Biosorption of uranium (VI) by immobilized Aspergillus fumigatus beads

Biosorption of uranium (VI) ions by immobilized Aspergillus fumigatus beads was investigated in a batch system. The influences of solution pH, biosorbent dose, U (VI) concentration, and contact time on U (VI) biosorption were studied. The results indicated that the adsorption capacity was strongly affected by the solution pH, the biosorbent dose and initial U (VI) concentration. Optimum biosorption was observed at pH 5.0, biosrobent dose (w/v) 2.5%, initial U (VI) concentration 60 mg L⁻¹. Biosorption equilibrium was established in 120 min. The adsorption process conformed to the Freunlich and Temkin isothermal adsorption models. The dynamic adsorption model conformed to pseudo-second order model.     

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.     

Cadmium desorption in sand

Desorption of cadmium (Cd) from sand was studied by both batch and flow-through methods. Batch experiments were conducted at three pH values (5.5, 6.0 and 6.5). In each case, the amount of Cd desorbed was low compared with the quantity of Cd adsorbed previously. Desorption of Cd in the batch experiments can be described adequately by a Freundlich isotherm. The Freundlich isotherm coefficient, Kf, increased with pH. Hysteresis between the sorption/desorption isotherms was observed in all batch experiments. Flow-through experiments in soil columns were conducted for the same three pH values, with the results used to determine transport and sorption/desorption parameters. Again, the desorption isotherms bore little resemblance to the corresponding adsorption isotherms. The experimental breakthrough curves were well fitted by a nonequilibrium desorption model, however the time scale of the desorption process was much larger than measured in batch experiments. This model was therefore rejected as lacking realism. A simple linear retardation (including hysteresis) model that utilises different isotherms was found to simulate column breakthrough curves well. The Freundlich isotherm coefficients, Kf, in all batch and flow-through desorption experiments were different to values evaluated from the corresponding adsorption experiments. However, in contrast to adsorption, desorption in flow-through experiments was not noticeably affected by changes in pH. The effect of pore-water velocity on desorption was also studied at pH 6.0. No trend was established between flow velocity and the desorption coefficient.     

Decolorization of Remazol Black-B using a thermotolerant yeast, Kluyveromyces marxianus IMB3

The ability of Kluyveromyces marxianus IMB3 to decolorize Remazol Black-B dye was investigated. The effect of environmental conditions, such as pH and temperature were examined. No noticeable effects on decolorization were observed when pH varied from 3.0-5.5. Maximum colour removal, 98%, was achieved at 37 degrees C. Little or no colour removal was detected when K. marxianus IMB3 was incubated under anaerobic conditions. Further investigation, in which decolorization was monitored under extreme temperatures and low pH (to inhibit growth) and using ten fold dense inoculum, revealed that decolorization was due to biosorption to the yeast cells and not due to a metabolic reaction.     

Study on biosorption kinetics and thermodynamics of uranium by Citrobacter freudii

Biosorption has been developed as an effective and economic method to treat wastewater containing low concentrations of metal pollutants. In this study, a bacterium, Citrobacter freudii, was used as a biosorbent to adsorb uranium ions. The thermodynamics and kinetics of this adsorption, as well as its mechanism, were investigated. The results indicated that the biosorption rate could be better described by a pseudo 2nd-order model than a pseudo 1st-order model. The adsorption of U (VI) proceeded very rapidly in the first 30min and subsequently slowed down continuously for a long period. The biosorption isotherm of uranium by C. freudii could be described well by the Langmuir or Freundlich isotherm, and the latter was better. The thermodynamics parameters, DeltaH degrees , DeltaG degrees , and DeltaS degrees were calculated according to the results of the experiment, which showed this biosorption as being endothermic and spontaneous. The authors investigated the active sites of bacteria for biosorption and the results proved that carboxyl in the cell wall played an important role in biosorption.     

