Sorption of metals onto natural organic matter as a function of complexation and adsorbent-adsorbate contact mode

The effect of complexing anion and adsorbate-adsorbent contact mode (static equilibrium or dynamic non-equilibrium) on binding and partition of Cu(2+), Cd(2+) and Zn(2+) onto organic matter (exemplified in a low-moor peat) was studied. The study comprised comparative batch and column flow-through sorption experiments on monometallic solutions of Me-Cl and Me-SO(4) salts, at pH 4.0, and sequential fractionation of sorbed metals with respect to binding strength. Both the presence of an anion having complexing properties (Cl(-)) as well as a contact mode was found to quantitatively and qualitatively affect the sorption capacity and binding strength of organic matter (peat) for metal ions. Complexing effect of Cl(-) on metal ions resulted mostly in reduction of metal ability to form strongly bound metal-organic compounds, in accordance with the order of stability constant of complex ions log K: Cd>Zn>Cu. Flow-through (dynamic) contact mode, which is the most appropriate to simulate environmental conditions, appeared to strongly attenuate the complexing effect of chloride ions on Cd and Zn sorption, and significantly enhance sorption capacity also in the absence of complexing ions. For Cd, it was mainly due to the enrichment in the strongly bound "insoluble organic" fraction, while for Zn the quantitative increase of sorption capacity did not alter significantly its partitioning. Neither a quantitative nor qualitative effect of contact mode on Cu binding was observed. Complex and diverse effects of different environmental parameters on metal sorption capacity and binding strength onto organic matter, which strongly influence metal mobility, leads to the conclusion that the correct simulation of these parameters for ecotoxicological testing is crucial for the reliable predicting of metal bioavailability under actual terrestrial environmental conditions.     

The effect of suspended particles coated by humic acid on the toxicity of pharmaceuticals, estrogens, and phenolic compounds

The sorption characteristics of 10 organic chemicals, categorized as pharmaceuticals, estrogens and phenols, onto synthetic suspended particle (i.e., alumina) coated with humic acid were investigated according to their octanol-water partition coefficient (K(ow)). Chemical analyses were performed with gas chromatography and mass spectrometry (GC/MS) and high performance liquid chromatography (HPLC). The effects of particles on the toxicity reduction were evaluated using bioassay tests, using Daphnia magna and Vibrio fisheri for phenols and pharmaceuticals, and the human breast cancer cell MCF-7 for estrogens. Sorption studies revealed that 22 and 38% of octylphenol and pentachlorophenol, respectively, were removed by suspended particle, whereas 2,4-dichlorophenol was not removed, which was directly proportional to the logK(ow) value. Similar to the sorption tests, suspended particles significantly reduced the acute toxicities of octylphenol and pentachlorophenol to D. magna and V. fisheri (p<0.01), but there was no significant difference in the toxicity of 2,4-dichlorophenol to D. magna (p=0.8374). Pharmaceuticals, such as ibuprofen, gemfibrozil and tolfenamic acid, showed no discernible sorption to the suspended particle, with the exception of diclofenac, which revealed 11% sorption. For estrogens, such as estrone, 17beta-estradiol and 17alpha-ethynylestradiol, the results indicated no reduction in the sorption test. This may be attributed to the polar interaction by functional groups in sorption between pharmaceuticals and estrogens and suspended particles. In the bioassays, presence of suspended particles did not significantly modify the toxicity of pharmaceuticals (regardless of their K(ow) values) to D. magna, V. fisheri or E-screen.     

Biosorption of uranium by chemically modified Rhodotorula glutinis

The present paper reports the biosorption of uranium onto chemically modified yeast cells, Rhodotorula glutinis, in order to study the role played by various functional groups in the cell wall. Esterification of the carboxyl groups and methylation of the amino groups present in the cells were carried out by methanol and formaldehyde treatment, respectively. The uranium sorption capacity increased 31% for the methanol-treated biomass and 11% for the formaldehyde-treated biomass at an initial uranium concentration of 140 mg/L. The enhancement of uranium sorption capacity was investigated by Fourier transform infrared (FTIR) spectroscopy analysis, with amino and carboxyl groups were determined to be the important functional groups involved in uranium binding. The biosorption isotherms of uranium onto the raw and chemically modified biomass were also investigated with varying uranium concentrations. Langmuir and Freundlich models were well able to explain the sorption equilibrium data with satisfactory correlation coefficients higher than 0.9.     

