Cesium migration in Hanford sediment: a multisite cation exchange model based on laboratory transport experiments

Cs+ transport experiments carried out in columns packed with uncontaminated Hanford formation sediment from the SX tank farm provide strong support for the use of a multisite, multicomponent cation exchange model to describe Cs+ migration in the Hanford vadose zone. The experimental results indicate a strong dependence of the effective Cs+ Kd on the concentrations of other cations, including Na+ that is present at high to extremely high concentrations in fluids leaking from the Hanford SX tanks. A strong dependence of the Cs+ Kd on the aqueous Cs+ concentration is also apparent, with retardation of Cs+ increasing from a value of 41 at a Cs+ concentration of 10(-4) M in the feed solution to as much as 282 at a Cs+ concentration of 5x10(-7) M, all in a background of 1 M NaNO3. The total cation exchange capacity (CEC) of the Hanford sediment was determined using 22Na isotopic equilibrium exchange in a flow-through column experiment. The value for the CEC of 120 microeq/g determined with this method is compatible with a value of 121.9 microeq/g determined by multi-cation elution. While two distinct exchange sites were proposed by Zachara et al. [Geochim. Cosmochim. Acta 66 (2002) 193] based on binary batch exchange experiments, a third site is proposed in this study to improve the fit of the Cs+-Na+ and Cs+-Ca+ exchange data and to capture self-sharpened Cs+ breakthrough curves at low concentrations of Cs+. Two of the proposed exchange sites represent frayed edge sites (FES) on weathered micas and constitute 0.02% and 0.22% of the total CEC. Both of the FES show a very strong selectivity for Cs+ over Na+ (K(Na-Cs)=10(7.22) and 10(4.93), respectively). The third site, accounting for over 99% of the total CEC, is associated with planar sites on expansible clays and shows a smaller Na+-Cs+ selectivity coefficient of 10(1.99). Parameters derived from a fit of binary batch experiments alone tend to under predict Cs+ retardation in the column experiments. The transport experiments indicate 72-90% of the Cs+ sorbed in experiments targeting exchange on FES was desorbed over a 10- and 24-day period, respectively. At high Cs+ concentrations, where sorption is controlled primarily by exchange on planar sites, 95% of the Cs+ desorption was desorbed. Most of the difficulty in desorbing Cs+ from FES is a result of the extremely high selectivity of these sites for Cs+, although truly irreversible sorption as high as 23% was suggested in one experiment. The conclusion that Cs+ exchange is largely reversible in a thermodynamic sense is supported by the ability to match Cs+ desorption curves almost quantitatively with an equilibrium reactive transport simulation. The model for Cs+ retardation developed here qualitatively explains the behavior of Cs+ in the Hanford vadose zone underneath a variety of leaking tanks with differing salt concentrations. The high selectivity of FES for Cs+ implies that future desorption and migration is very unlikely to occur under natural recharge conditions.     

Distribution coefficients (Kd) and desorption rates of Cs and Am in Black Sea sediments

The distribution coefficients (K_d) and desorption rates of ¹³⁷Cs and ²⁴¹Am radionuclides in bottom sediments at different locations in the Black Sea were studied under laboratory conditions. The K_d 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.     

Modeling interactions at the tributyltin-kaolinite interface

Tributyltin (TBT) is a common pollutant in natural environments and the interaction with mineral surfaces largely determine its solubility, speciation, bioavailability, and transport in aqueous systems. The present work aimed at quantifying the TBT adsorption using kaolinite and a kaolinite-rich sediment as sorbent materials. Experiments were conducted under conditions that are important from an environmental perspective. Proton adsorption data were determined for kaolinite as a function of pH and electrolyte concentrations to ascertain intrinsic acidity constants and site density values. The pH(zpc) of kaolinite sample KGa was determined at 4.9 by surface titration. The generalized diffused double layer model (DLM) was used to quantify both, proton and TBT adsorption. Following intrinsic acidity and TBT binding constants resulting from the TBT/kaolinite system were used: >SOH ==> >SO- + H+, logK = -5.4; >SOH + H+ ==> SOH2+, logK = 4.6; >XNa + H ==> XH + Na+, logK(X/H+) = -1.1; >SO- + TBT+ ==> >SOTBT, logK = 3.5; >XNa + TBT+ ==> Na+, logK(X/TBT) = 1.0. All surface-active variable charge sites on kaolinite, namely >AlOH and >SiOH are grouped and collectively refer to as >SOH in this paper. >XNa refers to ion exchange sites. Modeling of TBT adsorption onto kaolinite was conducted distinguishing selective (high affinity) sites (>S(S)OH) in addition to non-selective sites (>SOH). The inclusion of >S(S)OH was essential in order to quantify TBT adsorption successfully, while the inclusion of >XNa was optional. The reduction of surface coverage values by a 10-fold TBT adsorption modeling is in agreement with the results of molecular model calculations of the system. Parameters calculated for the monophase kaolinite were subsequently used to quantify the TBT adsorption onto kaolinite-rich sediment.     

