An analytical model for the interpretation of pulse injection experiments performed for testing the spatial variability of clay formations

This paper presents an analytical model to describe pulse injection experiments. This model solves the advection-diffusion equation while taking into account back diffusion from the clay core to the inlet and from the outlet to the clay core. In most analytical models, back diffusion is neglected. For sufficiently high Péclet numbers, this is a good approximation. However, in experiments where the Péclet number is low, back diffusion is important and must be taken into account. An additional advantage of the present model is that both concentration and flux are conserved at the inlet and at the outlet of the clay core. This model is used to fit pulse injection experiments with iodide and tritiated water (HTO) in clay cores. The (new) model is required for fitting the experimental results since in clay layers advection is very slow leading to a low Péclet number. The experiments are performed on clay cores taken from different depths from the Boom Clay and the Ypres Clay layer under the site of the nuclear power plant of Doel (Belgium). The quality of all fits is excellent and the obtained parameter values are coherent. For HTO, the fitted value for the diffusion accessible porosity is consistent with measurements of the water content in Ypres Clay cores. In both types of clays, the apparent diffusion coefficient at zero flow is between 10(-10) and 2 x 10(-10) m(2)/s for iodide and between 2 x 10(-10) and 3 x 10(-10) m(2)/s for HTO. The dispersion length is in the order of 10(-3) m. The average value for the diffusion accessible porosity is between 0.35 and 0.4 for HTO and between 0.2 and 0.25 for iodide.     

Caesium selectivity and fixation by vermiculite in the presence of various competing cations

Caesium selectivity coefficients (k(G)) that were determined with respect to Na-, Mg-, Ca-, Sr- and Ba-ions, for Kent and Libby vermiculites,ranged from 4.8 to 11 (litres/mol) [Formula: see text], much higher than those with respect to K- and NH(4)-ions (0.01 to 0.06), indicating the high affinity of vermiculite for the weakly hydrated cations. Higher K(G) values were also found for low and extremely low Cs concentrations. Vermiculite samples were very effective in removing (137)Cs from solutions containing traces of (137)Cs (4 ng litre(-1)) and extremely higher quantities of K-, NH(4)-, Na-, Mg- and Ca-ions (500 mg litre(-1)). 0.5N chloride solutions of H, NH(4), K, Na, Mg and Ca were unable to remove Cs from Cs-saturated v vermiculite samples which had undergone heating at 110 degrees C. Significant quantities (50-65%) of fixed Cs were removed from these samples only after treatment with strong acids. The high preference and fixing ability of vermiculite for Cs suggests the use of this mineral as a radioactive Cs decontaminating agent.     

Effect of eutrophication upon radionuclide dynamics in the Sacca di Goro lagoon (Po River Delta,Italy): a combined field,experimental and modeling study

The focus of this paper is on the relationship between eutrophication and radionuclide circulation at the whole ecosystem scale in the shallow estuarine environment of the Sacca di Goro (Po River Delta, Italy). This lagoon is frequently affected by dystrophic crises, due to decomposition of huge amounts of macroalgae (mainly Ulva rigida), and critical conditions created at the interface between sediment and water are such that Cs-137 accumulated in the sediment can be mobilized and made available in the water column. The release of cesium from sediment in this ecosystem has been evaluated through a field experiment in which chemical conditions typical of anoxic crises were artificially created in enclosures. Also a lab experiment was carried out to shed light on possible cesium release by decomposing macroalgae. The two experiments allowed drawing conclusions on crucial factors controlling cesium release in the Sacca di Goro, the first objective of this research. The second objective was understanding the fate of radiocesium once transported in the water column. To this end ecological information gathered during the experiments and a yearly sampling campaign, has been converted into whole-system seasonal networks describing ecosystem flow structure for the Sacca di Goro. Analyzed by network analysis this model has provided clues about the dynamics of Cs-137 in terms of preferential pathways, sinks, sources, and cycling activity. Sediment, together with seston and dissolved cesium, appear to be the most significant components in the circulation of Cs-137; while macroalgal biomasses play a crucial role as an indirect causal factor.     

