Transport of strontium and cesium in simulated hanford tank waste leachate through quartz sand under saturated and unsaturated flow

We investigated the effects of water saturation and secondary precipitate formation on Sr and Cs transport through quartz sand columns under saturated and unsaturated flow. Column experiments were conducted at effective water saturation ranging from 0.2 to 1.0 under steady-state flow using either 0.1 M NaNO(3) or simulated tank waste leachate (STWL; 1 M NaNO(3) and 1 M NaOH) mimicking Hanford (Washington, USA) tank waste. In 0.1 M NaNO(3) columns, Sr transported like a conservative tracer, whereas Cs was retarded relative to Sr. The transport of Sr and Cs in the 0.1 M NaNO(3) columns under all water saturations could be described with the equilibrium convection-dispersion equation (CDE). In STWL columns, Sr mobility was significantly reduced compared to the 0.1 M NaNO(3) column, because Sr was incorporated into or sorbed to neo-formed secondary precipitates. Strontium sequestration by precipitates was confirmed by additional batch and electron micrograph analyses. In contrast(,) the transport of Cs was less affected by the STWL; retardation of Cs in STWL columns was similar to that found in 0.1 M NaNO(3) columns. Analysis of STWL column data revealed that both Sr and Cs breakthrough curves showed nonideal behavior that suggest nonequilibrium conditions, although nonlinear geochemical behavior cannot be ruled out.     

High-temperature sorption of cesium and strontium on dispersed kaolinite powders

Sorption of cesium and strontium on kaolinite powders was investigated as a means to minimize the emissions of these metals during certain high-temperature processes currently being developed to isolate and dispose of radiological and mixed wastes. In this work, nonradioactive aqueous cesium acetate or strontium acetate was atomized down the center of a natural gas flame supported on a variable-swirl burner in a refractory-lined laboratory-scale combustion facility. Kaolinite powder was injected at a postflame location in the combustor. Cesium readily vaporized in the high-temperature regions of the combustor, but was reactively scavenged onto dispersed kaolinite. Global sorption mechanisms of cesium vapor on kaolinite were quantified, and are related to those available in the literature for sodium and lead. Both metal adsorption and substrate deactivation steps are important, so there is an optimum temperature, between 1400 and 1500 K, at which maximum sorption occurs. The presence of chlorine inhibits cesium sorption. In contrast to cesium, and in the absence of chlorine, strontium was only partially vaporized and was, therefore, only partially scavengeable. The strontium data did not allow quantification of global kinetic mechanisms of interaction, although equilibrium arguments provided insight into the effects of chlorine on strontium sorption. These results have implications for the use of sorbents to control cesium and strontium emissions during high-temperature waste processing including incineration and vitrification.     

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.     

Strontium speciation during reaction of kaolinite with simulated tank-waste leachate: bulk and microfocused EXAFS analysis

Radioactive strontium (90Sr) is an important constituent of the complex wastes from past nuclear weapons production and has been stored in underground tanks at U.S. DOE sites (e.g., Hanford, WA). Using bulk and microfocused EXAFS spectroscopy, we examined temporal changes in solid-phase Sr speciation in kaolinite samples reacted for 1-369 d with high-pH, high ionic strength synthetic tank-waste leachate containing Sr(2+) and Cs(+) at 10(-3) mol kg(-1). Analyses of bulk EXAFS spectra showed that Sr initially forms a precipitate by 7 d with a local structure similar to SrCO(3-) (s). At 33 d, microfocused EXAFS of individual particles in one sample revealed a mixture of hydrated and dehydrated Sr associated with neoformed sodalite-type phases. At aging times of 93 d and longer, bulk EXAFS spectra and supporting characterizations indicated nonexchangeable Sr with a local structure consistent with incorporation into increasingly crystalline aluminosilicate particles, particularly sodalite. These experimental studies suggest that irreversible trapping of radionuclides occurs if they are present during the formation and aging of feldspathoid alteration products of local Si-bearing sediment minerals. This may serve as an effective contaminant sequestration mechanism at sites such as Hanford.     

