Phytoremediation: role of terrestrial plants and aquatic macrophytes in the remediation of radionuclides and heavy metal contaminated soil and water.

Nuclear power reactors are operating in 31 countries around the world. Along with reactor operations, activities like mining, fuel fabrication, fuel reprocessing and military operations are the major contributors to the nuclear waste. The presence of a large number of fission products along with multiple oxidation state long-lived radionuclides such as neptunium ((237)Np), plutonium ((239)Pu), americium ((241/243)Am) and curium ((245)Cm) make the waste streams a potential radiological threat to the environment. Commonly high concentrations of cesium ((137)Cs) and strontium ((90)Sr) are found in a nuclear waste. These radionuclides are capable enough to produce potential health threat due to their long half-lives and effortless translocation into the human body. Besides the radionuclides, heavy metal contamination is also a serious issue. Heavy metals occur naturally in the earth crust and in low concentration, are also essential for the metabolism of living beings. Bioaccumulation of these heavy metals causes hazardous effects. These pollutants enter the human body directly via contaminated drinking water or through the food chain. This issue has drawn the attention of scientists throughout the world to device eco-friendly treatments to remediate the soil and water resources. Various physical and chemical treatments are being applied to clean the waste, but these techniques are quite expensive, complicated and comprise various side effects. One of the promising techniques, which has been pursued vigorously to overcome these demerits, is phytoremediation. The process is very effective, eco-friendly, easy and affordable. This technique utilizes the plants and its associated microbes to decontaminate the low and moderately contaminated sites efficiently. Many plant species are successfully used for remediation of contaminated soil and water systems. Remediation of these systems turns into a serious problem due to various anthropogenic activities that have significantly raised the amount of heavy metals and radionuclides in it. Also, these activities are continuously increasing the area of the contaminated sites. In this context, an attempt has been made to review different modes of the phytoremediation and various terrestrial and aquatic plants which are being used to remediate the heavy metals and radionuclide-contaminated soil and aquatic systems. Natural and synthetic enhancers, those hasten the process of metal adsorption/absorption by plants, are also discussed. The article includes 216 references.

Role of alkyl chain branching on aggregation behavior of two symmetrical diglycolamides: small angle neutron scattering studies.

The two long alkyl chain derivatives of diglycolamide (DGA), viz. N,N,N',N'-tetraoctyl diglycolamide (TODGA) and N,N,N',N'-tetra(2-ethylhexyl)-diglycolamide (T2EHDGA) have been found promising for actinide partitioning from high-level waste. The solvent extraction studies have suggested the participation of three to four DGA molecules in the extracted complex of trivalent actinides and lanthanides. However, coordination of 3-4 tridentate DGA ligands with trivalent f-elements seems to be unusual due to restricted coordination sites in these metal ions. Nonetheless, the extraction data have been explained in view of the formation of aggregates of these ligands in the organic phase. Small Angle Neutron Scattering (SANS) measurements were carried out to investigate the aggregation behavior of DGA ligands in deuterated n-dodecane. The aggregation of DGA molecules was facilitated by the presence of acid. However, the presence of nitrate ions in the aqueous phase had no significant effect on the aggregation of DGA. Similarly, the presence of metal ions such as Sr(II) or Eu(III) marginally affected the aggregation tendency of DGA molecules. TODGA displayed higher aggregation tendency than that of T2EHDGA. The extraction data of trivalent f-elements were in conformity with the aggregation tendency of the two DGA ligands.

Liquid-liquid extraction and flat sheet supported liquid membrane studies on Am(III) and Eu(III) separation using 2,6-bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine as the extractant.

