significant amounts of colloids. Forces acting on the colloids calculated from theory corroborate our experimental results, and confirm that the detachment forces (surface tension forces) during the advancing air-water interface movement were stronger than during the receding movement. Theory indicates that, for hydrophilic colloids, the advancing interface movement generally exerts a stronger detachment force than the receding, except when the hysteresis of the colloid-air-water contact angle is small and that of the channel-air-water contact angle is large.

Comparison of different methods to measure contact angles of soil colloids.

We compared five different methods, static sessile drop, dynamic sessile drop, Wilhelmy plate, thin-layer wicking, and column wicking, to determine the contact angle of colloids typical for soils and sediments. The colloids (smectite, kaolinite, illite, goethite, hematite) were chosen to represent 1:1 and 2:1 layered aluminosilicate clays and sesquioxides, and were either obtained in pure form or synthesized in our laboratory. Colloids were deposited as thin films on glass slides, and then used for contact angle measurements using three different test liquids (water, formamide, diiodomethane). The colloidal films could be categorized into three types: (1) films without pores and with polar-liquid interactions (smectite), (2) films with pores and with polar-liquid interactions (kaolinite, illite, goethite), and (3) films without pores and no polar-liquid interactions (hematite). The static and dynamic sessile drop methods yielded the most consistent contact angles. For porous films, the contact angles decreased with time, and we consider the initial contact angle to be the most accurate. The differences in contact angles among the different methods were large and varied considerably: the most consistent contact angles were obtained for kaolinite with water, and illite with diiodomethane (contact angles were within 3 degrees); but mostly the differences ranged from 10 degrees to 40 degrees among the different methods. The thin-layer and column wicking methods were the least consistent methods.

Cesium desorption from illite as affected by exudates from rhizosphere bacteria.

Biogeochemical processes in the rhizosphere can significantly alter interactions between contaminants and soil minerals. In this study, several strains of bacteria that exude aluminum (Al)-chelating compounds were isolated from the rhizosphere of crested wheatgrass (Agropyron desertorum) collected from the Idaho National Laboratory (INL). We examined the effects of exudates from bacteria in the genera Bacillus, Ralstonia, and Enterobacter on cesium (Cs) desorption from illite. Exudates from these strains of bacteria significantly enhanced Cs desorption from illite. In addition, Cs desorption increased with increasing Bacillus exudate concentrations. Cesium desorption from illite as a function of both exudate type and concentration was positively correlated with Al dissolution, suggesting that the Al-complexing ability of the exudates played an important role in enhancing Cs desorption. The density of frayed edge sites (FES) on illite increased as a result of treatment with bacterial exudates, while the Cs/K selectivity of FES decreased. These results suggestthat exudates from bacteria isolated from the rhizosphere can enhance Cs desorption from frayed edges of illite and, therefore, can alter Cs availability in micaceous soils.

Colloid-facilitated transport of cesium in variably saturated Hanford sediments.

Radioactive 137Cs has leaked from underground waste tanks into the vadose zone at the Hanford Reservation in south-central Washington State. There is concern that 137Cs, currently located in the vadose zone, can reach the groundwater. In this study, we investigated whether, and to what extent, colloidal particles can facilitate the transport of 137Cs at Hanford. We used colloidal materials isolated from Hanford sediments. Transport experiments were conducted under variably saturated, steady-state flow conditions in repacked, 20 cm long Hanford sediment columns, with effective water saturations ranging from 0.2 to 1.0. Cesium, pre-associated with colloids, was stripped off during transport through the sediments. The higher the flow rates, the less Cs was stripped off, indicating in part that Cs desorption from carrying colloids was a residence-time-dependent process. Depending on the flow rate, up to 70% of the initially sorbed Cs desorbed from colloidal carriers and was captured in the stationary sediments. Less Cs was stripped off colloids under unsaturated than under saturated flow conditions at similar flow rates. This phenomenon was likely due to the reduced availability of sorption sites for Cs on the sediments as the water content decreased and water flow was divided between mobile and immobile regions.

Colloid stability in vadose zone Hanford sediments.