Laboratory studies of the diffusive transport of Cs and Co through potential waste repository soils

Tests using reconstituted samples have been performed to assess the diffusive transport of ¹³⁷Cs and ⁶⁰Co through natural regolith materials from a region in South Australia being considered for a radioactive waste repository. A double diffusion cell apparatus made of polycarbonate resin was developed to estimate the effective diffusion (D_e) and sorption coefficients (K_d) that allowed large withdrawals from the source and collector cells and has enabled tests with low concentrations of radioactivity. An alternative to porous stainless steel filter plates has also been used to reduce uncertainty in test interpretation. Analysis of the transient data used a staged method of the Laplace transform to take into consideration the volume of the samples withdrawn from the apparatus during testing. At test completion samples were cut into slices and analysed for radionuclide concentration. Data obtained from the sliced samples confirmed that both numerical and experimental data produced acceptable mass balance. The D_e values obtained in this study were of the order of 10⁻⁶ cm² s⁻¹ for both species, higher than previously published data. The K_d values from the diffusion and batch sorption tests were in reasonable agreement for ¹³⁷Cs, but an order of magnitude different for ⁶⁰Co. The sorption of the latter radionuclide was strongly pH dependent, and this dependency during diffusion tests would benefit from further investigation.     

Removal of uranium(VI) from aqueous solutions by manganese oxide coated zeolite: discussion of adsorption isotherms and pH effect

This paper discusses the adsorption properties for uranium(VI) by manganese oxide coated zeolite (MOCZ). The removal of uranium(VI) from aqueous solution by adsorption onto MOCZ in a single-component system with various contact times, pH, competitive ions, temperatures and initial concentrations of uranium(VI) was investigated. The experimental results were fitted to the Langmuir, Freundlich and the three-parameter Redlich-Peterson model isotherms to obtain the characteristic parameters of each model. Both the Langmuir and Redlich-Peterson isotherms were found to best represent the measured adsorption data. According to the evaluation using the Langmuir equation, the maximum adsorption capacity of uranium(VI) ions onto MOCZ was 15.1 mg g(-1) at 293K and pH 4.0. Using the thermodynamic equilibrium constants obtained at different temperatures, various thermodynamic parameters, such as DeltaG(0), DeltaH(0) and DeltaS(0), have been calculated. The thermodynamics of uranium(VI) ion/MOCZ system indicates the spontaneous and endothermic nature of the process. It was noted that an increase in temperature resulted in a higher uranium loading per unit weight of the adsorbent.     

Sector field inductively coupled plasma mass spectrometry, another tool for plutonium isotopes and plutonium isotope ratios determination in environmental matrices

The transfer of radio nuclides into the different compartments of the environment are widely studied and leads to the elaboration of transfer models in order to evaluate potential impact onto the environment and humans. Accurate experimental data are needed to validate these models for all types of matrices (air, water, sediments, soils, biota and food...). Among these radionuclides, 238Pu, 239Pu, 240Pu and 241Pu, are often mentioned. They have been released into the environment by nuclear weapon tests, nuclear facilities, reactors or satellite accidents. These different sources have different 240Pu/239Pu ratios and therefore this ratio is used to provide information on the source of contamination into the environment. The most conventional analytical tools used for plutonium isotope determination are liquid scintillation and alpha spectrometry, and thermal ionisation mass spectrometry (TIMS) is still considered as the primary method for determination of plutonium isotope ratios. During the last decade, mass spectrometers equipped with plasma ion sources and sector field analysers were developed and can offer now another alternative method for the accurate determination of isotope content and ratios of long-lived radionuclides in environmental samples. This paper presents and discusses the results obtained for 239Pu, 240Pu and 241Pu content and isotope ratios by sector field ICP-MS in different environmental matrices.     