Solvent extraction and supported liquid membrane transport studies for the preferential removal of Am(3+) from feeds containing a mixture of Am(3+) and Eu(3+) was carried out using 2,6-bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine (n-Pr-BTP) as the extractant. Diluent plays an important role in these studies. It was observed that the distribution coefficients deteriorate significantly for both Am(3+) and Eu(3+) though the separation factors were affected only marginally. The transport studies were carried out at pH 2.0 in the presence of NaNO(3) to result in the preferential Am(3+) transport with high separation factors. Effect of different experimental parameters, viz. feed composition, stripping agents, diluents of the organic liquid membrane and membrane pore size was studied on the transport and separation behaviour of Am(3+) and Eu(3+). The supported liquid membrane studies indicated about 85% Am(3+) and 6% Eu(3+) transport in 6h using 0.03 M n-Pr-BTP in n-dodecane/1-octanol (7:3) diluent mixture for a feed containing 1M NaNO(3) at pH 2 and a receiver phase containing pH 2 solution as the strippant. Consequently, a permeability coefficient of (1.75 ± 0.21) × 10(-4)cms(-1) was determined for the Am(3+) transport. Stability of the n-Pr-BTP and its SLM was also studied by carrying out the distribution and transport experiment after different time intervals.

Chromatographic separation of carrier free 90Y from 90Sr using a diglycolamide based resin for possible pharmaceutical applications.

N,N,N',N'-tetraoctyl diglycolamide (TODGA) has been used as the stationary phase in an extraction chromatography resin (XCR) material prepared for evaluating the uptake and the separation behaviour of (90)Y and (90)Sr from acidic feeds. Chromosorb-W was used as the solid support material while the feed solution was usually 4M HNO(3). The batch uptake studies have suggested almost no Sr(II) uptake while Y(III) uptake increased with acidity up to 4M HNO(3) beyond which a decrease in the K(d,w) values were observed. Column studies were carried out and breakthrough profiles were obtained for both Y(III) and Sr(II). No breakthrough of Y(III) was noticed even when >50 column volumes of the feed (carrier free (90)Y at 4 M HNO(3)) was passed through the column while about 20 column volumes were required for the breakthrough of Y(III) when the feed contained 1 g/L Y in 4 M HNO(3) spiked with (90)Y tracer. The reusability of the column was also studied which indicated in the deterioration of the column performance as shown by the sharp fall in the breakthrough volumes and was attributed to the probable leaching of the reagent from the support material. The role of absorbed dose was also investigated for Y(III) uptake. Separation of carrier free (90)Y tracer was carried out by loading the column with (90)Sr and eluting with 0.01M solutions of HNO(3) as well as EDTA. The purity of the product was ascertained by half-life method.

Effect of humic acid on sorption of technetium by alumina.

Sorption of technetium by alumina has been studied in absence as well as in presence of humic acid using (95)Tc(m) as a tracer. Measurements were carried out at fixed ionic strength (0.1M NaClO(4)) under varying pH (3-10) as well as redox (aerobic and reducing anaerobic) conditions. Under aerobic conditions, negligible sorption of technetium was observed onto alumina both in absence and in presence of humic acid. However, under reducing conditions (simulated with [Sn(II)] = 10(-6)M), presence of humic acid enhanced the sorption of technetium in the low pH region significantly and decreased at higher pH with respect to that in absence of humic acid. Linear additive as well as surface complexation modeling of Tc(IV) sorption in presence of humic acid indicated the predominant role of sorbed humic acid in deciding technetium sorption onto alumina.

Studies on the selective Am3+ transport, irradiation stability and surface morphology of polymer inclusion membranes containing Cyanex-301 as carrier extractant.

Transport behaviour of Am(3+) across cellulose triacetate (CTA) based polymer inclusion membranes (PIM) containing Cyanex-301 (bis(2,4,4-trimethylpentyl)dithiophosphinic acid) as the carrier extractant and tri-n-butyl phosphate (TBP) or 2-nitrophenyloctylether (NPOE) as the plasticizer was investigated from different feed and strip conditions. The TBP plasticized membrane resulted back transport of Am when alpha-hydroxy iso-butyric acid was used as the complexing agent in the strip phase while no such effect was seen when ethylene diamine tetraacetic acid (EDTA) was used as the complexant. Effect of varying Cyanex-301 concentration and bipyridyl (bipy) concentration on Am transport was also investigated. Long term reusability of the membrane was studied by measuring the permeability coefficient (P) after exposing the PIMs to a maximum gamma ray dose of ∼ 200 kGy. The surface morphology of the membranes was analyzed by atomic force microscopy and the roughness parameter was correlated to transport efficiency.

