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1.
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.  相似文献   

2.
Sorption of 137Cs, 90Sr, 154Eu and 141Ce by magnetite has been studied at varying pH (4 to 11) in the presence and absence of humic acid. The sorption studies have also been carried out at varying ionic strength (0.01 to 0.2 M NaClO4) and humic acid concentration (2 to 20 mg/L). Percentage sorption of 137Cs and 90Sr was found to be pH dependent, with the sorption increasing with increasing pH of the suspension. At any pH, the percentage sorption of 90Sr was higher than that of 137Cs. The results have been explained in terms of the electrostatic interaction between the positively charged metal ions and the surface charge of the magnetite which becomes increasingly negative with increasing pH. On the other hand, 154Eu and 141Ce were found to be strongly sorbed by the magnetite at all pH values, with the sorption being independent of pH. The strong sorption of trivalent and tetravalent metal ions suggests the role of complexation reactions during sorption, apart from the electrostatic interactions. However, in the case of 141Ce surface precipitation of Ce(III) formed by reduction of Ce(IV) in the presence of magnetite cannot be ruled out. Presence of humic acid (2 mg/L) was found to have negligible effect on sorption of all metal ions.  相似文献   

3.
In order to determine the mechanisms of the retention of 60Co, 85Sr and 134Cs in natural silica sand columns, desorption experiments were performed by changes of pH and ionic strength and by injection of natural organic matter (NOM). Injection of KCl (0.1 M) resulted in a high release of 60Co (60-100%) and 85Sr (72-100%) but a smaller release of 134Cs (31-66%). Only limited release of 60Co (66%) and 85Sr (71%) and no release of 134Cs were observed by injection of NOM. The different percentages of desorption were related to the chemical characteristics of the organic colloids previously retained in columns before the desorption step. The results evidenced different sorption processes on energetically heterogeneous surface sites. According to the initial conditions, the binding of the radionuclides to the solid phase resulted from weak and easily reversible sorption processes to strong association probably by inner sphere complexes. The rather weak release of 134Cs by KCl was attributed to the strong retention of 134Cs by clay coatings on the natural silica sand surfaces.  相似文献   

4.
A sand column leaching system with well-controlled suction and flow rate was built to investigate the effects on bacterial transport of air-water interface effects (AWI) correlated to water content, particle size, and column length. Adsorption of Escherichia coli strain D to silica sands was measured in batch tests. The average % adsorption for coarse and fine sands was 45.9+/-7.8% and 96.9+/-3.2%, respectively. However, results from static batch adsorption experiments have limited applicability to dynamic bacterial transport in columns. The early breakthrough of E. coli relative to bromide was clear for all columns, namely c. 0.15 to 0.3 pore volume earlier. Column length had no significant effects on the E. coli peak concentration or on total recovery in leachate, indicating retention in the top layer of sands. Tailing of breakthrough curves was more prominent for all fine sand columns than their coarse sand counterparts. Bacterial recovery in leachate from coarse and saturated sand columns was significantly higher than from fine and unsaturated columns. Observed data were fitted by the convection-dispersion model, amended for one-site and two-site adsorption to particles, and for air-water interface (AWI) adsorption. Among all models, the two-site+AWI model achieved consistently high model efficiency for all experiments. Thus it is evident from experimental and modeling results that AWI adsorption plays an important role in E. coli transport in sand columns.  相似文献   

5.
Breakthrough curves of 137Cs and tritiated water injected instantaneously into artificial fractures in Lac du Bonnet granite were analyzed using the analytical solution for a single rock-fracture system and assuming the linear sorption isotherm of the solute. Parameters of nuclide diffusion and sorption in rock matrices, obtained by fitting, varied depending on the flow velocity in the fractures. According to theoretical calculations, different fracture flow velocities lead to different diffusion distances of nuclides in matrices at the same injection volume. As microscopic inhomogeneity is considered to exist in the rock matrix, the average diffusion-sorption characteristics of the matrix within the diffusion distance may have varied with the fracture flow velocity. Surface sorption was marked in fractures that had relatively high matrix sorption-diffusion capacities. The phenomenon was interpreted using the theoretical relationships developed between the surface sorption, matrix sorption and pore diffusion coefficient, and the porosity of matrices.The effect of the nonlinear sorption of solute was examined by numerically solving model equations that incorporate the nonlinear isotherm. This incorporation may contribute to the reduction of deviations between theoretical and experimental BTC's.  相似文献   