Foaming in simulated radioactive waste

Radioactive waste treatment process usually involves concentration of radionuclides before waste can be immobilized by storing it in stable solid form. Foaming is observed at various stages of waste processing like SRAT (sludge receipt and adjustment tank) and melter operations. This kind of foaming greatly limits the process efficiency. The foam encountered can be characterized as a three-phase foam that incorporates finely divided solids (colloidal particles). The solid particles stabilize foaminess in two ways: by adsorption of biphilic particles at the surfaces of foam lamella and by layering of particles trapped inside the foam lamella. During bubble generation and rise, solid particles organize themselves into a layered structure due to confinement inside the foam lamella, and this structure provides a barrier against the coalescence of the bubbles, thereby causing foaming. Our novel capillary force balance apparatus was used to examine the particle-particle interactions, which affect particle layer formation in the foam lamella. Moreover, foaminess shows a maximum with increasing solid particle concentration. To explain the maximum in foaminess, a study was carried out on the simulated sludge, a non-radioactive simulant of the radioactive waste sludge at SRS, to identify the parameters that affect the foaming in a system characterized by the absence of surface-active agents. This three-phase foam does not show any foam stability unlike surfactant-stabilized foam. The parameters investigated were solid particle concentration, heating flux, and electrolyte concentration. The maximum in foaminess was found to be a net result of two countereffects that arise due to particle-particle interactions: structural stabilization and depletion destabilization. It was found that higher electrolyte concentration causes a reduction in foaminess and leads to a smaller bubble size. Higher heating fluxes lead to greater foaminess due to an increased rate of foam lamella generation in the sludge system.     

Perrhenate uptake by iron and aluminum oxyhydroxides: an analogue for pertechnetate incorporation in Hanford waste tank sludges

Perrhenate (ReO4-), a nonradioactive surrogate for pertechnetate (99TcO4-), was partitioned during precipitation and aging of iron and aluminum oxyhydroxide solids from aqueous simulants of high-level nuclear waste stored at Hanford, WA. Neutralization of acidic metal nitrate solutions (Al/Fe mole ratio 0.25 and 13.5; 40 ppm Re) to a final pH > 13, followed by aging at 90 degrees C for up to 18 weeks, resulted in substantial amounts of reversibly sorbed Re (approximately 1-10 ppm). Irreversibly sorbed Re increased in the Fe-dominated system with aging, reaching a final value of approximately 83 ppb after 168 h, in a mixture of hematite with minor goethite. Irreversibly sorbed Re in the Al-dominated system generally decreased with time to approximately 30 ppb after 18 weeks in solids dominated by boehmite. Increasing the total amount of Re to 1000 ppm increased the extent of irreversible sorption. The presence of 100 ppm Si prevented transformation of and irreversible Re uptake by ferrihydrite in Fe-dominated systems. In Al-dominated systems, 200 ppm Ni prevented hematite formation but did not affect perrhenate uptake. Results suggest that 5% of the 99Tc inventory in the Hanford waste tanks may be associated with the sludges, and approximately 0.5% incorporated into the solids under oxidizing conditions.     

pH neutralization and zonation in alkaline-saline tank waste plumes

At the Hanford Site in Washington State, the pH values of contaminant plumes resulting from leaking of initially highly alkaline-saline radioactive waste solutions into the subsurface are now found to be substantially neutralized. However, the nature of plume pH neutralization has not previously been understood. As a master geochemical variable, pH needs to be understood in order to predict the fate and transport of contaminants carried by the waste plumes. Through this laboratory study, we found that the plume pH values spanned a broad range from 14 (within the near-source region) down to the value of 7 (lower than the pH value of the initial soil solution) while the plume was still connected to an actively leaking source. We defined two zones within a plume: the silicate dissolution zone (SDZ, pH 14-10) and the neutralized zone (NZ, pH 10-7). Quartz dissolution at elevated temperature and precipitation of secondary silicates (including sodium metasilicate, cancrinite, and zeolites) are the key reactions responsible for the pH neutralization within the SDZ. The rapid and thorough cation exchange of Na+ replacing Ca2+/Mg2+, combined with transport, resulted in a dynamic Ca2+/Mg2+-enriched plume front. Subsequent precipitation of calcite, sodium silicate, and possibly talc led to dramatically reduced pH within the plume front and the neutralized zone. During aging (after the plume source became inactive), continued quartz dissolution and the secondary silicate precipitation drove the pH value lower, toward pH 11 at equilibrium within the SDZ, whereas the pH values in the NZ remained relatively unchanged with time. A pH profile of 11 from the plume source to pH 7 at the plume front is expected for a historical plume. This laboratory-based study provided realistic plume pH profiles (consistent with that measured from borehole samples) and identified underlying mechanisms responsible for pH evolution.     