Diffusion of HTO, 36Cl- and 125I- in Opalinus Clay samples from Mont Terri. Effect of confining pressure

Diffusion coefficients (T=23 +/- 2 degrees C) and accessible porosities for HTO, 36Cl(-) and 125I(-) were measured on Opalinus Clay (OPA) samples from the Mont Terri Underground Rock Laboratory (URL) using the through-diffusion technique. The direction of transport (diffusion) was perpendicular to bedding. Special cells that allowed the application of confining pressure were designed and constructed. The pressures ranged from 1 to 5 MPa, the latter value simulating the overburden at the Mont Terri URL (about 200 m). The test solution used in the experiments was a synthetic version of the Opalinus Clay pore water, which has Na(+) and Cl(-) as the main components (I=0.42 M). The measured values of the effective diffusion coefficients (D(e)) and rock capacity factors (alpha) are: D(e)=1.2-1.5 x 10(-11) m(2) s(-1) and alpha=0.09-0.11 for HTO, D(e)=4.0-5.5 x 10(-12) m(2) s(-1) and alpha=0.05 for 36Cl(-) and D(e)=3.2-4.6 x 10(-12) m(2) s(-1) and alpha=0.07-0.10 for 125I(-). For non-sorbing tracers (HTO, 36Cl) the rock capacity factor alpha is equal to the diffusion-accessible porosity epsilon. The experimental results showed that pressure only had a small effect on the value of the diffusion coefficients. Increasing the pressure from 1 to 5 MPa resulted in a decrease of the diffusion coefficient of approximately 17% for HTO, approximately 28% for 36Cl(-) and approximately 30% for 125I(-). Moreover, the diffusion coefficients for 36Cl(-) and 125I(-) are smaller than for HTO, which is consistent with an effect arising from anion exclusion. The diffusion coefficients of HTO and 125I(-) measured in this study are in good agreement with recent measurements at three other laboratories performed within the framework of a laboratory comparison exercise. The values of the diffusion-accessible porosities show a larger degree of scatter.     

Effects of surface coatings on electrochemical properties and contaminant sorption of clay minerals

Surface charges play a major role in determining the interactions of contaminants with soils. The most important sources of soil charges are clay mineral colloids, whose electrochemical properties are usually modified by metal-oxides and organic matter in natural environments. In this study, effects of coatings of organic matter and Fe- and Al-oxides on a series of electrochemical properties and heavy metal sorption of three clay minerals (kaolinite, montmorillonite and illite) predominant in natural soils were investigated using batch techniques. The results indicate that the coatings increased the specific surface area of the clay minerals, except for the Al-oxide coated montmorillonite and organic matter coated 2:1 clay minerals. The sesquioxide coatings increased amount of positive charges but decreased negative charges. This causes great reduction of the negative potential on the clay surfaces, shift of the zero point of charge to a higher pH, and promotion of fluoride sorption due to presence of more OH- and OH2 on the oxide surfaces than on the clay surfaces. In contrast, the organic coating significantly increased the negativity of surface charges, and thus the zero point of charge and zeta-potential of the clays dropped down. The organic coating also induced a reduction of fluoride sorption on the clays. With respect to the sorption of lead and cadmium, the sesquioxide coatings produced insignificant effects. The experiments of lead/cadmium competitive sorption show that on both the oxide-coated surface and the original clay surface there exist different types of sites, each of which preferentially binds with a heavy metal.     

Formation of hydroxydibenzofurans from chlorophenols adsorbed on Fe-ion exchanged montmorillonite

Chlorophenols were adsorbed from gas phase on allophane, Na- and Fe(III)-ion exchanged montmorillonites at room temperature and the reaction on clay surfaces was followed by GC-MS analysis of extracts of the adsorbates. Besides chlorinated biphenyldiols and hydroxydiphenyl ethers, chlorinated hydroxydibenzofurans were formed on Fe(III)-montmorillonite.     