6.
In this study, rice husk was modified with NaOH and used as adsorbent for dynamic adsorption of methylene blue (MB) from aqueous solutions. Continuous removal of MB from aqueous solutions was studied in a laboratory scale fixed-bed column packed with NaOH-modified rice husk (NMRH). Effect of different flow rates and bed heights on the column breakthrough performance was investigated. In order to determine the most suitable model for describing the adsorption kinetics of MB in the fixed-bed column system, the bed depth service time (BDST) model as well as the Thomas model was fitted to the experimental data. An artificial neural network (ANN)-based model was also developed for describing the dynamic dye adsorption process. An extensive error analysis was carried out between experimental data and data predicted by the models by using the following error functions: correlation coefficient (R 2), average relative error, sum of the absolute error and Chi-square statistic test (χ 2). Results show that with increasing bed height and decreasing flow rate, the breakthrough time was delayed. All the error functions yielded minimum values for the ANN model than the traditional models (BDST and Thomas), suggesting that the ANN model is the most suitable model to describe the fixed-bed adsorption of MB by NMRH. It is also more rational and reliable to interpret dynamic dye adsorption data through a process of ANN architecture.  相似文献   

7.
《Chemosphere》2002,49(10)
The distribution coefficients (Kd) and desorption rates of 137Cs and 241Am radionuclides in bottom sediments at different locations in the Black Sea were studied under laboratory conditions. The Kd values were found to be 500 for 137Cs and 3800 for 241Am at the steady state and described exponential curves. Rapid uptake of the radionuclides occurred during the initial period and little accumulation happened after four days. The desorption rates for 137Cs in different bottom sediments were best described by a three-component exponential model. The desorption half-times of 137Cs ranged from 26 to 50 d at the slow components. However, the desorption rate of 241Am described one component for all sediment samples and desorption half-time was found to be 75 d. In general, the results showed that the 241Am radionuclide is more effectively transferred to bottom sediment and has longer turnover time than 137Cs under Black Sea conditions.  相似文献   

8.
In this note, we applied the temporal moment solutions of [Das and Kluitenberg, 1996. Soil Sci. Am. J. 60, 1724] for one-dimensional advective-dispersive solute transport with linear equilibrium sorption and first-order degradation for time pulse sources to analyse soil column experimental data. Unlike most other moment solutions, these solutions consider the interplay of degradation and sorption. This permits estimation of a first-order degradation rate constant using the zeroth moment of column breakthrough data, as well as estimation of the retardation factor or sorption distribution coefficient of a degrading solute using the first moment. The method of temporal moment (MOM) formulae was applied to analyse breakthrough data from a laboratory column study of atrazine, hexazinone and rhodamine WT transport in volcanic pumice sand, as well as experimental data from the literature. Transport and degradation parameters obtained using the MOM were compared to parameters obtained by fitting breakthrough data from an advective-dispersive transport model with equilibrium sorption and first-order degradation, using the nonlinear least-square curve-fitting program CXTFIT. The results derived from using the literature data were also compared with estimates reported in the literature using different equilibrium models. The good agreement suggests that the MOM could provide an additional useful means of parameter estimation for transport involving equilibrium sorption and first-order degradation. We found that the MOM fitted breakthrough curves with tailing better than curve fitting. However, the MOM analysis requires complete breakthrough curves and relatively frequent data collection to ensure the accuracy of the moments obtained from the breakthrough data.  相似文献   

9.

In this work, biochar (BC), activated carbon (AC), and graphene oxide (GO) were thiol-functionalized using 3-mercaptopropyltrimethoxysilane (3-MPTS) (named as BCS, ACS, and GOS, respectively). BCS, ACS, and GOS were synthesized mainly via the interaction between hydrolyzed 3-MPTS and surface oxygen-containing functional groups (e.g., –OH, O–C=O, and C=O) and π-π interaction. The materials before and after modification were characterized and tested for mercury removal, including sorption kinetics and isotherms, the effects of adsorbent dosage, initial pH, and ionic strength. Pseudo-second-order sorption kinetic model (R2 = 0.992~1.000) and Langmuir sorption isotherm model (R2 = 0.964~0.998) fitted well with the sorption data of mercury. GOS had the most –SH groups with the largest adsorption capacity for Hg2+ and CH3Hg+ (449.6 and 127.5 mg/g), followed by ACS (235.7 and 86.7 mg/g) and BCS (175.6 and 30.3 mg/g), which were much larger than GO (96.7 and 4.9 mg/g), AC (81.1 and 24.6 mg/g), and BC (95.6 and 9.4 mg/g). GOS and ACS showed stable mercury adsorption properties at a wide pH range (2~9) and ionic strength (0.01~0.1 mol/L). Mercury maybe removed by ligand exchange, surface complexation, and electrostatic attraction.