The occurrence and bioavailability of radioactive 137Cs in small forest lakes in Southern Finland

Following the Chernobyl accident in late April 1986, central Finland was subjected to considerable radioactive fallout. The radioactive isotope of caesium, (137)Cs, was potentially the most harmful isotope in the fallout because of its long half-life (30 years). (137)Cs activities remained unexpectedly low within the biota (algae, zooplankton, aquatic moss, fish) of some humic forest lakes in southern Finland compared to the clear water lakes within the same district. This observation suggested that humic substances, by binding (137)Cs chemically, may reduce its bioavailability in lake water. Our laboratory experiments (throughflow systems; gel chromatography) demonstrated that binding of (137)Cs by humic substances was negligible in untreated lake waters; only when most of the alkali metals had been removed with an ion exchange resin was any binding of (137)Cs by low molecular humic fractions apparent. Instead, the concentrations of cations (especially potassium) were of overwhelming importance for the bioavailability of (137)Cs within the lacustrine ecosystems. The concentrations of (137)Cs within food chains are expected to stay at a high level for many years especially in lakes with long water renewal times.     

Global fallout Pu recorded in lacustrine sediments in Lake Hongfeng, SW China

Studies on the distribution and isotope compositions of fallout Pu are important for source characterization of possible future non-fallout Pu contamination in aquatic environments, and useful for dating of recent sediments to understand the pollution history of environmental contaminants. We present the historical record of atmospheric Pu fallout reconstructed from a sediment core from Lake Hongfeng, China. The Pu activity profile was in agreement with the 137Cs profile. Inventories were 50.7 Bq m(-2) for 239+240Pu and 1586 Bq m(-2) for 137Cs. The average 240Pu/239Pu atom ratio was 0.185+/-0.009, indicating that Pu originated from global stratospheric fallout rather than from direct tropospheric or close-in fallout from the Chinese nuclear testing conducted in the 1970s. Our data suggested that Lake Hongfeng would be an ideal setting for monitoring atmospheric fallout and environmental changes in this region.     

生物对137Cs的吸收和富集

螺蛳等供试生物能很快地吸收水体中的＾１３７Ｃｓ,并随着时间的延长而不断增加,吸收过程可用直线方程来表达,螺蛳、喜旱莲子草和金鱼藻可以用来净化被＾１３７Ｃｓ的吸收较少,其中稗草和喜旱莲子草较高;由于Ｋ＾＋与Ｃｓ＾＋之间的拮抗作用,帮可用施钾肥方法减少作物以土壤中＾１３７Ｃｓ的吸收。     

Caesium-137 in Perch in Swedish Lakes after Chernobyl-present situation, relationships and trends

The Chernobyl accident, and the general acidification of Swedish water systems, form the base for this project. The aims of the work have been to present results on the linkage between the concentration of Cs-137 in fish, lake load of Cs and lake characteristics, to give a preliminary prognosis on the recovery, and to put the results within a wider framework of environmental hazard analysis. A broad set of data on limnology, morphometry and drainage area conditions from 41 lakes were collected during 1986 and 1987. Cs-137 was determined in 1 + perch (Cs-pe, 1-year-old perch), water, material collected by sediment traps and from surficial sediments. The main results are as follows. The average value of Cs-pe for all lakes has dropped from 9800 Bq kg(-1) (wet) to 5040 between the 2 years. Generally, the decrease is between 5 and 90%. We have tested if any factor(s) could be specifically linked to this decrease-no such factors have been found. The concentrations of Cs in sediment traps have, on average, decreased by 80%. Very high correlations exist between Cs-pe and the caesium load as determined from the sediment traps. Between 1 and 10% (mean 3.9%) of the initial fall-out deposition to the drainage area was transported from land to water during June to August 1986. The variation in initial fall-out deposition explains 65-69% of the variability in Cs-pe; the degree of explanation (= coefficient of determination, r2) increases to about 85% if one also takes into account the lake water hardness and totP. A map showing with lakes likely to have 1 + perch with higher mean Cs-concentrations than 1500 Bq kg(-1) wet is presented. Between 4000 and 7000 lakes in Sweden appear to have Cs-pe higher than 1500 Bq kg(-1) wet, figures which emphasize the serious impact of the Chernobyl accident on the environmental conditions in Sweden.     