Microwave enhanced advanced oxidation process for treating dairy manure at low pH

This study investigated the treatment of dairy manure using the microwave enhanced advanced oxidation process (MW-AOP) at pH 2. An experimental design was developed based on a statistical program using response surface methodology to explore the effects of temperature, hydrogen peroxide dosage and heating time on sugar production, nutrient release and solids destruction. Temperature, hydrogen peroxide dosage and acid concentration were key factors affecting reducing sugar production. The highest reducing sugar yield of 7.4% was obtained at 160°C, 0 mL, 15 min heating time, and no H(2)O(2) addition. Temperature was a dominant factor for an increase of soluble chemical oxygen demand (SCOD) in the treated dairy manure. The important factors for volatile fatty acids (VFA) production were microwave temperature and hydrogen peroxide dosage. Temperature was the most important parameter, and heating time, to a lesser extent affecting orthophosphate release. Heating time, hydrogen peroxide dosage and temperature were significant factors for ammonia release. There was a maximum of 96% and 196% increase in orthophosphate and ammonia concentration, respectively at 160°C, 0.5 mL H(2)O(2) and 15 min heating time. The MW-AOP is an effective method in dairy manure treatment for sugar production, nutrient solubilisation, and solids disintegration.     

Physicochemical controls on initiation and evolution of desiccation cracks in sand-bentonite mixtures: X-ray CT imaging and stochastic modeling

The shrink-swell behavior of active clays in response to changes in physicochemical conditions creates great challenges for construction of geotechnical barriers for hazardous waste isolation, and is of significant importance for management of agricultural and natural resources. Initiation and evolution of desiccation cracks in active clays are strongly dependent on physicochemical initial and boundary conditions. To investigate effects of bentonite content (20, 40, 60%), pore fluid chemistry (0.05 and 0.5M NaCl) and drying rates (40 and 60°C) on cracking behavior, well-controlled dehydration experiments were conducted and X-ray Computed Tomography (CT) was applied to visualize and quantify geometrical features of evolving crack networks. A stochastic model based on the Fokker-Plank equation was adopted to describe the evolution of crack aperture distributions (CAD) and to assess the impact of physicochemical factors on cracking behavior. Analyses of crack porosity and crack specific surface area showed that both clay content and temperature had larger impact on cracking than pore fluid concentration. More cracks formed at high bentonite contents (40 and 60%) and at high drying rate (60°C). The drift, diffusion and source terms derived from stochastic analysis indicated that evaporative demand had greater influence on the dynamics of the CAD than solution chemistry.     

Influence of clay minerals on the reduction of Cr6+ by citric acid

The influence of clay minerals on the reduction of Cr6+ by citric acid was investigated at pH values 4.0, 4.5 and 5.0 at 25 degrees C. The results indicate that montmorillonite and illite greatly accelerate the reduction reactions at pH 4.0 and 4.5, but their effects are dramatically reduced at pH 5.0. The role of clay minerals in accelerating the reactions is in the order: illite>montmorillonite>kaolinite, which has a positive correlation with the amount of Mn2+ adsorbed on the surfaces of these minerals. With light, Fe(3+) also significantly increases reaction rates. Ethylenediaminetetraacetic acid (EDTA) greatly suppresses the acceleration of the reduction reactions by these minerals, indicating that EDTA competes with citric acid for Mn2+. Thus, the formation of complexes between Mn(2+) and citric acid could be a prerequisite for the acceleration of the reductions of Cr6+ by clay minerals. In addition, there is no relationship between the specific surface area of clay minerals and the reduction rate of Cr6+ by citric acid.     

Adsorption and desorption variability of four herbicides used in paddy rice production