Sediment toxicity tests involving immobilized microalgae (Phaeodactylum tricornutum Bohlin)

Populations of calcium-alginate immobilized marine diatom Phaeodactylum tricornutum were exposed to two sediments containing different levels of surfactant (LAS). Toxic responses were compared for free and immobilized algae. Although there is a direct relation between LAS content in sediment and inhibition, immobilized algae suffered less inhibition than free cells, over all when fluorescence is chosen as a biomarker for biomass. When cells are counted from dissolved beads, inhibition of growth is closer to the values found for free cells. Immobilization can be useful for in situ experiments but protection of cells inside the alginate beads against toxic capacity of xenobiotics must be taken into account.     

Sorption of selenate on soils and pure phases: kinetic parameters and stabilisation

This study was conducted to identify the principle selenate carrier phases for two selected soils, by comparing their reactivity with selenate to that of pure phases of the solids. Silica, calcium carbonate, aluminium hydroxide, goethite, bentonite and humic acid were selected as the main soil carrier phases. Comparisons were made first on the parameter values obtained with the best fit of a kinetic sorption model which can discriminate instantaneous sorption from kinetically limited sorption. Then comparisons were made of the ability for each solid to stabilise selenate by measuring the ratio of the partition coefficient for sorption (Kd_sorption) over that of the desorption (Kd_desorption). Kinetics and stabilisation were used to help elucidate the nature of interactions with the test solid phases for a large range of selenate concentrations. The experiments were conducted over 165 h in batch reactors, the solid being isolated from the solution by dialysis tubing, at two pH (5.4 and 8) and three selenate concentrations (1 × 10⁻³, 1 × 10⁻⁶ and 1 × 10⁻⁸ mol L⁻¹). The results obtained showed that only aluminium hydroxide can sorb selenate throughout the studied pH range (pH 5.4 to 8.0). The sorption capacity on this mineral was high (Kd_sorption > 100 to 1 × 10⁴ L kg⁻¹) and the selenate was mainly stabilized by the formation of inner sphere complexes. The sorption on goethite occurred at pH 5.4 (Kd_sorption 52 L kg⁻¹), mainly as outer sphere complexes, and was null at pH 8. On silica, a weak sorption was observed only at pH 5.4 and at 165 h (Kd_sorption 4 L kg⁻¹). On bentonite, calcium carbonate and humic acid no significant sorption was observed. Concerning the two soils studied, different behaviours were observed for selenate. For soil Ro (pH 5.4), Kd_sorption was low (8 L kg⁻¹) compared to soil Bu (pH 8) (70 L kg⁻¹). The sorption behaviour of selenate on soil Ro was mainly due to outer sphere complexes, as for goethite, whereas for soil Bu the sorption was mainly attributed to inner sphere complexes followed by reduction mechanisms, probably initiated by microorganisms, in which no steady state was reached at the end of the 165 h experiments. The sorption of selenate decreased when concentrations reached 1 × 10⁻³ mol L⁻¹, due to solid saturation, except for aluminium hydroxide. Reduction of selenate seemed also to occur on goethite and soil Ro, for the same concentration, but without preventing a decrease in sorption. Thus, this work shows that the comparison of selenate behaviour between soil and pure phases helps to elucidate the main carrier phases and sorption mechanisms in soil.     

Kinetics of trace element uptake and release by particles in estuarine waters: effects of pH,salinity, and particle loading

The uptake and release of 109Cd, 51Cr, 60Co, 59Fe, 54Mn, and 65Zn were studied using end-member waters and particles from Port Jackson estuary, Australia. The kinetics of adsorption and desorption were studied as a function of suspended particulate matter (SPM) loading and salinity. Batch experiments showed that the position and slope of the pH edges are dependent on the metal and on the salinity of the water (except for Mn). The general effect of salinity was to move the adsorption edge to higher pH values, with the greatest change being found for Cd. Most of the metals showed relatively simple kinetics with an increase in uptake as a function of time and suspended particle concentrations. The time dependence of Cd uptake was more complex, with an initial adsorption phase being followed by strong mobilization from the suspended sediments, explained by chlorocomplexation and competition with seawater major cations. The reversibility of the sorption decreased in the order Co>Mn>Zn>Cd>Fe>Cr. The percentage of adsorbed metal released in desorption experiments was greater in seawater than freshwater for Cd, Zn, and Co. These results are important in understanding the cycling of pollutants in response to pH, salinity, and particle concentrations in estuarine environments. In addition, they give valuable insight into the important mechanisms controlling the partitioning of heavy metals in the Port Jackson estuary.     