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.     

黄河水中沉积物与锌、镉液-固界面的作用

研究了黄河水中沉积物与重金属污染物Zn^2 、Cd^ 的离子交换吸附作用。结果表明,Zn^2 、Cd^2 在黄河水中主要以M（OH）^ 的形式与沉积物进行－价阳离子交换反应;在天然黄河水pH范围内,Zn^2 、Cd^2 的离子交换率都大于70％;随温度升高,Zn^2 、Cd^2 与沉积物的交换率增加,E-pH曲线向pH值减小的方向位移。     

In situ tracer tests to determine retention properties of a block scale fracture network in granitic rock at the Aspö Hard Rock Laboratory, Sweden

Experiments were conducted at the Asp? Hard Rock Laboratory in order to improve the understanding of radionuclide retention properties of fractured crystalline bedrock in the 10-100 m scale (TRUE Block Scale Project, jointly funded by ANDRA, ENRESA, Nirex, JNC, Posiva and SKB). A series of tracer experiments were performed using sorbing tracers in three different flow paths. The different flow paths had Euclidian lengths of 14, 17 and 33 m, respectively, and one to three water conducting structures. Four tests were performed using different cocktails made up of radioactive sorbing tracers (22,24Na+, 42K+, 47Ca2+, 85Sr2+, 83,86Rb+, 131,133Ba2+ and 134,137Cs+). For each tracer injection, the breakthrough of sorbing tracers was compared to the breakthrough of a conservative tracer, 82Br-, 131I-, HTO and 186ReO4-, respectively. In the two longer flow paths, no breakthrough of 83Rb+ and 137Cs+ was observed after 8 months of pumping. Selected tracer tests were subject to basic modelling in which a one-dimensional (1D) advection-dispersion model, including surface sorption, and an unlimited matrix diffusion were used for the interpretation of the results. The results of the modelling indicated that there is a slightly higher mass transfer into a highly porous material in the block-scale experiment compared with in situ experiments performed over shorter distances and significantly higher than what would have been expected from laboratory data obtained from studies of the interactions in nonaltered intact rock.     

Evaluation of transport and storage of 60Co, 134Cs, 137Cs and 65Zn by river sediments in the lower Susquehanna River

The Peach Bottom Atomic Power Station (PBAPS) has contributed measurable quantities of radioactivity to Conowingo Reservoir, an impoundment of the lower Susquehanna River. As part of an ongoing radiological assessment program, concentrations of plant-related radionuclides in sediments have been monitored in spring and fall since 1980. Mass balance estimates derived from grab samples of surface sediments (< 10 cm) indicate that less than 20% of reactor released (60)Co, (65)Zn, (134)Cs and (137)Cs is present in these sediments. Significant seasonal variations in radionuclide trapping efficiency by the reservoir are not apparent. Deep core samples (c. 200 cm) confirm that some, but not all, of this surface sediment radionuclide inventory remains within the reservoir-trapped in discrete locations by subsequent sediment accumulation. The remaining radionuclide mass, in dissolved or particle-associated form, appears to be transported downstream, through Conowingo Dam, to upper Chesapeake Bay. The detection of PBAPS-derived radionuclides in the sediments of upper Chesapeake Bay, primarily the Susquehanna Flats, confirms the transport of these radionuclides from the lower Susquehanna River.     

Assessment of adsorption behavior of dibutyltin (DBT) to clay-rich sediments in comparison to the highly toxic tributyltin (TBT)

The sorption behavior of dibutyltin (DBT) to four types of natural clay-rich sediments as a function of pH and salinity was studied. The strongest affinity of DBT was found to the montmorillonite-rich sediment, which is characterized by the highest specific surface area and cation exchange capacity of the four used sediments. Kd values range between 12 and 40 (l/kg) on simulated marine conditions (pH 8, salinity 32%). A maximum of DBT adsorption was found at a salinity of 0% and pH 6. Desorption occurred over the entire studied pH range (4-8) when contaminated sediments interact with butyltin-free water. The maximum of desorption coincided with the minimum of adsorption, and vice versa. The results of DBT adsorption are compared with tributyltin (TBT), and the mechanism of the adsorption process is discussed.     