  相似文献   

10.
Avila MA  Breiter R 《Chemosphere》2008,72(11):1807-1815
The competitive sorption of 1,2-cis-dichloroethene (cis-DCE) and trichloroethene (TCE) was investigated by means of column experiments using a model porous mineral solid represented by silica gel. The experimental isotherms were obtained by employing a chromatographic method. The competitive sorption isotherms were modelled with the extended Freundlich and extended Langmuir isotherms, using the parameters from single-solute experiments. The breakthrough curves were modelled with the advection-dispersion transport equation coupled with the lumped pore diffusion model. The best results were obtained when the extended Freundlich isotherm was employed. The competitive sorption was revealed with the presence of an overshoot in the breakthrough curve of cis-DCE and a decrease in the degree of sorption of cis-DCE (20%) and TCE (12%). A linear dependency of the overshoot with an increase in the concentration of cis-DCE at a fixed concentration of TCE was observed, between 16% and 20%, and at least at concentrations <6 mg L(-1) in the liquid phase. The displaced molecules of cis-DCE by TCE were accumulated through the column causing its overshoot; thus short columns may hinder its observation. Thermodynamic analysis shows an exothermic adsorption process of -34 to -41 kJ mol(-1), which is enhanced by sorption in micropores. The Gibbs free energy is positive for cis-DCE in the multi-component case, due to its displacement by TCE.  相似文献   

11.
A three-site cation exchange model is proposed to describe the concentration dependent uptake of Cs on natural argillaceous rock systems. Major premises in the model are that the sorption of Cs is dominated by the illite mineral component in the rock and that there is a fixed relationship between the site capacities of the three site types denoted as frayed edge, type II and planar sites. The definition of a “reference illite” with a cation exchange capacity of 0.2 equiv. kg-1 allows the three site capacities to be fixed in the model calculations over the weight fraction of illite in the argillaceous rocks. Up to Cs equilibrium concentrations of 10-3 M sorption occurs predominantly on the frayed edge and type II sites (higher affinity sites), with the planar site type playing only a minor role. Competition with Cs for sorption on the former two site types arises predominantly from monovalent cations such as K, Rb and NH4 which have low hydration energies. H and Na (except at high concentrations) are considerably less competitive and bivalent cations such as Mg, Ca and Sr are effectively non-competitive. A consistent set of selectivity coefficients for Cs with respect to K, Rb, NH4 and Na was derived from analyses and modelling of a wide range of Cs sorption data available in the open literature on pure illites from many different sources. The model was tested against four Cs sorption isotherm data sets determined on argillaceous rocks: Boom clay, Oxford clay, Palfris marl and Opalinus clay. The water chemistries and illite contents given in these experiments allowed the Cs sorption isotherms to be predicted. It is concluded that the Cs sorption model presented here, in which there are no free parameters, can be used to predict the uptake of Cs at equilibrium concentrations below 10-3 M to within a factor of 2 to 3 in natural argillaceous rock systems.  相似文献   

12.
For several years tracer migration experiments are performed at Nagra's Grimsel Test Site in the Swiss Alps as a joint undertaking of Nagra, PNC and PSI. The aim is to develop methods for field experiments at possible sites for nuclear waste repositories and to test radionuclide transport models.A hydraulic dipole field is generated in a well-defined fracture zone in granite. The tracers used are non-sorbing (uranine, 3He, 4He, 82Br, 123I), mildly sorbing (22Na+, 24Na+), and more strongly sorbing (85Sr2+, 86Rb+, 134Cs+, 137Cs+). These experiments have been complemented by extensive laboratory investigations on petrography, on water-rock and nuclide-rock interaction as well as by migration experiments with bore cores.The main questions addressed are: What are the relevant geometric factors and mechanisms for transport, how well can breakthrough curves be extrapolated from one dipole arrangement to another, which parameters are scale dependent, is there a difference in sorption values between laboratory and field experiments or between static and dynamic experiments. Evaluating the experimental results for the non-sorbing uranine and the mildly sorbing tracers sorption, Strontium, we show that a consistent picture of tracer transport, and specifically of tracer sorption, is obtained when exploiting all available experimental information and using not too simplistic models.  相似文献   

