Biosorption of uranium and thorium

Selected samples of waste microbial biomass originating from various industrial fermentation processes and biological treatment plants have been screened for biosorbent properties in conjunction with uranium and thorium in aqueous solutions. Biosorption isotherms have been used for the evaluation of biosorptive uptake capacity of the biomass which was also compared to an activated carbon and the ion exchange resin currently used in uranium production processes. Determined uranium and thorium biosorption isotherms were independent of the initial U or Th solution concentration. Solution pH affected the exhibited uptake. In general, lower biosorptive uptake was exhibited at pH 2 than at pH 4. No discernible difference in uptake was observed between pH 4 and pH 5 where the optimum pH for biosorption lies. The biomass of Rhizopus arrhizus at pH 4 exhibited the highest uranium and thorium biosorptive uptake capacity (g) in excess of 180 mg/g. At an equilibrium uranium concentration of 30 mg/liter, R. arrhizus removed approximately 2.5 and 3.3 times more uranium than the ion exchange resin and activated carbon, respectively. Under the same conditions, R. arrhizus removed 20 times more thorium than the ion exchange resin and 2.3 times more than the activated carbon. R. arrhizus also exhibited higher uptake and a generally more favorable isotherm for both uranium and thorium than all other biomass types examined.     

Interaction of Heavy Metals in Multimetal Biosorption by Galerina vittiformis from Soil

ABSTRACT Soil heavy metal contamination, a major threat due to industrialization, can be tackled by an efficient and economical process called bioremediation. Mushrooms are employed to accumulate heavy metals from soil due to their high metal accumulation potential and better adaptability. The bioaccumulation potential of Galerina vittiformis was already reported for individual metals. At natural conditions, since soil consists of more than one polluting metal, more focus has to be given to multimetal systems. In this study, multimetal accumulation potential was analyzed using central composite design, and the responses obtained were analyzed using response surface methodology. Heavy metals such as Cu(II), Cd(II), Cr(VI), Pb(II), and Zn(II) were subjected to biosorption at 10–250 mg/kg concentrations along with pH 5–8. The results showed that the preference of the organism for the five metals under study was in the order Pb(II) > Zn(II) > Cd(II) > Cu(II) > Cr(VI) at pH 6.5 under multimetal condition. The study also indicates that the metal interaction pattern in multimetal interaction is a property of their ionic radii. The response surface methodology clearly explains the effect of interaction of heavy metals on the accumulation potential of the organism using three-dimensional response plots. The present work suggests that the fungus Galerina vittiformis could be employed as a low-cost metal removal agent from heavy metal–polluted soil.     

Investigation of uranium recovery from dilute aqueous solutions using silk fibroin

The uranium uptake ability of silk fibroin was investigated. High ability to uptake uranium from nonsaline water containing 2.500 mg of uranium was observed with the silk fibroin tested. The uranium uptake was very rapid and was dependent on pH, uranium concentration, temperature, and retention time. Almost all uranium taken up is easily eluted with 1 mol/L CH₃COONH₄. This biomatrix, therefore appears to have potential for use in a commercial process for uranium recovery from uranium-containing waste water.     

Biosorption of heavy metals by Saccharomyces cerevisiae

Abundant and common yeast biomass has been examined for its capacity to sequester heavy metals from dilute aqueous solutions. Live and non-living biomass of Saccharomyces cerevisiae differs in the uptake of uranium, zinc and copper at the optimum pH 4–5. Culture growth conditions can influence the biosorbent metal uptake capacity which normally was: living and non-living brewer's yeast: U > Zn > Cd > Cu; non-living baker's yeast: Zn > (Cd) > U > Cu; living baker's yeast: Zn > Cu (Cd) > U. Non-living brewer's yeast biomass accumulated 0.58 mmol U/g. The best biosorbent of zinc was non-living baker's yeast ( 0.56 mmol Zn/g). Dead cells of S. cerevisiae removed approximately 40% more uranium or zinc than the corresponding live cultures. Biosorption of uranium by S. cerevisiae was a rapid process reaching 60% of the final uptake value within the first 15 min of contact. Its deposition differing from that of other heavy metals more associated with the cell wall, uranium was deposited as fine-needle-like crystals both on the inside and outside of the S. cerevisiae cells.     