This investigation was performed to determine the effect of physicochemical soil properties on penoxsulam, molinate, bentazon, and MCPA adsorption-desorption processes. Four soils from Melozal (35° 43' S; 71° 41' W), Parral (36° 08' S; 71° 52' W), San Carlos (36° 24' S; 71° 57' W), and Panimavida (35° 44' S; 71° 24' W) were utilized. Herbicide adsorption reached equilibrium after 4 h in all soils. The Freundlich L-type isotherm described the adsorption process, which showed a high affinity between herbicides and sorption sites mainly because of hydrophobic and H-bonds interaction. Penoxsulam showed the highest adsorption coefficients (4.23 ± 0.72 to 10.69 ± 1.58 mL g?1) and were related to soil pH. Molinate showed K(d) values between 1.72 ± 0.01 and 2.3 ± 0.01 mL g?1 and were related to soil pH and organic matter, specifically to the amount of humic substances. Bentazon had a high relationship with pH and humic substances and its K(d) values were the lowest, ranging from 0.11 ± 0.01 to 0.42 ± 0.01 mL g?1. MCPA K(d) ranged from 0.14 ± 0.02 to 2.72 ± 0.01 mL g?1, however its adsorption was related to humic acids and clay content. According to these results, the soil factors that could explain the sorption process of the studied herbicides under paddy rice soil conditions, were principally humic substances and soil pH. Considering the sorption variability observed in this study and the potential risk for groundwater contamination, it is necessary to develop weed rice management strategies that limit use of herbicides that exhibit low soil adsorption in areas with predisposing conditions to soil leaching.     

Evaluation of impacts of soil fractions on phenanthrene sorption

Phenanthrene sorption to soils and soil fractions was investigated using two contrasting soils with different clay mineral and organic carbon (OC) contents in an attempt to evaluate the contribution of each soil fraction to phenanthrene sorption and the applicability of the carbon-normalized distribution constant (K(OC)) in soils. Sorbents were characterized using surface analysis, solid-state (13)C NMR analysis, and glass transition temperature (T(g)) analysis to gain a insight into the chemical nature of OC in soils. Dissolved organic carbon (DOC) in the soil solution impeded the phenanthrene sorption, while humins accounted for the predominant phenanthrene sorption in soils. The contribution of OC to phenanthrene sorption in soil would be overestimated if only a K(OC)-approach was adopted, since clay minerals could account for much of the sorption, especially when OC was low in soils. Nitrogen gas was shown to be inappropriate for probing non-polar sorption capacity. The results obtained highlight the importance of clay minerals in governing the sorption of phenanthrene in soil, and emphasize the inapplicability of the carbon-normalized distribution coefficient K(OC) in soils.     

Influences of thermal decontamination on mercury removal, soil properties, and repartitioning of coexisting heavy metals

Thermal treatment is a useful tool to remove Hg from contaminated soils. However, thermal treatment may greatly alter the soil properties and cause the coexisting contaminants, especially trace metals, to transform and repartition. The metal repartitioning may increase the difficulty in the subsequent process of a treatment train approach. In this study, three Hg-contaminated soils were thermally treated to evaluate the effects of treating temperature and duration on Hg removal. Thermogravimetric analysis was performed to project the suitable heating parameters for subsequent bench-scale fixed-bed operation. Results showed that thermal decontamination at temperature >400 °C successfully lowered the Hg content to <20 mg kg⁻¹. The organic carbon content decreased by 0.06-0.11% and the change in soil particle size was less significant, even when the soils were thermally treated to 550 °C. Soil clay minerals such as kaolinite were shown to be decomposed. Aggregates were observed on the surface of soil particles after the treatment. The heavy metals tended to transform into acid-extractable, organic-matter bound, and residual forms from the Fe/Mn oxide bound form. These results suggest that thermal treatment may markedly influence the effectiveness of subsequent decontamination methods, such as acid washing or solvent extraction.     

The reactor accident at chernobyl: A possibility to test colloid-controlled transport of radionuclides in a shallow aquifer

Radioactive fall-out from the damaged nuclear power station at Chernobyl (USSR) has been measured in May 1986 in the River Glatt (Zürich, Switzerland) and in a shallow groundwater stream. This aquifer is hydraulically connected to the river and recharged by river water. Ruthenium-103, I-131, Te-132, Cs-134 and Cs-137 were measured several times using gamma-ray spectroscopy. By filtration through 0.45 μm, 0.2 μm and 0.05 μm filters the radionuclides were partitioned between solution (filtrate < 0.05 μm) and particles/colloids.In the river, the main radioactivity for all the investigated nuclides was found in the water passing the 0.05 μm filter. Among the particulates the highest radioactivity was detected in the fraction > 0.45 μm, the two smaller sizes contributing only little.In the water infiltrating into the groundwater Ru-103, I-131 and Te-132 were found almost exclusively in the filtrate (< 0.05 μm). No Cs-134, 137 was detected in this fraction indicating complete sorption on the aquifer material during infiltration. Only a very small radioactivity was found on colloids > 0.05 μm suggesting their retention by the heterogeneous glaciofluvial outwash deposits (stones, gravel, sand, clays).     