Modelling the joint effects of a metal and a pesticide on reproduction and toxicokinetics in Lumbricid earthworms

It is important to understand the aetiology of interactive mixtures effects (i.e. synergism and antagonism) if results from known cases are to be extrapolated to untested combinations. The key role of toxicokinetics in determining internal concentrations at target sites means that understanding chemical uptake in mixtures is an essential requirement for mechanistic understanding of interactions. In this paper, a combined approach using mixture toxicity testing, toxicokinetic studies and modelling has been used to address the link between joint toxicity and internal concentration. The study is conducted in Lumbricid earthworms with a binary mixture of a metal (nickel) and an organophosphate insecticide (chlorpyrifos) not a priori expected to show interactive toxicity. As expected from their dissimilar modes of action and detoxification, exposure to combinations of nickel and chlorpyrifos resulted in additive toxicity. Measurement of internal concentrations indicated that both chemicals were rapidly accumulated (within 3 days) to equilibrium. When exposed as a mixture, Ni uptake followed the same pattern as found for the single chemical. This was not the case for chlorpyrifos which showed a faster rate of uptake and elimination and a slightly higher equilibrium concentration in a mixture. That the difference in chlorpyrifos kinetics in the mixture did not result in interactive toxicity highlights the need to assess chemical toxicodynamics as well as toxicokinetics. Measurement of chlorpyrifos-oxon identified the presence of this toxic form but implementation of more complex approaches encompassing toxicogenomics and epigenetics are ultimately needed to resolve the toxicokinetic to toxicodynamic link for these chemicals.     

Adsorption studies on coir pith for heavy metal removal

Biosorption efficiency of coir pith, a waste product from coir industry, was investigated in this study for the removal of metallic pollutants such as Ni, Cu and Zn from aqueous solutions. The disposal of coir pith is a major problem associated with the coir industries, especially working in the small-scale sector. The present study explores the effectiveness of utilization of coir pith, an accumulating waste, as a biosorbent for heavy metal removal. Batch mode studies were done to evaluate the efficiency of removal of metals under varying adsorption conditions of pH, metal concentration and contact time. Characterization studies of the biosorbent and SEM analysis were done. Kinetic modelling studies were tried using Lagergren pseudo-first-order and second-order models. Equilibrium studies were done using well-known Freundlich, Langmuir and D–R isotherm models. It was found that all isotherms are fitting well indicating the efficiency of coir pith as an adsorbent of heavy metals. The applicability of all the three isotherms to the sorption processes shows that both monolayer adsorption and heterogeneous energetic distribution of active sites on the surface of the adsorbent are possible. Due to the abundance and low cost of these materials, adsorption technologies developed can act as good sustainable options for the future in heavy metal removal from industrial effluents.     

Irreversible sorption of pentachlorophenol to sediments: experimental observations

The partitioning behavior of pentachlorophenol (PCP) in five sediments was studied using equilibrium sorption experiments and multiple cycles of sorption and desorption experiments. The results of the equilibrium sorption experiments showed that the isotherms of PCP on five sediments were linear and the partitioning coefficients (Kd) were proportional to the organic carbon content of the sediments. The average organic carbon content normalized partitioning coefficient (logK oc) of five sediments was 2.83 +/- 1.48. In multiple cycles of sorption and desorption experiments, the five sediments were found to exhibit statistically significant sorption-desorption hysteresis, and the hysteresis indices (HI) varied over a wide range (0.72 - 11.82). Correlations between the HI value and the percentage of lipid in the total organic matter in the sediment indicated that lipid was the main fraction to affect the hysteresis phenomenon, i.e., the higher the lipid percentage the greater the HI value. The hysteresis phenomenon was mostly caused by irreversible sorption of PCP on lipids, including entrapment by lipids, which induced the slow desorption rate from the sediment. Because of hysteresis in the sorption and desorption, the PCP ecological toxicity would be lower than expected.     