The mechanism of thorium biosorption by Rhizopus arrhizus

Inactive cells of Rhizopus arrhizus have been documented to exhibit a high thorium biosorptive uptake (170 mg/g) from aqueous solutions. The mechanism of thorium sequestering by this biomass type was investigated following the same method as for the uranium biosorption mechanism. The thorium sequestering mechanism appeared somewhat different from that of uranium. Experimental evidence is presented which indicates that, at optimum biosorption pH (4), thorium coordinates with the nitrogen of the chitin cell wall network and, in addition, more thorium is absorbed by the external section of the fungal cell wall. At pH 2 the overall thorium uptake is reduced. The kinetic study of thorium biosorption revealed a very rapid rate of uptake. Unlike uranium at optimum solution pH, Fe(2+) and Zn(2+) did not interfere significantly with the thorium biosorptive uptake capacity of R. arrhizus.     

Heavy metal accumulation in frogs surrounding an e-waste dump site and human health risk assessment

Abstract

This study was performed heavy metals (As, Cd, Cr, and Pb) in water, soil and frogs around an electronic-waste dump site. The bioaccumulation factors (BAFs) of heavy metals in three frog species and potential human health risks were assessed. Heavy metals were analyzed using inductively coupled plasma-optical emission spectrometry. The Cd and Pb concentrations in water samples and As and Pb concentrations in soil samples from within the e-waste dump site exceeded the standards. The heavy metal concentrations in the muscles of three frog species were as follows: Cr?>?Pb?>?As?>?Cd, and there were no significant differences among frog species except in the case of Pb (p?<?0.05). Only the Cr concentrations exceeded the food quality standards. The relative order of the BAFs for heavy metals in frogs as a result of uptake from the water and soil was Cr?>?As?>?Pb?>?Cd and Cr?>?As?>?Cd?>?Pb, respectively, which indicated that the uptake from water was greater than that from the soil. The assessment of the health risk index and carcinogenic risk (CR) indicated potential human health effects from As, Cr, and Pb via the consumption of frogs.     

Mineral and chemical characteristics,textural parameters,and the mobility of the selected elements of flotation waste,originating from the Polish copper-mining industry

This article discusses the mineralogy and geochemical characteristics of the fresh copper-flotation waste samples. The mobility of As, Cd, Cr, Cu, Ni, Pb, Tl, Zn was investigated by leaching tests. The main mineral phases identified concerned dolomite, quartz, clay minerals, feldspars, and copper-bearing minerals. Chemically, CaO and silica were dominating, along with a significant concentration of precious (Cu), refractory (Cr, Ti, V, Zr), and toxic (As, Cd, Pb) metals. Elements were bound mainly to the residual fraction and sulphides in the following order: Pb > Cu ≈ Tl > As ≈ Zn > Ni ≈ Cr > Cd. The metal mobility patterns expressed as a percentage of total concentrations, were as follows: Cd (42%) > Cr (26%)> Ni (24%) > Zn (23%) > As (22%) > Tl (20%) > Cu (18%) > Pb (2%). Those constituents were released earlier in lower pH values, although Cu, Cr, and Pb were also released in higher alkaline pH values. However, Zn release was not dependent on pH. When L/S values decreased, elements like As, Cr, Cu, Pb, and Tl were released. That process caused decrease of Cd, Ni, and Zn release.     

Substrate role in the accumulation of heavy metals in sporocarps of wild fungi

The distribution of neodymium, lead, thorium and uranium was investigated in about 100 samples of 12 different species of common, edible and non-edible mushrooms collected in unpolluted areas in the province of Ciudad Real, Central Spain. The quantitative analysis of heavy metals was performed by X-ray fluorescence spectrometry (a simple, accurate and non-destructive method). The concentration of these elements was related to three factors: mushroom specie, life style/substrate and study area. The results reveal considerable amounts of the four metals in all species analyzed as well as significant differences on the capability to accumulate these elements. The maximum absorption of Nd and Pb was found in the ectomycorrhizal Cantharellus cibarius, reaching values of 7.10 and 4.86 μg g⁻¹, respectively. Thorium and uranium were mainly accumulated (3.63 and 4.13 μg g⁻¹, respectively) in Hypholoma fasciculare although it is an epiphyte species, isolated from the mineral particles of soil. The distribution patterns of these metals in sporocarps of different habitats and locations showed no significant differences, except for thorium, mainly accumulated in mushrooms living on wood regarding these living on soil organic matter. The species-specific is therefore the determining factor for accumulation of Nd, Pb, Th and U, more than substrate, in this study.     