13.
以天然土壤为吸附材料,处理水溶液中的Pb2+,研究3种土壤对水溶液中Pb2+的吸附过程并结合土壤的理化性质对吸附规律进行初步分析。结果表明,棕壤和钙层土对Pb2+的吸附能力远大于红壤,3种土壤对Pb2+的吸附动力学曲线与二次动力学方程有较好的拟合性;3种土壤吸附Pb2+的吸附等温线用Langmuir方程描述最为合适,其次是Temkin方程,再次是Frenudlich方程,钙层土对Pb2+的吸附受温度影响较为明显;由实验数据得出的反应热力学参数说明3种土壤对Pb2+的吸附是自发的吸热过程;Pb2+在饱和吸附的土壤表面覆盖率并不高;土壤对Pb2+的吸附能力受各种土壤理化性质的综合影响。  相似文献   

14.
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.  相似文献   

15.
Movement of metolachlor and terbuthylazine in core and packed soil columns   总被引:2,自引:0,他引:2  
Singh N  Kloeppel H  Klein W 《Chemosphere》2002,47(4):409-415
Movement of metolachlor and terbuthylazine including a bromide tracer was studied in core and packed soil columns in PVC pipes (80 mm diameter, 15 mm depth) with two German soil types viz: silt loam and loamy silt. The breakthrough curves (BTCs) for bromide indicated some preferential flow of water both under conventional tillage (CN) and no-till (NT) simulation with silt loam soil. The herbicides leached to a greater extent in NT columns than in CN columns. Leaching was higher in loamy silt soil than in silt loam soil under CN conditions. This result is in agreement with the higher sorption capacity of silt loam having higher organic carbon compared to loamy silt having low organic carbon. Adsorption strength of the herbicides did not affect their breakthrough time, but was reflected in the slope and maximum height of the BTCs. The BTCs showed the expected inverse relationship between leaching and adsorption with greater mobility of the weakly-sorbed metolachlor than the more strongly sorbed terbuthylazine. Maximum amounts of the applied herbicides were recovered from the top soil layer in intact columns. Metolachlor was more mobile in packed columns than in core columns.  相似文献   

16.
A theoretical and experimental study of cation exchange in high ionic strength electrolytes was performed using pristine subsurface sediments from the U.S. Department of Energy Hanford site. These sediments are representative of the site contaminated sediments impacted by release of high level waste (HLW) solutions containing 137Cs+ in NaNO3 brine. The binary exchange behavior of Cs+-Na+, Cs+-K+, and Na+-K+ was measured over a range in electrolyte concentration. Vanselow selectivity coefficients (Kv) that were calculated from the experimental data using Pitzer model ion activity corrections for aqueous species showed monotonic increases with increasing electrolyte concentrations. The influence of electrolyte concentration was greater on the exchange of Na+-Cs+ than K+-Cs+, an observation consistent with the differences in ion hydration energy of the exchanging cations. A previously developed two-site ion exchange model [Geochimica et Cosmochimica Acta 66 (2002) 193] was modified to include solvent (water) activity changes in the exchanger phase through application of the Gibbs-Duhem equation. This water activity-corrected model well described the ionic strength effect on binary Cs+ exchange, and was extended to the ternary exchange system of Cs+-Na+-K+ on the pristine sediment. The model was also used to predict 137Cs+ distribution between sediment and aqueous phase (Kd) beneath a leaked HLW tank in Hanfordd's S-SX tank using the analytical aqueous data from the field and the binary ion exchange coefficients for the pristine sediment. The Kd predictions closely followed the trend in the field data and were improved by consideration of water activity effects that were considerable in certain regions of the vadose zone plume.  相似文献   