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.     

常见绿化植物角质层对PAHs的吸附作用

为准确预测萘(Naphthalene,Nap)菲(Phenanthrene,Phe)、芴(Fluorene,Fl)和芘(Pyrene,Pyr)在植物叶面的吸附行为,用化学分离法分离得到马尾松(Pinus massoniana)、海桐(Pittosporum.tobira)、桂花(Osmanthus fragrans)叶面角质层,研究了角质层对Nap、Phe、Fl和Pyr的吸附特征及影响因素。结果表明:3种植物角质层吸收Nap、Phe、Fl和Pyr的作用机理是分配作用。根据线性等温吸附曲线斜率K_d值表明,3种植物角质层对Nap的吸附性能非常强,表现为桂花强于海桐和马尾松;马尾松和桂花对Phe的吸附性能相似,略强于海桐;马尾松对的Fl吸附性能强于桂花和海桐,桂花对Pyr的吸附性能强于马尾松和海桐。通过扫描电镜观测发现,马尾松角质层具有丰富的微观形貌,两侧气孔器排列紧密。桂花角质层表面粗糙呈褶皱状,海桐角质层表面平滑,但两者都未观察到气孔器。植物角质层微观结构的不同是导致植物吸附多环芳烃(polycyclic aromatic hydrocarbons, PAHs)存在种间差异的重要原因。通过傅里叶红外光谱观测显示:海桐、桂花和马尾松在C=O(～1 734 cm~(-1))均有信号,表明其表皮都有明显的酯键吸收峰;3种植物表皮角质层的C-O-C峰(～1 057 cm~(-1))也最为突出,这与其叶片中糖类含量有关。     

Impact of water quality parameters on the sorption of U(VI) onto hematite

In this study, the sorption of U(VI) from aqueous solution on hematite was studied as a function of various water quality parameters such as contact time, pH, ionic strength, soil humic acid (HA) or fulvic acid (FA), solid content and temperature by using a batch technique. The results demonstrated that the sorption of U(VI) was strongly dependent on ionic strength at pH < 6.0, and outer-sphere surface complexation may be the main sorption mechanism. The sorption was independent of ionic strength at pH > 6.0 and the sorption was mainly dominated by inner-sphere surface complexation. The presence of HA/FA increases U(VI) sorption at low pH, whereas decreases U(VI) sorption at high pH. The thermodynamic parameters (ΔH⁰, ΔS⁰, and ΔG⁰) were calculated from the temperature dependent sorption isotherms, and the results suggested that U(VI) sorption was a spontaneous and endothermic process. The results might be important for the application of hematite in U(VI) pollution management.     

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.     

Biodegradation of phthalic acid esters by immobilized microbial cells

Microorganisms capable of degrading di-n-butyl phthalate (DBP) were immobilized by polyvinyl alcohol (PVA) and used for DBP degradation. The characteristics of DBP degradation by immobilized and free cells were investigated. The experimental results showed that the degradation rate of immobilized cells was higher than that of free cells. The optimal pH and temperature for DBP degradation were determined to be 7.0 and 25°C, respectively. The semi-continuous degradation test demonstrated that high-frequency feeding of low concentration (50 mg/L) was more favourable than low-frequency feeding of high concentration (150 mg/L) for DBP degradation. The main intermediates of DBP degradation by immobilized cells were identified using a gas chromatography/mass spectrometry method. The results revealed the presence of monobutyl phthalate, phthalic acid, and protocatechuate. A tentative pathway for DBP degradation was proposed, which demonstrated that the metabolic mechanism of immobilized cells remained the same as that of the free cells.     