Adsorption of paraquat on the physically activated bleaching earth waste from soybean oil processing plant

A series of regeneration experiments with physical activation were carried out on bleaching earth waste from the soybean refining process in a rotary reactor. The influence of activation parameters on the spent clay by varying the holding time of 1 to approximately 4 hours and temperature of 700 to approximately 900 degrees C was determined. The variations of pore properties as well as the change of chemical characteristics in the resulting solids were also studied. Results showed that the resulting samples were type IV with hysteresis loops corresponding to type H3 from nitrogen adsorption-desorption isotherms, indicating slit-shaped mesoporous characteristics. However, the regenerated clays had smaller surface areas (70 to approximately 117 m2/g) than that (245 m2/g) of fresh bleaching earth. Under the physical activation conditions investigated, the holding time of 1 hour and temperature of 700 degrees C were found to be optimal conditions for producing mesoporous clay with physical activation. The adsorption of paraquat on regenerated sample was also evaluated. The isotherm showed that the regenerated sample still had a high affinity for this herbicide. Thus, the regeneration of this agro-industrial waste is one option for utilizing the clay resource, and it may be used for water treatment applications to remove organic contaminants.     

Evaluation of pressurized liquid extraction for determination of organophosphorus and pyrethroid pesticides in soybean

The purpose of this study was to develop an analytical method for the determination of organophosphorus and pyrethroid pesticides in soybean by pressurized liquid extraction (PLE). Two organic solvents, acetone and acetonitrile, were evaluated as extraction solvents. In both cases, the amount of extract was enhanced with increasing extraction temperature. The extracts obtained using acetonitrile were measured by gas chromatography/mass spectrometry after a cleanup process based on the analytical method for the Japanese Positive List System for Agricultural Chemicals Remaining in Foods. The effect of extraction temperature (range: 40- 130°C) on extraction efficiency was evaluated by a recovery study using 21 organophosphorus pesticides and 10 pyrethroid pesticides as target analytes and acetonitrile as the solvent. The results indicated that at 130°C, some organophosphorus pesticides might be degraded, whereas extraction temperatures between 70°C and 100°C were optimal. Next, a prepared sample containing fenitrothion and permethrin was analyzed. Although the sample was not soaked in water prior to analysis, PLE provided analytical results comparable to those obtained by solvent extraction with homogenization. Therefore, PLE is considered a simple and alternative technique for the extraction of organophosphorus and pyrethroid pesticides in soybean.     

Heavy metals in soils: distribution, relationship with soil characteristics and radionuclides and multivariate assessment of contamination sources

The study is dealing with the distribution and the origin of heavy metals (Cd, Cr, Cu, Mn, Ni, Pb and Zn) in soils from a priori non-polluted areas. Positive correlations with organic matter and clay content but not with pH have been observed for most of elements analyzed in this study. Correlations of some metals (Cr, Pb and Zn) and radionuclides (238U and 137Cs) observed for analyzed soils could be explained by their common affinity for clay minerals. Enrichment factor (EF) analysis and cluster analysis (CA) highlighted the lithogenic origin of Cr, Cu, Mn, Ni, Pb and Zn and pointed out the primary input of Cd from anthropogenic sources. It also revealed the need for detailed geochemical surveys in the future in order to decrease the uncertainty of discrimination between lithogenic and anthropogenic origin of metals of interest.     