Growth of gram-positive mastogenic bacteria in normal, simulated bulk tank, and mastitic milk held at simulated fluctuating temperatures of farm bulk tank

Growth of Staphylococcus aureus, Staphylococcus epidermidis, Streptococcus agalactiae, Streptococcus dysgalactiae, Streptococcus bovis, and Streptococcus uberis was studied in normal milk, simulated bulk tank milk, and aseptic mastitic milk held at simulated fluctuating temperatures of farm bulk tank for 48 h. With the exception of S. bovis, growth rates of the other five bacteria were similar in both normal and simulated bulk tank milk. Mastitic milk inhibited growth of all bacteria studied. A 24-h adjustment period occurred before most of the bacteria started growing. The mastitis level in a dairy herd may be monitored by cultures of bulk tank milk samples and by calculations as discussed in this study.     

Impact of electronic waste disposal on lead concentrations in landfill leachate

Lead is the element most likely to cause discarded electronic devices to be characterized as hazardous waste. To examine the fate of lead from discarded electronics in landfills, five columns were filled with synthetic municipal solid waste (MSW). A mix of electronic devices was added to three columns (6% by weight), while two columns served as controls. A sixth column contained waste excavated from an existing MSW landfill. Leachate quality was monitored for 440 days. In columns with the synthetic waste, leachate pH indicated that the simulated landfill environment was characteristic of the acid phase of waste decomposition; lead leachability should be greater in the acid phase of landfill degradation as compared to the methanogenic phase. Lead concentrations ranged from 7 to 66 microg/L in the columns containing electronic waste and ranged from < 2 to 54 microg/L in the control columns. Although the mean lead concentrations in the columns containing electronic devices were greater than those in the controls, the difference was not found to be statistically significant when comparing the data sets over the entire monitoring period. Lead results from the excavated waste column suggest that lead concentrations in all columns will decrease as the pH increases toward more neutral methanogenic conditions.     

Adhesion of oil to kaolinite in water

Uniform coats of kaolinite particles on a flat glass substrate were prepared to be sufficiently smooth and thin to allow reliable measurement of contact angles of captive crude oil drops in a range of salt solutions, without any particle removal. The contact angle hysteresis was used to infer the extent of oil adhesion via rupture of the intervening water film and anchoring of charged groups to kaolinite. For sodium chloride solutions, adhesion decreases monotonically with pH and/or salinity, with strong adhesion only manifested under acidic conditions with salinity at most 0.1 M. Calcium chloride solutions at pH around 6 switch from strong adhesion in the range 0.001-0.01 M to weak adhesion at higher concentrations. For all mixtures of sodium and calcium chlorides investigated, a total ionic strength above 0.1 M guarantees a weak adhesion of oil to kaolinite. Results are qualitatively consistent with theoretical expectations of electrostatic interactions, with H(+) and Ca(2+) being potential-determining ions for both interfaces.     

Raman study of aluminum speciation in simulated alkaline nuclear waste

The chemistry of concentrated sodium aluminate solutions stored in many of the large, underground storage tanks containing high-level waste (HLW) at the Hanford and Savannah River Nuclear Reservations is an area of recent research interest. Not only is the presence of aluminate in solution important for continued safe storage of these wastes, the nature of both solid and solution aluminum oxyhydroxides is important for waste pretreatment. Moreover, for many tanks that have leaked high aluminum waste in the past, little is known about the speciation of Al in the soil. In this study, Raman spectroscopy has been used to investigate the speciation of the aqueous species in the Al2O3-Na2O-H2O system over a wide range of solution compositions and hydration. A ternary phase diagram has been used to correlate the observed changes in the spectra with the composition of the solution and with dimerization of aluminate that occurs at elevated aluminate concentrations (>1.5 M). Dimerization is evidenced by growth of new Al-O stretching bands at 535 and 695 cm(-1) at the expense of the aluminate monomer band at 620 cm(-1). The spectrum of water was strongly influenced by the high concentrations of Na+ and OH- (>17 M). Upon increasing the concentration of NaOH in solution, the delta-(H-O-H) bending band of water (v2 mode) increased in frequency to 1663 cm(-1), indicating that the water contained in the concentrated caustic solution was more strongly hydrogen bonded at the higher base content. In addition, the sharp, well-resolved band at 3610 cm(-1), assigned to the v(O-H) of free OH-, increased in intensity with increasing NaOH. Analysis of the v(O-H) bands in the 3800-2600 cm(-1) region supported the overall increase in hydrogen bonding as evidenced by the increase in relative intensity of a strongly hydrated water band at 3118 cm(-1). Taking into consideration the activity of water, the molar concentrations of the monomeric and dimeric aluminate species were estimated using the relative intensities of the Al-O stretching bands from the Raman spectra. A constant apparent log Kdimer value was obtained at aluminate concentrations >1.5 M with a value of 0.97+/-0.04 at approximately 25 degrees C. This study represents the first spectral-based estimation of a thermodynamic equilibrium constant for the Al2O3-Na2O-H2O system.     