Sorption-desorption tests to assess the risk derived from metal contamination in mineral and organic soils

We obtained the sorption isotherms of Cd, Cu, Pb and Zn from seven soils with contrasting properties, including mineral and organic soils. The distribution coefficients (Kd) were determined from batch tests in a solution that simulated the soil solution cationic composition. The Kd values of the target metals varied greatly depending on soil type and initial metal concentration. Sorption isotherms were fitted to Freundlich and Langmuir models, and derived parameters were correlated to soil properties through the construction of a correlation matrix and application of Principal Component Analysis. The batch Kd showed a satisfactory agreement with the Kd obtained from field-contaminated soils. The sorption tests were complemented with the estimation of the reversibility of metal sorption by the application of an extraction test. The extraction yields, which did not relate to the initial metal concentration, depended on the metal-soil combination, and showed no correlation to batch Kd values. The risk derived from a contamination event was estimated through the quantification of a Retention Factor, defined as the ratio of the Kd versus the extraction yield. Results showed that this was an excellent index to highlight which metal and soil represent the most vulnerable scenarios after a contamination event.     

Sorption behavior of selenium on humic acid under increasing selenium concentration or increasing solid/liquid ratio

The sorption of selenium (Se) on humic acid (HA) was investigated in order to better understand the fate of stable and radioactive Se in soils and sediments. An ultrafiltration technique was used to determine size distributions of HA-sorbed-Se when increasing Se concentration and solid/liquid ratio. The results showed that the Se sorption onto HA followed the Freundlich isotherm. No solid/liquid ratio-dependence was observed especially when <3 kDa molecular size fraction was used from solid/liquid separation. The Freundlich isotherm parameters K(F) and n obtained using the <3 kDa molecular size fraction for solid/liquid separation were 3.7 x 10(2) and 0.82, respectively. In addition, since dissolved HA increased with decreased ionic strength in the HA suspension, ionic strength could promote aggregation of HA. The conformational change of HA could affect the sorption behavior of Se on HA.     

The interaction of heavy metals with urban soils: sorption behaviour of Cd, Cu, Cr, Pb and Zn with a typical mixed brownfield deposit

This study investigated the sorption characteristics and release of selected heavy metals (Cd, Cu, Cr, Pb and Zn) from a typical urban soil material from a derelict brownfield site in Western Scotland, UK. The study aimed to evaluate contaminant interactions with an urban substrate, comprising a mix of mineral soil and residue materials (e.g. brick, concrete, wood). This type of material has received little consideration in the literature to date. Soil samples were subject to a sequence of test involving batch equilibration and dynamic leaching, in single (non-competitive) and multi-element (competitive) solutions. The batch experiments were carried out in unadjusted and close to soil field pH conditions (pH 2 and 7, respectively). The equilibrium adsorption capacity for heavy metals was measured and extrapolated using the Langmuir isotherm. The parameters of the isotherms x(m) (the maximum amount adsorbed per unit mass of adsorbent (mg/g)) and b (adsorption constant (m(3)/g)) were calculated for Cd, Cu, Cr, Pb as single-element and multi-element solutions. The adsorption from the single-element solution was more effective than adsorption under multi-element conditions, due to competitive effects. For example, the adsorption of copper from a single-element solution was over four times greater than for a multi-element solution. In the case of Cr and Zn, migration of metal from soil to solution was observed. Adsorption capacity at pH 2 followed the order Cr>Cu>Pb>Cd and at pH 7 Cd>Zn, with precipitation affecting Cu and Pb behaviour. During the column leaching experiment, most of the heavy metals were irreversibly bound to the soil, but in the case of Cr some movement from soil into solution was observed. The results also showed that Cd, Cu, Pb and Zn were removed from the solution and adsorbed on the soil. No significant difference in the metal removal from single- and multi-element solutions was observed. Overall, the urban residue behaved in a similar manner to mineral soils despite a significant component of anthropogenic solid materials.     

Efficiency of locally available filter media on fluoride and phosphate removal for household water treatment system