Regularities of lateral distribution of uranium and thorium decay series radionuclides in the anthropogenically changed soils from the area of radium production waste storage

Cartographical investigations of the territory of radium production waste storage has shown some changes in lateral differentiation of radionuclides of uranium and thorium decay series to occur during 27 years (1981-2008). Those changes are caused mostly by flat denudation typical for fluvial terrace. At present radionuclides of uranium and thorium decay series are concentrated mostly in flood lands and relief depressions. At the same time, decrease in the radionuclide activity concentration in 0-20 cm soil layer is observed with changes in lateral distribution. Total stocks of 226Ra, 210Pb and 210Po within catena soils studied in the northern and southern parts of the waste storage decreased 3-6 times, 238U - 2 times, and did not significantly change in case of 232Th during 27 years. Nonetheless, most of the samples studied are referred to radioactive waste both according to Russian standards (SPORO-2002) and IAEA safety norms (IAEA, 2004).     

Biosorption of uranium(VI) by Aspergillus fumigatus

Aspergillus fumigatus removed uranium(VI) very rapidly and reached equilibrium within 1 h of contact of biomass with the aqueous metal solution. Biosorption data fitted to Langmuir model of isotherm and a maximum loading capacity of 423 mg U g^–1 dry wt was obtained. Distribution coefficient as high as 10,000 (mg U g^–1)/(mg U ml^–1) at a residual metal ion concentration of 19 mg l^–1 indicates its usefulness in removal of uranium(VI) from dilute waste streams. Optimum biosorption was seen at pH 5.0 and was independent of temperature (5–50°C ). Initial metal ion concentration significantly influenced uptake capacity which brought down % (w/w) uranium(VI) removal from 90 at 200 mg U l^–1 to 35 at 1000 mg U l^–1. Presence of 0.84 mmol Fe²⁺, Fe³⁺, Ca²⁺ and Zn²⁺ had no effect on uranium(VI) biosorption unlike Al³⁺ (0.84 mM) which was inhibitory.     

Uptake and recovery of gold ions from electroplating wastes using eggshell membrane.

The animal byproduct, hen eggshell membrane (ESM), was evaluated for its ability to sorb gold ions (dicyanoaurate(I) and tetrachloroaurate(III)) from solutions and electroplating wastewater. The gold uptake was dependent on pH, temperature and co-ions present in the solutions, with pH 3.0 being the optimum value. The equilibrium data followed the Langmuir isotherm model with maximum capacities of 147 mg Au(I)/g dry weight and 618 mg Au(III)/g, respectively. Desorption of sorbed gold(I) with 0.1 mol/l NaOH resulted in no changes of the biosorbent gold uptake capacity through five consecutive sorption/desorption cycles. In column experiments, selective recovery of gold from electroplating wastewater containing various metal ions was noted. The affinity of metal sorption was in the order Au > Ag > Co > Cu > Pb > Ni > Zn.     

Effect of Cd,Zn, and Pb Compound Pollution on Celery in a Ferric Acrisol

A pot experiment with an orthogonal experimental design L₉(3⁴) was conducted to study the combined effects of Cd, Zn, and Pb on the growth and metal content of celery grown in a ferric acrisol. The uptake of Cd, Zn, and Pb by celery was not only affected by the individual elements, but also by combinations of the elements. The effect of coexisting elements on plant uptake of the heavy metals depended on the concentration ratios of the elements. There is a given ratio where a maximum antagonism or synergism effect occurs. The combinations of elements clearly affected the dry weight of celery and the heavy metal concentration in celery. The removal rate (the ratio of plant total uptake to the total metal content in soil) was in the order of Cd > Zn > Pb, with no obvious difference between the removal rate under single pollution and that under compound pollution.     

Chromatography and Atomic Absorption Spectrometry for the Assessment of Heavy Metal Distribution among Amino Acids Used in Parenteral Nutrition Formulations—Studies with Cadmium and Lead

The distribution of Cd (II) and Pb (II) among amino acids in parenteral nutrition formulations was investigated by coupling ion-chromatography (HPLC/IC) and electrothermal atomic absorption spectrometry. The methodology was based on ion-exchange separation and fluorimetric amino acid detection after post-column derivatization. Cd (II) and Pb (II) were assayed in 500-µL fractions of the column effluent. The distribution of Cd (II) and Pb (II) in alanine (Ala), aspartic acid (Asp), glutamic acid (Glu), glycine (Gly), histidine (His), methionine (Met), phenylalanine (Phe), serine (Ser), and threonine (Thr) were analyzed by monitoring changes in the concentration of free amino acids by HPLC/IC. The results indicated that Cd (II) and Pb (II) were distributed according to the following trend: Gly–Cd?>?Gly–Pb?>?Ala–Cd?>?Ala–Pb?>?His–Cd?～?His–Pb?>?Thr–Cd?>?Thr–Pb?>?Phe–Cd?～?Phe–Pb?～?Asp–Cd?～?Asp–Pb?～?Met–Cd?～?Met–Pb?～?Glu–Cd?～?Glu–Pb?>?Ser–Cd?～?Ser–Pb. The effects of amino acid concentration and stability constants of amino acid–metal complexes are discussed.     