Facilitated transport of uranium(VI) across supported liquid membranes containing T2EHDGA as the carrier extractant.

Facilitated transport of uranyl ion from nitric acid feed solutions was investigated across PTFE supported liquid membranes using N,N,N',N'-tetra-2-ethylhexyl-3-pentane-diamide (T2EHDGA) in n-dodecane as the carrier extractant containing 30% iso-decanol as the phase modifier. Solvent extraction studies indicated extraction of species of the type, UO(2)(NO(3))(2)·T2EHDGA. The distribution coefficients increased in the presence of NaNO(3) as compared to equivalent concentration of HNO(3) which was exactly the opposite of what was reported for Am(III)-TODGA extraction system. Supported liquid membrane studies indicated about 11h were required for quantitative transport of U(VI) from a feed of 3M HNO(3) using 0.2M T2EHDGA in n-dodecane containing 30% iso-decanol as the carrier extractant. Effect of various parameters such as feed acidity, T2EHDGA concentration, and nature of the strippant on the transport rate was investigated. The transport was found to be diffusion controlled in the membrane phase and the permeability coefficient was calculated to be (3.20 ± 0.13)× 10(-4)cm/s for the feed composition of 3M HNO(3), receiver phase composition of 0.01 M HNO(3) and membrane carrier phase of 0.2M T2EHDGA in n-dodecane containing 30% iso-decanol. The present results may be useful for the separation of U from lean solutions or radioactive wastes considered hazardous due to the presence of alpha-particle emitting radionuclides.

Sorption of curium by silica colloids: effect of humic acid.

Sorption of curium by silica colloids has been studied as a function of pH and ionic strength using (244)Cm as a tracer. The sorption was found to increase with increasing pH and reach a saturation value of ∼95% at pH beyond 5.3. The effect of humic acid on the sorption of (244)Cm onto silica was studied by changing the order of addition of the metal ion and humic acid. In general, in the presence of humic acid (2 mg/L), the sorption increased at lower pH (<5) while it decreased in the pH range 6.5-8 and above pH 8, the sorption was found to increase again. As curium forms strong complex with humic acid, its presence results in the enhancement of curium sorption at lower pH. At higher pH the humic acid present in the solution competes with the surface sites for curium thus decreasing the sorption. The decrease in the Cm sorption in presence of humic acid was found to be less when humic acid was added after the addition of curium. Linear additive model qualitatively reproduced the profile of the Cm(III) sorption by silica in presence of humic acid at least in the lower pH region, however it failed to yield quantitative agreement with the experimental results. The results of the present study evidenced the incorporation of Cm into the silica matrix.

Separation of 90Y from 90Sr by a solvent extraction method using N,N,N',N'-tetraoctyl diglycolamide (TODGA) as the extractant.

The relative extraction efficiency of N,N,N',N'-tetraoctyl diglycolamide (TODGA) towards Y(3+) and Sr(2+) was investigated from HNO(3) as well as HCl medium. The separation factor (S.F.) values were found to be much higher in HCl medium as compared to those obtained from HNO(3) medium. Based on the high separation factor values obtained in the HCl media, a separation method for (90)Y from (90)Sr (containing (90)Y in secular equilibrium) has been developed in the present work. The purity of the separated (90)Y was ascertained from its decay profile and half-life measurements. The extracted species was determined to be Y(X)(3) · 3TODGA where X(-) is the nitrate or the chloride anion. The thermodynamic parameters were also determined and the two phase extraction constants (log K(ex)) were calculated. The extraction of Y(III) was highly exothermic and entropy destabilized and was equally favourable from both HNO(3) medium as well as HCl medium.

Selective separation of radio-cesium from acidic solutions using supported liquid membrane containing chlorinated cobalt dicarbollide (CCD) in phenyltrifluoromethyl sulphone (PTMS).