We experimentally determined colloid stability of natural colloids extracted from vadose zone sediments from the U.S. Department of Energy's Hanford Reservation. We also used reference minerals, kaolinite, montmorillonite, and silica,for comparative purposes. Colloid stability was assessed with two different methods: the batch turbidity method and dynamic light scattering. Critical coagulation concentrations (CCCs) were determined for pure Na and pure Ca electrolyte solutions, as well for mimicked Hanford vadose zone pore waters with varying sodium adsorption ratios (SARs). Critical coagulation concentrations obtained from the batch turbidity method were sensitive to initial colloid mass concentrations, settling time, and CCC criteria. The lower the initial colloid concentration and the shorter the settling times were, the larger was the CCC. The CCCs determined from the dynamic light scattering, where diluted colloidal suspensions are used, were not dependent on settling time and arbitrary CCC criteria, so dynamic light scattering is therefore the preferred method to determine colloid stability. The CCC values determined from dynamic light scattering ranged from 90 to 200 mmol/L for Na systems and 1.7 to 3.8 mmol/L for Ca systems. The stability of natural colloids was intermediate between that of pure kaolinite and montmorillonite. The results indicate that colloids in the Hanford vadose zone form stable suspensions, i.e., are in the slow aggregation regime. Nonetheless, due to the long travel times in the vadose zone, nearly all colloids will aggregate and be removed from the water column before reaching groundwater levels.

Colloid formation in Hanford sediments reacted with simulated tank waste.

Solutions of high pH, ionic strength, and aluminum concentration have leaked into the subsurface from underground waste storage tanks atthe Hanford Reservation in Washington State. Here, we test the hypothesis that these waste solutions alter and dissolve the native minerals present in the sediments and that colloidal (diameter < 2 microm) feldspathoids form. We reacted Hanford sediments with simulated solutions representative of Hanford waste tanks. The solutions consisted of 1.4 or 2.8 mol/kg NaOH, 0.125 or 0.25 mol/kg NaAlO4, and 3.7 mol/kg NaNO3 and were contacted with the sediments for a period of 25 or 40 days at 50 degrees C. The colloidal size fraction was separated from the sediments and characterized in terms of mineralogy, morphology, chemical composition, and electrophoretic mobility. Upon reaction with tank waste solutions, native minerals released Si and other elements into the solution phase. This Si precipitated with the Al present in the waste solutions to form secondary minerals, identified as the feldspathoids cancrinite and sodalite. The solution phase was modeled with the chemical equilibrium model GMIN for solution speciation and saturation indices with respect to sodalite and cancrinite. The amount of colloidal material in the sediments increased upon reaction with waste solutions. At the natural pH found in Hanford sediments (pH 8) the newly formed minerals are negatively charged, similar to the unreacted colloidal material present in the sediments. The formation of colloidal material in Hanford sediments upon reaction with tank waste solutions is an important aspect to consider in the characterization of Hanford tank leaks and may affect the fate of hazardous radionuclides present in the tank waste.

Cesium migration in saturated silica sand and Hanford sediments as impacted by ionic strength.

Large amounts of 137Cs have been accidentally released to the subsurface from the Hanford nuclear site in the state of Washington, USA. The cesium-containing liquids varied in ionic strengths, and often had high electrolyte contents, mainly in the form of NaNO3 and NaOH, reaching concentrations up to several moles per liter. In this study, we investigated the effect of ionic strengths on Cs migration through two types of porous media: silica sand and Hanford sediments. Cesium sorption and transport was studied in 1, 10, 100, and 1000 mM NaCl electrolyte solutions at pH 10. Sorption isotherms were constructed from batch equilibrium experiments and the batch-derived sorption parameters were compared with column breakthrough curves. Column transport experiments were analyzed with a two-site equilibrium-nonequilibrium model. Cesium sorption to the silica sand in batch experiments showed a linear sorption isotherm for all ionic strengths, which matched well with the results from the column experiments at 100 and 1000 mM ionic strength; however, the column experiments at 1 and 10 mM ionic strength indicated a nonlinear sorption behavior of Cs to the silica sand. Transport through silica sand occurred under one-site sorption and equilibrium conditions. Cesium sorption to Hanford sediments in both batch and column experiments was best described with a nonlinear Freundlich isotherm. The column experiments indicated that Cs transport in Hanford sediments occurred under two-site equilibrium and nonequilibrium sorption. The effect of ionic strength on Cs transport was much more pronounced in Hanford sediments than in silica sands. Effective retardation factors of Cs during transport through Hanford sediments were reduced by a factor of 10 when the ionic strength increased from 100 to 1000 mM; for silica sand, the effective retardation was reduced by a factor of 10 when ionic strength increased from 1 to 1000 mM. A two order of magnitude change in ionic strength was needed in the silica sand to observe the same change in Cs retardation as in Hanford sediments.