Since conventional water treatment is not affordable in developing countries,looking for locally available and alternative treatment options is mandatory.Removal of fluoride and phosphate can be achieved by designing appropriate filtration media from different materials such as sand,calcined clay,pumice,scoria and bone char.This study was designed to determine the removal efficiency of these locally available filter media with respect to detention time and pH.The filtration apparatuses(tank)were filled separately with stone,gravel with grain size 0.6-4.75 mm and 40 cm deep,sand(ES=0.15-0.35 mm and UC=1.5-3),calcined clay,pumice,scoria and bone char with grain size 0.25-0.5 inch.Water samples were prepared using glass bottles with fluoride concentrations of 6 and 8 mg/l and phosphate concentration of 4 mg/1.Laboratory analysis was carried out before and after filtration to determine the removal efficiency of each medium.It was found that the highest removal of fluoride was achieved by bone char(89.65%),followed by pumice(82.4%).However,bone char has rather increased the concentration of phosphate by 63.8%.Sand was the most efficient media to remove phosphate,managing to remove by 70%.Therefore,it is an attractive option to use these locally available,environmental friendly and appropriate technologies for efficient removal of both fluorine and phosphate at the household or community water treatment level.     

Validating riverine transport and speciation models using nuclear reactor-derived radiocobalt

Risk assessment of intentional or accidental discharges of toxic substances into river systems requires combined hydraulic and chemical modeling. Periodic discharges of known volumes with low radioactivity by the Beznau nuclear reactor (Switzerland) serve as validation tracers for both river flow and chemical speciation simulation. Validation of the former has been achieved by comparison of modeled and measured arrival times of radiocobalt along a 65 km transect with a maximum reaction period of 24 hours. Modeled breakthrough curves coincide well with measurements collected during three field campaigns, in spite of the fact that sorption and sedimentation processes were not activated during simulation. This gives indirect evidence of inefficient cobalt sorption. Particle/solution distribution measurements carried out during breakthrough allow further validation of our speciation approach, which is based on Tableau setup of inorganic reactions combined with sorption and organic complexation. Modeled and measured speciation results confirm recent observations of enhanced complexation of cobalt with dissolved organic substances, which significantly reduces particle sorption. The large variability of conditional stability constants for sorption and complexation reactions, for sorption site densities, and for organic ligand concentrations explains the variability of published particle-solution distribution coefficients.     

Fixation of Cs to marine sediments estimated by a stochastic modelling approach

Dumping of nuclear waste in the Kara Sea represents a potential source of radioactive contamination to the Arctic Seas in the future. The mobility of 137Cs ions leached from the waste will depend on the interactions with sediment particles. Whether sediments will act as a continuous permanent sink for released 137Cs, or contaminated sediments will serve as a diffuse source of 137Cs in the future, depends on the interaction kinetics and binding mechanisms involved. The main purpose of this paper is to study the performance of different stochastic models using kinetic information to estimate the time needed for Cs ions to become irreversibly fixed within the sediments. The kinetic information was obtained from 134Cs tracer sorption and desorption (sequential extractions) experiments, conducted over time, using sediments from the Stepovogo Fjord waste dumping site, on the east coast of Novaya Zemlya. Results show that 134Cs ions interact rapidly with the surfaces of the Stepovogo sediment, with an estimated distribution coefficient Kd(eq) of 300 ml/g (or 13m2/g), and the 134Cs ions are increasingly irreversibly fixed to the sediment over time. For the first time, stochastic theory has been utilised for sediment-seawater systems to estimate the mean residence times (MRTs) of Cs ions in operationally defined sediment phases described by compartment models. In the present work, two different stochastic models (i) a Markov process model (MP) being analogous to deterministic compartment models, and (ii) a semi-Markov process model (SMP) which should be physically more relevant for inhomogeneous systems, have been compared. As similar results were obtained using the two models, the less complicated MP model was utilised to predict the time needed for an average Cs ion to become irreversibly fixed in the Stepovogo sediments. According the model, approximately 1100 days of contact time between Cs ions and sediments is needed before 50% of the 134Cs ion becomes fixed in the irreversible sediment phase. while about 12.5 years are needed before 99.7% of the Cs ions are fixed. Thus, according to the model estimates the contact time between 137Cs ions leached from dumped waste and the Stepovogo Fjord sediment should be about 3 years before the sediment will act as an efficient permanent sink. Until then a significant fraction of 137Cs should be considered mobile. The stochastic modelling approach provides useful tools when assessing sediment-seawater interactions over time, and should be easily applicable to all sediment-seawater systems including a sink term.     