Total,dissolved, and bioavailable metals at Lake Texoma marinas

Dissolved metals in water and total metals in sediments were measured at marina areas in Lake Texoma during June 1999 to October 2001, and October 2001, respectively. The metals most often found in the highest concentrations in marina water were Na and Ca, followed by Mg and K. Elevated Cu levels detected in lake water appeared to be associated with Cu based anti-fouling paint used on boats. Metal concentrations in sediment were much higher than in water. The relative order of the concentration in sediment was Ca > Al > Fe > K > Mg > Na. Elevated Cu level at specific locations appeared to be associated with local anthropogenic sources of boat repair activities. There were positive relationships between several metal elements in water and sediment. Metals in 16 sediments from lake marinas were extracted with a weak electrolyte solution [0.1 M Ca(NO3)2] to predict the bioavailability of metals. Among the five heavy metals studied (As, Cd, Cr, Cu and Zn), Cu was the most bioavailable in Lake Texoma marinas.     

Sediment accumulation of organic halogens in pristine forest lakes

Sediment accumulation of organic halogen was studied in two forest lakes, one pristine and one which received 30 m³ of biologically purified bleaching wastewater from a kraft pulp mill in 1979 equivalent to ca. 2 kg of adsorbable organic halogen (AOX). Lake sediments were dated with²¹⁰Pb,¹³⁴Cs and¹³⁷Cs and the annual deposition rates of organic halogens and organic matter were calculated. Organic bound halogen contents of the sediment aged 150 years was 180 μg Cl g^?1 d.w. in both lakes. The concentration of organic bound halogen at the topmost 6 cm of the sediments (less than 20-years-old) ranged from 45 to 80 μg Cl g^?1 d.w. This suggests that solvent extractable halogen had enriched in the older sediment layers. The deposition of extractable organic halogen (EOX) in the lakes in 1950’s was 4 to 5 mg Cl m^?2 a^?1. Since then, the depositon of EOX doubled in both lakes. The deposition of organic matter increased concomitantly from 50 g m^?2 a^?1 to 110 g m^?2 a^?1 in Lake Mustalampi and from 35 g m^?2 a^?1 to 62 g m^?2 a^?1 in Lake Pyylampi suggesting that the increase in the deposition of organic halogen followed the increase in the deposition of organic matter. Of the 2 kg of organic halogen discharged into the lake, 5% or less was detected in the sediment in tetrahydrofuran extractable form 15 years later.     

Dissolution of resin acids, retene and wood sterols from contaminated lake sediments

The dissolution potency of hydrophobic resin acids (RAs), retene and wood sterols from sediments was studied. These wood extractives and their metabolites are sorbed from pulp and paper mill effluents to downstream sediments. With harmful components like these, sediments can pose a hazard to the aquatic environment. Therefore, sediment elutriates with water were produced under variable conditions (agitation rate and efficiency, time), and concentrations of the dissoluted compounds were analyzed. Both naturally contaminated field sediments and artificially spiked sediments were studied. By vigorous agitation RAs can be released fast from the sediment matrix and equilibrium reached within 3 days. Compared to RAs, desorption of retene from lake sediment was slower and did not completely reach equilibrium in 23 days. Sterols spiked to pristine sediment with a 33-day contact time desorbed faster than those associated authentically with industrial sediment of from a contaminated lake. Simulating the water turbulence adjacent to a sediment surface by low and high rate of agitation in the laboratory, an increase in the mixing rate after 43-day elutriation suddenly released a high amount of wood sterols. The results indicate wide variation between hazardous chemicals in their tendency to dissolution from sediment solids. Erosion and hydrology adjacent to the sediment surface, as well as risks from dredging activities of sediments, may expose lake biota to bioactive chemicals.     

Simultaneous heavy metal removal mechanism by dead macrophytes

The use of dead, dried aquatic plants, for water removal of metals derived from industrial activities as a simple biosorbent material has been increasing in the last years. The mechanism of simultaneous metal removal (Cd2+, Ni2+, Cu2+, Zn2+ and Pb2+) by 3 macrophytes biomass (Spirodela intermedia, Lemna minor and Pistia stratiotes) was investigated. L. minor biomass presented the highest mean removal percentage and P. stratiotes the lowest for all metals tested. Pb2+ and Cd2+ were more efficiently removed by the three of them. The simultaneous metal sorption data were analysed according to Langmuir and Freundlich isotherms. Data fitted the Langmuir model only for Ni and Cd, but Freundlich isotherm for all metals tested, as it was expected. The K(F) values showed that Pb was the metal more efficiently removed from water solution. The adsorption process for the three species studied followed first order kinetics. The mechanism involved in biosorption resulted ion exchange between monovalent metals as counter ions present in the macrophytes biomass and heavy metal ions and protons taken up from water. No significant differences were observed in the metal exchange amounts while using multi-metal or individual metal solutions.     