A supported liquid membrane method was developed using chlorinated cobalt dicarbollide (CCD) in phenyltrifluoromethyl sulphone (PTMS) as the carrier, impregnated in PTFE flat sheet membranes for the selective separation of Cs(I) from nitric acid feed solution. Solvent extraction studies were carried out for optimizing the feed as well as strip conditions. >95% Facilitated transport of Cs(I) was observed in about 3h when 1M HNO(3) and 8M HNO(3) were used as the feed and strip solutions, respectively while 0.025M CCD in PTMS was used as the carrier extractant. Selectivity studies, carried out using a mixture of radiotracers viz. (51)Cr, (59)Fe, (99)Mo, (99m)Tc, (106)Ru, (137)Cs, (152)Eu and (241)Am, indicated selective transport of Cs(I) with DF values >100. Though reproducibility of the transport data was excellent when carried out in two successive transport experiments with freshly loaded carrier solvent, the stability of the membrane was poor which restricts its long term use.

Sorption of 137Cs, 133Ba and 154Eu by synthesized sodium aluminosilicate (Na-AS).

Sodium aluminosilicate has been synthesized by solution route for use as a sorbent for various radionuclides. It was characterized by XRD, zeta potential, BET surface area, FTIR spectroscopy and site density measurement. Sorption studies of (137)Cs, (133)Ba and (154)Eu on synthesized sodium aluminosilicate have been carried out at varying pH (3-10). Sorption of all the metal ions was found to increase with pH of suspension with the saturation value increasing with the oxidation state of metal ion. Effect of Aldrich humic acid (2mg/l) on sorption was also investigated. In case of (137)Cs, the sorption was not affected by the presence of humic acid, while in case of (133)Ba and (154)Eu, sorption was enhanced at lower pH and decreased at higher pH in presence of HA. A series of experiments were carried out for (154)Eu sorption on sodium aluminosilicate at various conditions. Sorption of europium was analyzed by different sorption isotherms, viz., Freundlich and D-R isotherm. Thermodynamic data reveal sorption phenomena as endothermic and spontaneous. Studies were further extended to find out effect of diverse ions (Ca(2+) and CO(3)(2-)) on sorption of europium.

Direct determination of metallic impurities in graphite by EDXRF.

Energy dispersive X-ray fluorescence (EDXRF) methods have been developed for the direct determination of 14 trace metallic impurities in graphite powder without any need for sample dissolution. Using synthetic standards, calibration curves were established for different elements after optimizing the spectrometer parameters. Two synthetic samples were analyzed to evaluate the performance of the developed analytical methods. The estimates for most of the analytes were in good agreement with the added amounts. Three graphite powder samples were analyzed by the present method as well as by D.C. arc emission spectrometric technique for comparison and the agreement between the analyte values determined, using both methods was good. Samples in pellet form were analyzed using a separate calibration with standards in pellet form. The present method is rapid, as it alleviates the need for any chemical treatment and gives good precision.

Dynamic light scattering study on the aggregation behaviour of N,N,N',N'-tetraoctyl diglycolamide (TODGA) and its correlation with the extraction behaviour of metal ions.

Dynamic light scattering (DLS) studies were carried out to investigate the aggregation behaviour of N,N,N',N'-tetraoctyl diglycolamide (TODGA) in n-dodecane and 1-octanol. The effect of the nature and concentration of different acids such as HCl, HNO(3) and HClO(4) on aggregation behaviour was investigated. The aggregation tendency of TODGA in different acids followed the order: HClO(4)>HNO(3)>HCl, which is similar to the extraction pattern of trivalent actinides/lanthanides in these acids. A direct correlation was observed between the extraction behaviour of Am(III) and the aggregation behaviour of TODGA in the presence of these acids. The aggregation of TODGA increased with increasing concentration of HNO(3), HCl and HClO(4). However, the aggregation tendency of TODGA was independent of its concentration at fixed acidity. The presence of Eu(III) ions facilitated the aggregation of TODGA. The aggregation studies revealed that about 2nm aggregate size of ligand was the critical size required for efficient extraction of trivalent actinide and lanthanide ions.