Accumulation of Ag, Cd, Co, Cu, Hg, Ni and Pb in Pavlova viridis Tseng (Haptophyceae)

The flagellate alga Pavlova viridis Tseng was investigated in the laboratory for accumulation of the heavy metals, silver, cadmium, cobalt, copper, mercury, nickel and lead. The cultures were grown in an artificial seawater medium mixed with the individual metals at different concentrations. Based on data from the controls, the baseline metal concentrations in P. viridis were shown to be in an order of Cu > Pb > Co > Cd > Ni > Ag > Hg. In the experimental groups, the seven metals displayed different isotherm equilibrium patterns and the metal uptake capacity of the alga was Ni > Pb > Co > Hg > Cu > Cd > Ag at equilibrium. When assessed using the bioconcentration factors, metal accumulation by P. viridis was demonstrated to be the most efficient at a concentration of 0.001 mg L-1 for Ag, Cd and Co, and at 0.01 mg L-1 for Cu, Hg, Ni and Pb. This study suggests that P. viridis can be a source of mineral supplements in mariculture. The alga is not, however, recognized as an effective agent for removing heavy metals from wastewater. This revised version was published online in June 2006 with corrections to the Cover Date.     

Heavy metal contamination and health risk assessment in soil-rice system near Xinqiao mine in Tongling city,Anhui province,China

In this study, paddy soil and rice grain samples were collected from the vicinity around the Xinqiao mine in Tongling, China to test for the presence of heavy metals (Cd, Ni, Cr, Cu, Zn, and Pb) in soil-rice system. Results indicated that the soil samples were primarily contaminated with Cd and Cu and followed with Zn and Pb. In rice grains, Cd, Cu, and Cr concentrations exceeded recommended guidelines. However, the regional distribution of heavy metals in rice grains and soil was inconsistent. The bioaccumulation factor of heavy metals in rice grains decreased in the order of Cd > Zn > Cu > Ni > Cr > Pb. The BAF was significantly positively correlated with TCLP-extractable metals and significantly negatively correlated with soil pH. However, the relationship between soil organic matter and the BAF in rice grains was complex. Health risk assessment through rice intake showed that hazard quotients of Cu and Cd were greater than 1 and could pose a considerable non-cancer health risk to adults and children; meanwhile, Cr, Ni, and Cd could pose an unacceptable cancer risk. The results indicated that the government must take measures to reduce heavy metal contents in paddy soil and rice.     

Effects of Municipal Sewage Sludge Doses on the Chlorophyll Contents and Heavy Metal Concentration of Sugar Beet (Beta vulgaris var. saccharifera)

The present study was conducted to assess the suitability of sewage sludge amendment (SSA) in soil for Beta vulgaris var. saccharifera (sugar beet) by evaluating the heavy metal accumulation and physiological responses of plants grown at a 10%, 25%, and 50% sewage sludge amendment rate. The sewage sludge amendment was modified by the physicochemical properties of soil, thus increasing the availability of heavy metals in the soil and consequently increasing accumulation in plant parts. Cd, Pb, Ni, and Cu concentrations in roots were significantly higher in plants grown at 25% as compared to 50% SSA; however, Cr and Zn concentration was higher at 50% than 25% SSA. The concentrations of heavy metal showed a trend of Zn > Ni > Cu > Cr > Pb > Cd in roots and Zn > Cu > Ni > Cr > Pb > Cd in leaves. The only instance in which the chlorophyll content did not increase after the sewage sludge treatments was 50%. There were approximately 1.12-fold differences between the control and 50% sewage sludge application for chlorophyll content. The sewage sludge amendment led to a significant increase in Pb, Cr, Cd, Cu, Zn, and Ni concentrations of the soil. The heavy metal accumulation in the soil after the treatments did not exceed the limits for the land application of sewage sludge recommended by the US Environmental Protection Agency (US EPA). The increased concentration of heavy metals in the soil due to the sewage sludge amendment led to increases in heavy metal uptake and the leaf and root concentrations of Ni, Zn, Cd, Cu, Cr, Pb, and Zn in plants as compared to those grown on unamended soil. More accumulation occurred in roots and leaves than in shoots for most of the heavy metals. The concentrations of Cd, Cr, and Pb were more than the permissible limits of national standards in the edible portion of sugar beet grown on different sewage sludge amendment ratios. The study concludes that the sewage sludge amendment in the soil for growing sugar beet may not be a good option due to risk of contamination of Cr, Pb, and Cd.     