17.
Carbonised beet pulp (BPC) produced from agricultural solid waste by-product in sugar industry was used as adsorbent for the removal of Remazol Turquoise Blue-G 133 (RTB-G 133) dye in this study. The kinetics and equilibrium of sorption process were investigated with respect to pH, temperature and initial dye concentration. Adsorption studies with real textile wastewater were also performed. The results showed that adsorption was a strongly pH-dependent process, and optimum pH was determined as 1.0. The maximum dye adsorption capacity was obtained as 47.0 mg g?1at the temperature of 25 °C at this pH value. The Freundlich and Langmuir adsorption models were used for describing the adsorption equilibrium data of the dye, and isotherm constants were evaluated depending on sorption temperature. Equilibrium data of RTB-G 133 sorption fitted very well to the Freundlich isotherm. Mass transfer and kinetic models were applied to the experimental data to examine the mechanisms of adsorption and potential rate-controlling steps. It was found that both external mass transfer and intra-particle diffusion played an important role in the adsorption mechanisms of dye and adsorption kinetics followed the pseudo second-order type kinetic model. The thermodynamic analysis indicated that the sorption process was exothermic and spontaneous in nature.  相似文献   

18.
Abstract

This paper presents the results of long-term investigations of 137Cs activity concentrations in chicken meat and eggs from northwest Croatia for the period 1987–2018. The research has been done as a part of monitoring program of radioactive contamination in Croatia. The highest activity concentrations in both of these foodstuffs were measured in 1987 and have been decreasing exponentially ever since. The Fukushima-Daiichi accident in 2011 did not cause any increase of 137Cs activity concentrations. The ecological half-life for 137Cs was estimated to be 8.0 and 8.4?years for chicken meat and eggs respectively. The correlation between 137Cs in fallout and chicken meat as well as between 137Cs in fallout and eggs is very good, the respective correlation coefficients being 0.79 and 0.72, indicating that fallout was the main source of 137Cs contamination in both foodstuffs. The estimated effective doses received by adult members of the Croatian population due to the intake of radiocaesium by chicken meat and egg consumption for the overall observed period are very small, 2.0 and 0.6 µSv respectively. Therefore, chicken meat and chicken egg consumption was not a critical pathway for the transfer of radiocaesium to humans.  相似文献   

19.
The transport of contaminants in fractured media is a complex phenomenon with a great environmental impact. It has been described with several models, most of them based on complex partial differential equations, that are difficult to apply when equilibrium and nonequilibrium dynamics are considered in complex boundaries. With the aim of overcoming this limitation, a combination of two lattice Bathnagar, Gross and Krook (BGK) models, derived from the lattice Boltzmann model, is proposed in this paper. The fractured medium is assumed to be a single fissure in a porous rock matrix. The proposed approach permits us to deal with two processes with different length scales: advection–dispersion in the fissure and diffusion within the rock matrix. In addition to the mentioned phenomena, sorption reactions are also considered. The combined model has been tested using the experimental breakthrough curves obtained by Garnier et al. (Garnier, J.M., Crampon, N., Préaux, C., Porel, G., Vreulx, M., 1985. Traçage par 13C, 2H, I et uranine dans la nappe de la craie sénonienne en écoulement radial convergent (Béthune, France). J. Hidrol. 78, 379–392.) giving acceptable results. A study on the influence of the lattice BGK models parameters controlling sorption and matrix diffusion on the breakthrough curves shape is included.  相似文献   

20.
为了研究2,4-二氯苯酚在土壤中的吸附及比较其批实验与柱实验的分配系数Kd,开展了2,4-二氯苯酚的批实验(不同液固比条件下)和柱实验。通过分析结果可知,在批实验中,不同液固比条件下2,4-二氯苯酚达到平衡的时间类似,都在60~70 h,吸附动力学曲线符合伪二级动力学方程,吸附规律是:液固比越大,平衡吸附量增大,反应速率常数K2减小,初始吸附速率常数减小;Kd随液固比增大而降低,范围在2.91~2.12 L/kg。柱实验结果表明,2,4-二氯苯酚的贯穿曲线可以很好地用化学非平衡模型来拟合,通过模型拟合得到的Kd值要低于批实验的结果。该研究对表征2,4-二氯苯酚在环境中的行为、预测其对土壤和地下水的污染及其治理提供了依据。  相似文献   

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