Evaluation of polymer inclusion membranes containing crown ethers for selective cesium separation from nuclear waste solution.

Transport behaviour of (137)Cs from nitric acid feed was investigated using cellulose triacetate plasticized polymer inclusion membrane (PIM) containing several crown ether carriers viz. di-benzo-18-crown-6 (DB18C6), di-benzo-21-crown-7 (DB21C7) and di-tert-butylbenzo-18-crown-6 (DTBB18C6). The PIM was prepared from cellulose triacetate (CTA) with various crown ethers and plasticizers. DTBB18C6 and tri-n-butyl phosphate (TBP) were found to give higher transport rate for (137)Cs as compared to other carriers and plasticizers. Effect of crown ether concentration, nitric acid concentration, plasticizer and CTA concentration on the transport rate of Cs was also studied. The Cs selectivity with respect to various fission products obtained from an irradiated natural uranium target was found to be heavily dependent on the nature of the plasticizer. The present work shows that by choosing a proper plasticizer, one can get either good transport efficiency or selectivity. Though TBP plasticized membranes showed good transport efficiency, it displayed poor selectivities. On the other hand, an entirely opposite separation behaviour was observed with 2-nitrophenyloctylether (NPOE) plasticized membranes suggesting the possible application of the later membranes for the removal of bulk (137)Cs from the nuclear waste. The stability of the membrane was tested by carrying out transport runs for nearly 25 days.

Interaction of Eu3+ with N,N,N',N'-tetraoctyl diglycolamide: a time resolved luminescence spectroscopy study.

N,N,N',N'-tetraoctyl diglycolamide (TODGA) has been identified as one of the promising extractants for the partitioning of minor actinides from high-level nuclear waste solutions. Solvent extraction studies have shown that stoichiometry of the extracted species of Eu(3+) with TODGA depend on the nature of diluent. Time resolved luminescence spectroscopy (TRLS) has been employed to investigate the complexation of Eu(3+) with TODGA under different experimental conditions. The effects of different experimental parameters such as aqueous phase acidity, nature of diluent, and TODGA concentration on the luminescence lifetime of Eu(3+) ions have been investigated. The lifetime measurements of the complexed fraction of Eu(3+) with TODGA suggested the absence of water molecules in the inner coordination sphere of the metal ion in different solvents. In ethanol-water (60/40%) mixture, the complexation of Eu(3+) with TODGA under varying ligand-to-metal ratios suggested the formation of 1:1, 1:2, and 1:3 species, viz., Eu(TODGA)(3+), Eu(TODGA)(2)(3+), and Eu(TODGA)(3)(3+), respectively. The conditional stability constants logbeta(1), logbeta(2), and logbeta(3) were calculated as 6.1+/-0.5, 10.8+/-0.7, and 14.3+/-0.6, respectively. The nature of diluent did not influence the luminescence spectra of Eu(3+) in the presence of TODGA.

Role of magnetite and humic acid in radionuclide migration in the environment.

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

A novel malonamide grafted polystyrene-divinyl benzene resin for extraction, pre-concentration and separation of actinides.

A new chelating polymeric extraction chromatographic resin was prepared by chemical anchoring of N,N'-dimethyl-N,N'-dibutyl malonamide (DMDBMA) with chloromethylated Merrifield resin((R)). The grafted resin exhibited stronger binding for hexavalent and tetravalent actinides such as U(VI), Th(IV) and Pu(IV) over trivalent actinides, viz. Am(III) and Pu(III). Batch studies on solid phase extraction performed over a wide range of acid solution (0.01-6M HNO(3)) revealed that ternary mixer of uranium, americium and plutonium or thorium, americium and plutonium could be separated from each other at 1M HNO(3). Desorption of U(VI), Pu(IV) and Am(III) from the loaded resin was efficiently carried out using 0.1M alpha-HIBA, 0.25M oxalic acid and 0.01M EDTA, respectively. Quantitative pre-concentration of actinide ions such as Th(IV) and U(VI) was possible from 3M HNO(3) solution. The practical utility of the grafted resin was evaluated by uranium sorption measurements in several successive cycles. The sorption efficiency of the resin with respect to uranyl ion remained unchanged even after 30 days of continuous use. The surface morphology of the resin was monitored with the help of scanning electron microscopy (SEM) technique.