Effect of pH on the biosorption of nickel and other heavy metals by Pseudomonas fluorescens 4F39

Accumulation of heavy metals by Pseudomonas fluorescens 4F39 was rapid and pH-dependent. The affinity series for bacterial accumulation of metal cations decreased in the order Ni>>Hg>U>>As>Cu>Cd>Co>Cr>Pb. Metal cations were grouped into those whose accumulation increased as the pH increased, with a maximum accumulation at the pH before precipitation (Ni, Cu, Pb, Cd, Co), and those whose maximum accumulation was not associated with precipitation (Cr, As, U, Hg). High Ni²⁺ accumulation was studied. Electron microscopy indicated that at pH 9, Ni²⁺ accumulated on the cell surface as needle and hexagon-like precipitates, whose crystalline structure was confirmed by electron diffraction analysis and corresponded to two different orientations of the nickel hydroxide crystals. Crystals on cells showed marked anisotropy by X-ray powder diffraction, which differentiated them from crystals observed in nickel solution at pH 10 and 11 and from commercial nickel hydroxide. Nickel biosorption by Pseudomonas fluorescens 4F39 was a microprecipitation consequence of an ion exchange. Journal of Industrial Microbiology & Biotechnology (2000) 24, 146–151. Received 22 June 1999/ Accepted in revised form 04 December 1999     

The continuous recovery of uranium from biologically leached solutions using immobilized biomass

The potential of uranium recovery from the dilute uranium ore bioleach solutions of the Elliot Lake district of Canada was examined using immobilized microbial biomass. Batch and continuous laboratory scale pilot plant experiments were carried out. The results have shown that the immobilized microbial biomass can successfully recover all of the uranium from dilute (less than 300 mg U/L) solutions. The uranium can subsequently be eluted producing a high uranium concentration eluate perhaps exceeding 5000 mg U/L. The biomass maintained its biosorption capacity of about 50 mg U/g over 12 examined successive adsorption-elution cycles with no apparent indication of failure.     

Removal of lead from aqueous solutions by Penicillium biomass

The removal of lead ions from aqueous solutions by adsorption on nonliving Penicillium chrysogenum biomass was studied. Biosorption of the Pb(+2) ion was strongly affected by pH. Within a pH range of 4 to 5, the saturated sorption uptake of Pb(+2) was 116 mg/g dry biomass, higher than that of activated charcoal and some other microorganisms. At pH 4.5, P. chrysogenum biomass exhibited selectivity for Pb(+2) over other metal ions such as Cd(+2), Cu(+2), Zn(+2), and As(+3) Sorption preference for metals decreased in the following order: Pb > Cd > Cu > Zn > As. The sorption uptake of Pb(+2) remained unchanged in the presence of Cu(+2) and As(+3), it decreased in the presence of Zn(+2), and increased in the presence of Cd(+2). (c) 1993 John Wiley & Sons, Inc.     

Solid-Phase Chemical Fractionation of Selected Trace Metals in Some Northern Kentucky Soils

The fractionation and distribution with depth of Cd, Cr, Cu, Ni, Pb, and Zn in 26 soils of Northern Kentucky were determined through a sequential extraction procedure in response to environmental concerns about increasing anthropogenic inputs in a fast-paced, urbanizing area. The selected sites have not received any biosolid- or industrial-waste applications. Average total concentrations per metal in soil profiles derived from alluvial, glacial till, and residual materials ranged from 0.43 to 56.00 mg kg^?1 in the sequence Zn > Ni > Pb > Cr > Cu > Cd, suggesting relatively small anthropogenic inputs. The distribution of Cu, Cr, Ni, and Zn increased with soil depth, whereas Cd and Pb remained stable, indicating a strong geological or pedogenic influence. Residual forms were most important for the retention of Cu, Zn, and Ni. Cadmium and Pb exhibited a strong affinity for the Fe-Mn oxide fraction, while Cr showed the strongest association with the organic fraction. In terms of metal mobility and toxicity potential inferred from metal concentrations in labile fractions, Cd posed the greatest risk, followed by Cr ～ Pb > Ni > Zn > Cu. Soil pH, OM, and clay content were the most important parameters explaining the partitioning of metals in labile and residual fractions, emphasizing the importance of metal fractionation in soil management decisions. Alluvial soils generally contained the highest total and labile metal concentrations, suggesting potential metal enrichment through anthropogenic additions and depositional processes. These environments exhibit the highest risk for metal mobilization due to drastic changes in redox conditions, which can destabilize existing metal retention pools.