Sorption of trihalomethanes in foods

Trihalomethanes (THMs, namely, CHCl₃, CHCl₂Br, CHClBr₂ and CHBr₃) are disinfection by-products that are present in drinking water. These toxic chemicals are also present in meat, dairy products, vegetables, baked goods, beverages and other foods, although information regarding their concentrations and origin is very limited. This study investigates sorption of THMs occurring during rinsing and cooking of foods and the significance of food as an exposure source.Initial estimates of THM uptake were measured in experiments representing rinsing with tap water at 25 C using nine types of food, and for cooking in tap water at 90 C for fourteen other foods. A subset of foods was then selected for further study over a range of THM concentrations (23.7–118.7 μg/l), temperatures (25 C and 90 C), food concentrations (0.2–1.4, food weight: water weight), and contact times (5–240 min). Data were analyzed using regression and exponential models, and diffusion models were used to help explain the trends of THM uptake.Among vegetables, sorbed THM concentrations at 25 C were 213 to 774 ng/g for CHCl₃, 53 to 609 ng/g for CHCl₂Br, and 150–845 ng/g for CHClBr₂. Meats at 90 C tended to have higher concentrations, e.g., 870–2634 ng/g for CHCl₃. Sorbed concentrations increased with contact time and THM concentration, and decreased with food concentration in rinsing tests (using spinach, iceberg-head lettuce and cauliflower) and cooking tests (using tomato, potato, beef and miso–tofu soup). For most foods, THM uptake was diffusion limited and several hours were needed to approach steady-state levels. Swelling, hydrolysis and other physical and chemical changes in the food can significantly affect sorption. Screening level estimates for CHCl₃ exposures, based on experimental results and typical food consumption patterns, show that uptake via foods can dominate that due to direct tap water consumption, suggesting the importance of sorption and the need for further evaluation of THM intake due to foods.     

Cadmium biosorption by cells of Spirulina platensis TISTR 8217 immobilized in alginate and silica gel

The biosorption of cadmium by immobilized Spirulina platensis on alginate gel and silica gel was studied. The maximum biosorption capacities for alginate immobilized cells and silica immobilized cells were 70.92 and 36.63 mg Cd/g biomass, respectively. Temperature did not have an influence on metal sorption, whereas an initial pH solution did. Sorption occurred in a wide pH range (pH 3-8). The highest adsorption of alginate immobilized cells was at pH 6, while silica immobilized cell adsorption was not affected at pH between 4 and 7. The immobilized cells were reused in consecutive adsorption-desorption. The results showed that immobilized cells could be repeatedly used in the sorption process up to five times.     

An overview of BORIS: Bioavailability of Radionuclides in Soils

The ability to predict the consequences of an accidental release of radionuclides relies mainly on the level of understanding of the mechanisms involved in radionuclide interactions with different components of agricultural and natural ecosystems and their formalisation into predictive models. Numerous studies and databases on contaminated agricultural and natural areas have been obtained, but their use to enhance our prediction ability has been largely limited by their unresolved variability. Such variability seems to stem from incomplete knowledge about radionuclide interactions with the soil matrix, soil moisture, and biological elements in the soil and additional pollutants, which may be found in such soils. In the 5th European Framework Programme entitled Bioavailability of Radionuclides in Soils (BORIS), we investigated the role of the abiotic (soil components and soil structure) and biological elements (organic compounds, plants, mycorrhiza, and microbes) in radionuclide sorption/desorption in soils and radionuclide uptake/release by plants. Because of the importance of their radioisotopes, the bioavailability of three elements, caesium, strontium, and technetium has been followed. The role of one additional non-radioactive pollutant (copper) has been scrutinised in some cases. Role of microorganisms (e.g., K(d) for caesium and strontium in organic soils is much greater in the presence of microorganisms than in their absence), plant physiology (e.g., changes in plant physiology affect radionuclide uptake by plants), and the presence of mycorrhizal fungi (e.g., interferes with the uptake of radionuclides by plants) have been demonstrated. Knowledge acquired from these experiments has been incorporated into two mechanistic models CHEMFAST and BIORUR, specifically modelling radionuclide sorption/desorption from soil matrices and radionuclide uptake by/release from plants. These mechanistic models have been incorporated into an assessment model to enhance its prediction ability by introducing the concept of bioavailability factor for radionuclides.