Solute transport properties of compacted Ca-bentonite used in FEBEX project

The present Spanish concept of a deep geological high level waste repository includes an engineered clay barrier around the canister. The clay presents a very high sorption capability for radionuclides and a very small hydraulic conductivity, so that the migration process of solutes is limited by sorption and diffusion processes. Therefore, diffusion and distribution coefficients in compacted bentonite (i.e. in "realistic" liquid to solid ratio conditions) are the main parameters that have to be obtained in order to characterise solute transport that could be produced after the canister breakdown. Through-Diffusion (TD) and In-Diffusion (ID) experiments with HTO, Sr, Cs and Se were carried out using compacted FEBEX bentonite, which is the reference material for the Spanish concept of radioactive waste disposal. Experiments were interpreted by means of available analytical solutions that allow the estimation of diffusion coefficients and, in some cases, distribution coefficients. Analytical solutions are simple to use, but rely on hypotheses that do not hold in all the experiments. These experiments were interpreted also using an automatic parameter estimation code that overcomes the limitations of analytical solutions. Numerical interpretation allows the simultaneous estimation of porosity, diffusion and distribution coefficients, accounts for the role of porous sinters and time-varying boundary concentrations, and can use different types of raw concentration data.     

Plant uptake of radionuclides in lysimeter experiments

The results of seven years lysimeter experiments to determine the uptake of 60Co, 137Cs and 226Ra into agricultural crops (endive, maize, wheat, mustard, sugarbeet, potato, Faba bean, rye grass) are described. The lysimeter consists of twelve monolithic soil profiles (four soil types and three replicates) and is located in Seibersdorf/Austria, a region with a pannonian climate (pronounced differences between hot and semi-arid summers and humid winter conditions, annual mean of precipitation: 517 mm, mean annual temperature: 9.8 degrees C). Besides soil-to-plant transfer factors (TF), fluxes were calculated taking into account biomass production and growth time. Total median values of TF's (dry matter basis) for the three radionuclides decreased from 226Ra (0.068 kg kg(-1)) to 137Cs (0.043 kg kg(-1)) and 60Co (0.018 kg kg(-1)); flux values exhibited the same ranking. The varying physical and chemical properties of the four experimental soils resulted in statistically significant differences in transfer factors or fluxes between the investigated soils for 137Cs and 226Ra, but not for 60Co. Differences in transfer between plant species and plant parts are distinct, with graminaceous species showing, on average, TF values 5.8 and 15 times lower than dicotyledonous species for 137Cs and 60Co, respectively. This pattern was not found for 226Ra. It can be concluded that 137Cs transfer is heavily influenced by soil characteristics, whilst the plant-specific factors are the main source of TF variability for 60Co. The variability of 226Ra transfer originates both from soil properties and plant species behaviour.     

Transport of radionuclides in natural fractures: some aspects of laboratory migration experiments

Results are reported for a series of migration experiments performed in a hydraulically characterized, single, natural fracture in a block of granite with overall dimensions of 1 × 1 × 0.7 m (all approximate), using the conservative, poorly sorbing and strongly sorbing radionuclides ³H₂0, ¹³¹I, ²²Na, ⁸⁵Sr, ¹³⁷Cs, ⁶⁰Co, ^154,155Eu, ²³⁷Np, and ²³⁸Pu. The volumetric flow velocity of the transport solution was 3 ml h⁻¹, giving a residence time in the fracture of approximately 50 h. Elution profiles were obtained for ³H₂0, ¹³¹I, ²²Na, ⁸⁵Sr and ¹³⁷Cs but no evidence of the other radionuclides was observed in the eluent. Results from supporting static sorption measurements on crushed geological materials and granite coupons showed in general higher sorption on alteration minerals than on granite. Sorption was lowest for ²²Na and ⁸⁵Sr.The migration of ¹³¹I, ²²Na, ⁸⁵Sr through the fracture in real time was followed using end-window Geiger-Müller probes located in unused boreholes. Additional information, obtained by alpha and gamma scanning of the fracture surfaces after separating the block along the fracture, confirmed that transport had occurred along the flow path predicted from the hydraulic characterization of the fracture and that, over a 5.5 month period, the bulk of the injected ¹³⁷Cs had migrated only 75 cm along the flow path. The ⁶⁰Co, the rare earths and the actinides had not moved beyond the location of the injection borehole, suggesting that fracture infilling minerals played a major role in retarding radionuclide transport. Additional confirmation of the role of secondary minerals in radionuclide retardation was obtained using selective sequential extraction on the fracture surfaces. These observations support the inclusion of sorption data for fracture infilling minerals in the sorption database developed for the geosphere model for the Canadian Nuclear Fuel Waste Management Program.