Investigation of 85Sr adsorption on selected soils of different horizons

Studies on the mechanism of (90)Sr migration in soil require many processes to be considered. One of the most important is sorption on the surface of mineral components of the soil. In this study adsorption of (85)Sr on a variety of soil types from different horizons has been investigated. Adsorption isotherms show various affinities of (85)Sr, depending on soil type and to a lesser extent the horizon. An important effect of pH was found with a maximum in the range 5-7. The influence of calcium ions on the extent of adsorption of (85)Sr isotope on soil samples from surface horizons of four sites is presented. Depending on the soil type differing degrees of competitive adsorption of Sr and Ca were observed. Desorption of (85)Sr by distilled water as well as Ca(NO(3))(2) solution was also examined. Both methods resulted in the removal of a considerable proportion of the adsorbed isotope from the soil. Additionally the kinetics of the desorption process were studied.     

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.     

Soil-water distribution coefficients and plant transfer factors for (134)Cs, (85)Sr and (65)Zn under field conditions in tropical Australia

Measurements of soil-to-plant transfer of (134)Cs, (85)Sr and (65)Zn from two tropical red earth soils ('Blain' and 'Tippera') to sorghum and mung crops have been undertaken in the north of Australia. The aim of the study was to identify factors that control bioaccumulation of these radionuclides in tropical regions, for which few previous data are available. Batch sorption experiments were conducted to determine the distribution coefficient (K(d)) of the selected radionuclides at pH values similar to natural pH values, which ranged from about 5.5 to 6.7. In addition, K(d) values were obtained at one pH unit above and below the soil-water equilibrium pH values to determine the effect of pH. The adsorption of Cs showed no pH dependence, but the K(d) values for the Tippera soils (2300-4100 ml/g) exceeded those for the Blain soils (800-1200 ml/g) at equilibrium pH. This was related to the greater clay content of the Tippera soil. Both Sr and Zn were more strongly adsorbed at higher pH values, but the K(d) values showed less dependence on the soil type. Strontium K(d)s were 30-60 ml/g whilst Zn ranged from 160 to 1630 ml/g for the two soils at equilibrium pH. With the possible exception of Sr, there was no evidence for downward movement of radionuclides through the soils during the course of the growing season. There was some evidence of surface movement of labelled soil particles. Soil-to-plant transfer factors varied slightly between the soils. The average results for sorghum were 0.1-0.3 g/g for Cs, 0.4-0.8 g/g for Sr and 18-26 g/g for Zn (dry weight) with the initial values relating to Blain and the following values to Tippera. Similar values were observed for the mung bean samples. The transfer factors for Cs and Sr were not substantially different from the typical values observed in temperate studies. However, Zn transfer factors for plants grown on both these tropical soils were greater than for soils in temperate climates (by more than an order of magnitude). This may be related to trace nutrient deficiency and/or the growth of fungal populations in these soils. The results indicate that transfer factors depend on climatic region together with soil type and chemistry and underline the value of specific bioaccumulation data for radionuclides in tropical soils.     

Sorption of selenium anionic species on apatites and iron oxides from aqueous solutions

The sorption of selenite and selenate ions from aqueous solutions was investigated on hydroxyapatite, fluorapatite, goethite and hematite, in order to simulate the behavior of radioactive selenium in natural or artificial sorbing media. Correlation studies with acido-basic properties and solubility of the solids were also performed. The sorption is pH dependant, but these solids are very efficient for retaining selenite at pH values generally encountered in natural waters, with however higher K(d) values for oxides than apatites. Selenate ions are much less sorbed than selenite. Several methods such as electron microscopy and spectroscopic techniques were used to identify the sorption mechanisms. In the case of hydroxyapatite, sorption proceeds by substitution of phosphate groups in the lattice of the apatite crystal in the superficial layers of the solid. In the case of goethite and hematite, sorption can be interpreted and modeled by a surface complexation process, but there is a discrepancy between sorption site densities for selenite and for protons.     