Effect of simulated rainfall and weathering on release of preservative elements from CCA treated wood

The release of arsenic from wood pressure-treated with chromated copper arsenate (CCA) can be decreased by application of wood finishes, but little is known about the types of finishes that are best suited for this purpose. This study evaluated the effects of finish water repellent content and ultraviolet (UV) radiation on the release of arsenic, copper, and chromium from CCA-treated wood exposed to simulated rainfall. Deck boards treated with CCA were either left unfinished or dipped in a finish prepared with 1%, 3%, or 5% water repellent. All specimens were exposed to leaching from simulated rainfall, and a subset of specimens was also exposed to UV radiation. The rainfall was collected and analyzed for total elemental arsenic, copper, and chromium. The water repellent significantly decreased the amounts of these elements in the runoff, but for the short duration of this study there was no difference among the three water repellent concentrations. It is possible that water repellent content would have a greater effect over a longer exposure period. Exposure to UV radiation caused a significant increase in leaching from both finished and unfinished specimens. This effect may be a result of increased surface area during weathering as well as loss of fibers caused by UV-induced surface erosion.     

Transport behavior of surrogate biological warfare agents in a simulated landfill: effect of leachate recirculation and water infiltration

An understanding of the transport behavior of biological warfare (BW) agents in landfills is required to evaluate the suitability of landfills for the disposal of building decontamination residue (BDR) following a bioterrorist attack on a building. Surrogate BW agents, Bacillus atrophaeus spores and Serratia marcescens, were spiked into simulated landfill reactors that were filled with synthetic building debris (SBD) and operated for 4 months with leachate recirculation or water infiltration. Quantitative polymerase chain reaction (Q-PCR) was used to monitor surrogate transport. In the leachate recirculation reactors, <10% of spiked surrogates were eluted in leachate over 4 months. In contrast, 45% and 31% of spiked S. marcescens and B. atrophaeus spores were eluted in leachate in the water infiltration reactors. At the termination of the experiment, the number of retained cells and spores in SBD was measured over the depth of the reactor. Less than 3% of the total spiked S. marcescens cells and no B. atrophaeus spores were detected in SBD. These results suggest that significant fractions of the spiked surrogates were strongly attached to SBD.     

Factors influencing luxury uptake of phosphorus by microalgae in waste stabilization ponds

Phosphorus removal in waste stabilization ponds (WSP) is highly variable, but the reasons for this are not well understood. Luxury uptake of phosphorus by microalgae has been studied in natural systems such as lakes but not under the conditions found in WSP. This work reports on the effects of phosphate concentration, light intensity, and temperature on luxury uptake of phosphorus by WSP microalgae in continuous culture bioreactors. Increasing temperature had a statistically significant "positive effect" on intracellular acid-insoluble polyphosphate concentration. It is likely that elevated temperature increased the rate of polyphosphate accumulation, but because the biomass was not starved of phosphate, the stored acid-insoluble polyphosphate was not utilized. Increasing light intensity had no effect on acid-insoluble polyphosphate but had a "negative effect" on the acid-soluble polyphosphate. A possible explanation for this is that the faster growth rate at high light intensity results in this form of polyphosphate being utilized by the cells for synthesis of cellular constituents at a rate that exceeds replenishment. The variability in the phosphorus content of the microalgal biomass shows that with this new understanding ofthe luxury uptake mechanism there is the potential to optimize WSP for biological phosphorus removal.     