Optode for uranium(VI) determination in aqueous medium.

A colorimetric method for simultaneous preconcentration and determination of uranium(VI) anions from aqueous samples was developed using a membrane optode formed by physical inclusion of a chromophore 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (Br-PADAP) into a plasticized cellulose triacetate matrix. The optode was tested for uranium uptake in bicarbonate/carbonate medium (approximately 10(-4) M) at pH 7-8 in the presence of triethanolamine buffer. The inclusion of an anion-exchanger tricaprylylmethyl ammonium chloride (Aliquat-336) was found to be necessary for the formation of U(VI)-Br-PADAP complex in the optode matrix, resulting into distinct color change of the optode from yellow to magenta after uranium sorption. The composition of the optode was optimized by varying the amounts of different plasticizers and Aliquat-336 to obtain minimum response time towards U(VI) in aqueous bicarbonate medium. The proportionality in intensity of the magenta color of the optode samples loaded with varying amounts of U(VI) suggested its potential applications for screening of U(VI) in aqueous samples by visual colorimetry. The effects of experimental parameters involved in the detection and quantification of U(VI) using optode were optimized. The optode analytical performance was evaluated in terms of interference of cations and anions, equilibration time, reusability, detection limit, etc. and compared with the conventional spectrophotometric method for U(VI) using same chromophore Br-PADAP. The optode developed in the present work was tested in real alkaline Mg(NO(3))(2) effluent sample obtained from uranium extraction process.

Effect of barium on diffusion of sodium in borosilicate glass.

Diffusion coefficients of sodium in barium borosilicate glasses having varying concentration of barium were determined by heterogeneous isotopic exchange method using (24)Na as the radiotracer for sodium. The measurements were carried out at various temperatures (748-798 K) to obtain the activation energy (E(a)) of diffusion. The E(a) values were found to increase with increasing barium content of the glass, indicating that introduction of barium in the borosilicate glass hinders the diffusion of alkali metal ions from the glass matrix. The results have been explained in terms of the electrostatic and structural factors, with the increasing barium concentration resulting in population of low energy sites by Na(+) ions and, plausibly, formation of more tight glass network. The leach rate measurements on the glass samples show similar trend.

Synthesis of N,N'-dimethyl-N,N'-dibutyl malonamide functionalized polymer and its sorption affinities towards U(VI) and Th(IV) ions.

A novel chelating polymeric material was synthesized by chemical anchoring of N,N'-dimethyl-N,N'-dibutyl malonamide (DMDBMA) with chloromethylated polystyrene-divinyl benzene polymer. The polymeric material thus prepared was characterized by (13)C NMR, FT-IR spectroscopy and CHN elemental analysis. The fabricated polymeric material exhibited superior binding for hexa-valent and tetra-valent metal ions such as U(VI) and Th(IV). Various physico-chemical properties of the functionalized polymer like phase adsorption kinetics, metal sorption mechanism and metal sorption capacity was studied in the static method. Adsorption kinetics studies show that <20min was sufficient for >99.99% adsorption of Th(IV) and U(VI). The kinetics for adsorption of U(VI) and Th(IV) was found to follow the first order Lagergren rate kinetics. Adsorption of U(VI) on the malonamide functionalized polymer followed the Langmuir adsorption isotherm. The Langmuir monolayer adsorption phenomenon was also confirmed by the theoretical approach calculated based on the adsorption kinetics. The metal sorption capacities for uranium and thorium were found to be 18.78+/-1.53mg and 15.74+/-1.59mg/g of the chelating polymer at 3M HNO(3), respectively.