Chemisorption and Physical Adsorption Roles in Cadmium Biosorption by Chlamydomonas Reinhardtii

Abstract

The aim of this study was to investigate the mechanism of cadmium (Cd) adsorbed by microalgae Chlamydomonas reinhardtii (C.reinhardtii). The kinetic and adsorption isotherm of the process could be well described by mathematical models. Chemical modification experiments and Fourier transform infrared spectra indicated that carboxyl and amine groups were the important functional groups for adsorption of Cd. The maximum contribution of physical adsorption in the overall adsorption process was evaluated as 5.5%. These results indicated that chemisorption was the dominating mechanism of Cd biosorption by C.reinhardtii.     

Metal bioremediation through growing cells

Heavy-metal pollution represents an important environmental problem due to the toxic effects of metals, and their accumulation throughout the food chain leads to serious ecological and health problems. Metal remediation through common physico-chemical techniques is expensive and unsuitable in case of voluminous effluents containing complexing organic matter and low metal contamination. Biotechnological approaches that are designed to cover such niches have, therefore, received great deal of attention in the recent years. Biosorption studies involving low-cost and often dead/pretreated biomass have dominated the literature and, subsequently, extensive reviews focusing on equilibrium and kinetics of metal biosorption have also come up. However, the low binding capacity of biomass for certain recalcitrant metals such as Ni and failure to effectively remove metals from real industrial effluents due to presence of organic or inorganic ligands limit this approach. At times, when pure biosorptive metal removal is not feasible, application of a judicious consortium of growing metal-resistant cells can ensure better removal through a combination of bioprecipitation, biosorption and continuous metabolic uptake of metals after physical adsorption. Such approach may lead to simultaneous removal of toxic metals, organic loads and other inorganic impurities, as well as allow optimization through development of resistant species. However, sensitivity of living cells to extremes of pH or high metal concentration and need to furnish metabolic energy are some of the major constraints of employing growing cells for bioremediation. The efforts to meet such challenges via isolation of metal-resistant bacterial/fungal strains and exploitation of organic wastes as carbon substrates have began. Recent studies show that the strains (bacteria, yeast and fungi) isolated from contaminated sites possess excellent capability of metal scavenging. Some bacterial strains possess high tolerance to various metals and may be potential candidates for their simultaneous removal from wastes. Evidently, the stage has already been set for the application of metal-resistant growing microbial cells for metal harvesting. This review focuses on the applicability of growing bacterial/fungal/algal cells for metal removal and the efforts directed towards cell/process development to make this option technically/economically viable for the comprehensive treatment of metal-rich effluents.     

Effect of pH on the sorption of uranium in soils

This work was undertaken to study the influence of soil type and chemical composition on uranium sorption ratios (SR in 1 kg-1) in order to reduce the uncertainty associated with this parameter in risk assessment models. Thirteen soil samples were collected from three different locations in France under different geological conditions. Clay content varied from 7.0 to 50.0%, pH ranged from 5.5 to 8.8 and organic matter content from 1.0 to 4.6%. Soils were incubated at room temperature in polyethylene packets for 28 days in the presence of 1 mg U kg-1 soil. Sorption ratio values varied from 0.9 to 3198 for all soils with no significant effect of soil texture or of organic matter. However, soil pH was highly linearly correlated with (log SR) as a probable consequence of the existence of different uranium complexes as a function of soil pH. The sorption behaviour differences between UO2(2+) and UO2(2+)-carbonate complexes are so great that any other effect of soil properties on U sorption is hidden. Thus, soil pH should be the focus variable for reduction of the uncertainty associated with the soil Kd value used in environmental risk assessments, even for reducing the uncertainty in site-specific Kd values.