Microscale distribution of cesium sorbed to biotite and muscovite

Individual 1-3 mm biotite and muscovite clasts from Hanford sediment were contacted with 0.08 M CsNO3. They were examined using electron or X-ray microprobe methods, as intact specimens or sectioned perpendicular to their basal planes. Cs+ was observed to preferentially sorb to mica edges, steps on mica surfaces, or fractured regions. The localization of Cs conformed to hypothesized strong binding to frayed edge sites in preference to sites on basal planes. In section, Cs+ was found to penetrate the mica interior, forming discrete zones of concentration, particularly in muscovite. In biotite, Cs was more abundant, permeating the clasts, but also forming discrete zones of higher concentration. Concentrated Cs on both clast edges and within clast interiors corresponded to microscopic but relatively extensive zones where K was depleted. The localization of sorbed Cs in areas where K was depleted suggested that weathering reactions had caused the formation of frayed edge sites within the micas. Cs+ accessed crystal interiors by diffusion along channels following crystal defects, cracks, or partings where pore fluids had previously migrated to form the interior alteration zones. On the nanometer scale, areas with localized Cs were disrupted, confirming that frayed edge sites were developed in clast interiors.     

Mechanisms of strontium and uranium removal from high-level radioactive waste simulant solutions by the sorbent monosodium titanate

High-level waste (HLW) is a waste associated with the dissolution of spent nuclear fuel for the recovery of weapons-grade material. It is the priority problem for the U.S. Department of Energy's Environmental Management Program. Current HLW treatment processes at the Savannah River Site (Aiken, SC) include the use of monosodium titanate (MST, with a similar stoichiometry to NaTi2O5 x xH2O) to concentrate strontium (Sr) and actinides. The high affinity of MST for Sr and actinides in HLW solutions rich in Na+ is poorly understood. Mechanistic information about the nature of radionuclide uptake will provide insight about MST treatment reliability. Our study characterized the morphology of MST and the chemistry of sorbed Sr2+ and uranium [U(VI)] as uranyl ion, UO2(2+), on MST, which were added (individually) from stock solutions of Sr and 238U(VI) with spectroscopic and transmission electron microscopic techniques. The local structure of sorbed U varied with loading, but the local structure of Sr did not vary with loading. Sorbed Sr exhibited specific adsorption as partially hydrated species whereas sorbed U exhibited specific adsorption as monomeric and dimeric U(VI)-carbonate complexes. Sorption proved site specific. These differences in site specificity and sorption mechanism may account forthe difficulties associated with predicting Sr and U loading and removal kinetics using MST.     

A mechanistic model for the uptake of waterborne strontium in the common carp (Cyprinus carpio L.)

The release of radioactive strontium to the environment is of concern due to the strong accumulation of this calcium resembling element in the bone and other tissues. To predict the effects of changes in environmental conditions on the uptake of Sr2+ and Ca2+ by freshwater fish, a Michaelis-Menten type model is introduced that accounts for the effects of chemical speciation, hydrogen ion activity, and metal ion competition. The uptake kinetics were characterized in vivo from short-term exposure experiments using the common carp (Cyprinus carpio) as the model organism. Fish were exposed to a wide range of waterborne Sr2+ (0.2-10,000 microM) and Ca2+ (10-10,000 microM) concentrations and water pH (5.0-8.5). Strontium uptake by the whole body of fish increased with increasing Sr2+ activity, displaying saturation kinetics, but decreased significantly with increasing Ca2+ and H+ activities in the water. Likewise, calcium uptake by the fish decreased with increasing Sr2+ and H+ activities in the water. The model fitted to the pooled data explains 97.5% of the variation in Sr2+ uptake and 86% in Ca2+ uptake over the wide range of exposure conditions and reveals that Sr2+ and Ca2+ inhibit each other completely competitively, while H+ inhibits the uptake of both metal ions in a partially noncompetitive way. This model can be used as a mechanistic tool to predict the uptake of these metals in carp under variable conditions.     

Comparison of wood coating durability in natural weathering and artificial weathering using fluorescent UV-lamps and water

Panels of pine sapwood coated with 30 different coating systems were exposed to natural weathering in Vienna as well as artificial weathering using fluorescent UV-lamps and water. The aim was to compare coating durability in natural and artificial weathering in terms of the exposure time until the panels reached a defined limit state where the coatings required maintenance. For both weathering methods the durability of the coating systems was influenced by film thickness and for the semi-transparent systems also by pigmentation. Three opaque coating systems lasted over 10,000 h of artificial weathering. Comparison of the natural and artificial weathering regarding durability of the coating systems (time to limit state) with the present results (after 30 months natural weathering) revealed a non-linear correlation. The collected data can provide a basis for rough service life estimation of exterior wood coatings based on standardised weathering methods.