Dating of marine sediments and time evolution of heavy metal concentrations in the Bay of Cádiz, Spain

In this paper the time evolution of heavy metal concentration of Pb, Zn, Cd and Hg, in the sediments of the Bay of Cádiz (southwest of Spain) is studied during the past century, as a result of the industrial influence in the zone. The study has been performed using sedimentary profiles that have been extracted from the seabed. The measurement of 210Pb and 137Cs radionuclides has provided the dating of the sediment layers, up to a depth corresponding to the age of 115 years. The relative sedimentation rates obtained are around 0.2 cm/year. The 137Cs activity profile reflects the concentration of this radionuclide in the atmosphere and into aquatic systems during the second half of the twentieth century. This profile has been used to ratify the results provided by the 210Pb dating method.     

Limited microbial degradation of pyrene metabolites from the estuarine polychaete Nereis diversicolor

We compared microbial mineralization of [4,5,9,10-14C]pyrene and its eukaryotic [4,5,9,10-14C]pyrene metabolites in estuarine sediments. Metabolites were obtained by exposing the estuarine deposit-feeding polychaete Nereis diversicolor to sediment-associated 14C-pyrene, followed by homogenization of the worms and extraction of the pyrene-metabolites. In sediment from a pristine Danish Fjord only 2.6% of the added metabolite-label and 1.7% of the pyrene-label were mineralized to 14CO2 during 175 days incubation. Pre-exposure of the pristine sediment to unlabelled pyrene for 60 days increased the mineralization potential for 14C-pyrene substantially, as 81.2% was mineralized to 14CO2 during 95 days incubation, whereas 14C-pyrene metabolite label was unaffected by pre-exposure to pyrene. In comparison, naturally aged bunker-oil contaminated sediment did not show elevated potentials for mineralization of neither 14C-pyrene nor 14C-metabolites. Six bacterial strains of known pyrene degraders were tested for growth on crystalline 1-hydroxypyrene. 1-Hydroxypyrene is the only intermediate eucaryotic metabolite of pyrene. The results indicate that 1-hydroxypyrene was not utilized as a sole source of carbon and energy by any of them. In addition, respiration was depressed in all six strains when exposed to crystalline 1-Hydroxypyrene, demonstrating an acute toxic effect of 1-hydroxypyrene. The results presented here suggest that microbial degradation of pyrene is not enhanced by release of aqueous and polar metabolites by marine invertebrates.     

Cesium-137 and mercury contamination in lake sediments.

The contribution of fluvial discharge and global fallout of 137Cs and mercury to sedimentation fluxes in Lake Shinji and Lake Nakaumi, Japan, was studied. The fluvial flux through soil erosion accounted for 11 to 27% of accumulated 137Cs in the sediments in the 1950's and 1960's, which were the periods of the most extensive atmospheric input, and for 90 to 100% in the 1990's. The vertical profiles of mercury concentrations in the lake sediments studied showed a maximum between 1959 and 1963, which was originated mostly from the extensive use of mercury-agrochemicals in paddyfields of the watershed in the past. These findings are representative examples of long-term contamination of lake sediments caused by the contaminated ground soil erosion.     

Impact of soil movement on carbon sequestration in agricultural ecosystems

Recent modeling studies indicate that soil erosion and terrestrial sedimentation may establish ecosystem disequilibria that promote carbon (C) sequestration within the biosphere. Movement of upland eroded soil into wetland systems with high net primary productivity may represent the greatest increase in storage capacity potential for C sequestration. The capacity of wetland systems to capture sediments and build up areas of deposition has been documented as well as the ability of these ecosystems to store substantial amounts of C. The purpose of our work was to assess rates of sediment deposition and C storage in a wetland site adjacent to a small first-order stream that drains an agricultural area. The soils of the wetland site consist of a histosol buried by sediments from the agricultural area. Samples of deposited sediments in the riparian zone were collected in 5 cm increments and the concentration of 137Cs was used to determine the 1964 and 1954 deposition layers. Agricultural activity in the watershed has caused increased sediment deposition to the wetland. The recent upland sediment is highly enriched in organic matter indicating that large amounts of organic C have been sequestered within this zone of sediment deposition. Rates of sequestration are much higher than rates that have occurred over the pre-modern history of the wetland. These data indicate the increased sedimentation rates in the wetland ecosystem are associated with increased C sequestration rates.