Highly Sensitive Detection of Arsenite Based on Its Affinity toward Ruthenium Nanoparticles Decorated on Glassy Carbon Electrode.

Metallic ruthenium nanoparticles (Ru NPs) are formed on the glassy carbon electrode (GC) at electrodeposition potential of -0.75 V, as observed from X-ray photoelectron spectroscopy. Thus formed Ru NPs have the arsenite selective surface and conducting core that is ideally suited for designing a highly sensitive and reproducible response generating matrix for the arsenite detection at an ultratrace concentration in aqueous matrices. Contrary to this, arsenate ions sorb via chemical interactions on the ruthenium oxide (RuO2 and RuO3) NPs formed at -0.25 V, but not on the Ru NPs. For exploring a possibility of the quantification of arsenite in the ultratrace concentration range, the Ru NPs have been deposited on the GC by a potentiostatic pulse method of electrodeposition at optimized -0.75 V for 1000 s. Arsenite preconcentrates onto the Ru surface just by dipping the RuNPs/GC into the arsenite solution as it interacts chemically with Ru NPs. Electrochemical impedance spectroscopy of As(III) loaded RuNPs/GC shows a linear increase in the charge transfer resistance with an increase in As(III) conc. Using a differential pulse voltammetric technique, arsenite is oxidized to arsenate leading to its quantitative determination without any interference of Cu(2+) ions that are normally encountered in the water systems. Thus, the use of RuNPs/GC eliminates the need for a preconcentration step in stripping voltammetry, which requires optimization of the parameters like preconcentration potential, time, stirring, inferences, and so on. The RuNPs/GC based differential pulse voltammetric (DPV) technique can determine the concentration of arsenite in a few min with a detection limit of 0.1 ppb and 5.4% reproducibility. The sensitivity of 2.38 nA ppb(-1) obtained in the present work for As(III) quantification is considerably better than that reported in the literature, with a similar detection limit and mild conditions (pH = 2). The RuNPs/GC based DPV has been evaluated for its analytical performance using the lake water, ground water, and seawater samples spiked with known amounts of As(III).

Tailored bifunctional polymer for plutonium monitoring.

Monitoring of actinides with sophisticated conventional methods is affected by matrix interferences, spectral interferences, isobaric interferences, polyatomic interferences, and abundance sensitivity problems. To circumvent these limitations, a self-supported disk and membrane-supported bifunctional polymer were tailored in the present work for acidity-dependent selectivity toward Pu(IV). The bifunctional polymer was found to be better than the polymer containing either a phosphate group or a sulfonic acid group in terms of (i) higher Pu(IV) sorption efficiency at 3-4 mol L(-1) HNO3, (ii) selective preconcentration of Pu(IV) in the presence of a trivalent actinide such as Am(III), and (iii) preferential sorption of Pu(IV) in the presence of a large excess of U(VI). The bifunctional polymer was formed as a self-supported matrix by bulk polymerization and also as a 1-2 µm thin layer anchored on a microporous poly(ether sulfone) by surface grafting. The proportions of sulfonic acid and phosphate groups in both the self-supported disk and membrane-supported bifunctional polymer were found to be the same as expected from the mole proportions of monomers in polymerizing solutions used for syntheses. α radiography by a solid-state nuclear track detector indicated fairly homogeneous anchoring of the bifunctional polymer on the surface of the membrane. Pu(IV) preconcentrated on a single bifunctional bead was used for determination of the Pu isotopic composition by thermal ionization mass spectrometry. The membrane-supported bifunctional polymer was used for preconcentration and subsequent quantification of Pu(IV) by α spectrometry using the absolute efficiency at a fixed counting geometry. The analytical performance of the membrane-supported-bifunctional-polymer-based α spectrometry method was found to be highly reproducible for assay of Pu(IV) in a variety of complex samples.

Redox decomposition of silver citrate complex in nanoscale confinement: an unusual mechanism of formation and growth of silver nanoparticles.

We demonstrate for the first time the intrinsic role of nanoconfinement in facilitating the chemical reduction of metal ion precursors with a suitable reductant for the synthesis of metal nanoparticles, when the identical reaction does not occur in bulk solution. Taking the case of citrate reduction of silver ions under the unusual condition of [citrate]/[Ag(+)] ≫ 1, it has been observed that the silver citrate complex, stable in bulk solution, decomposes readily in confined nanodomains of charged and neutral matrices (ion-exchange film and porous polystyrene beads), leading to the formation of silver nanoparticles. The evolution of growth of silver nanoparticles in the ion-exchange films has been studied using a combination of (110m)Ag radiotracer, small-angle X-ray scattering (SAXS) experiments, and transmission electron microscopy (TEM). It has been observed that the nanoconfined redox decomposition of silver citrate complex is responsible for the formation of Ag seeds, which thereafter catalyze oxidation of citrate and act as electron sink for subsequent reduction of silver ions. Because of these parallel processes, the particle sizes are in the bimodal distribution at some stages of the reaction. A continuous seeding with parallel growth mechanism has been revealed. Based on the SAXS data and radiotracer kinetics, the growth mechanism has been elucidated as a combination of continuous autoreduction of silver ions on the nanoparticle surfaces and a sudden coalescence of nanoparticles at a critical number density. However, for a fixed period of reduction, the size, size distribution, and number density of thus-formed Ag nanoparticles have been found to be dependent on physical architecture and chemical composition of the matrix.

Omicron BA.2 lineage predominance in severe acute respiratory syndrome coronavirus 2 positive cases during the third wave in North India.

Background: Recent studies on severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) reveal that Omicron variant BA.1 and sub-lineages have revived the concern over resistance to antiviral drugs and vaccine-induced immunity. The present study aims to analyze the clinical profile and genome characterization of the SARS-CoV-2 variant in eastern Uttar Pradesh (UP), North India. Methods: Whole-genome sequencing (WGS) was conducted for 146 SARS-CoV-2 samples obtained from individuals who tested coronavirus disease 2019 (COVID-19) positive between the period of 1 January 2022 and 24 February 2022, from three districts of eastern UP. The details regarding clinical and hospitalized status were captured through telephonic interviews after obtaining verbal informed consent. A maximum-likelihood phylogenetic tree was created for evolutionary analysis using MEGA7. Results: The mean age of study participants was 33.9 ± 13.1 years, with 73.5% accounting for male patients. Of the 98 cases contacted by telephone, 30 (30.6%) had a travel history (domestic/international), 16 (16.3%) reported having been infected with COVID-19 in past, 79 (80.6%) had symptoms, and seven had at least one comorbidity. Most of the sequences belonged to the Omicron variant, with BA.1 (6.2%), BA.1.1 (2.7%), BA.1.1.1 (0.7%), BA.1.1.7 (5.5%), BA.1.17.2 (0.7%), BA.1.18 (0.7%), BA.2 (30.8%), BA.2.10 (50.7%), BA.2.12 (0.7%), and B.1.617.2 (1.3%) lineages. BA.1 and BA.1.1 strains possess signature spike mutations S:A67V, S:T95I, S:R346K, S:S371L, S:G446S, S:G496S, S:T547K, S:N856K, and S:L981F, and BA.2 contains S:V213G, S:T376A, and S:D405N. Notably, ins214EPE (S1- N-Terminal domain) mutation was found in a significant number of Omicron BA.1 and sub-lineages. The overall Omicron BA.2 lineage was observed in 79.5% of women and 83.2% of men. Conclusion: The current study showed a predominance of the Omicron BA.2 variant outcompeting the BA.1 over a period in eastern UP. Most of the cases had a breakthrough infection following the recommended two doses of vaccine with four in five cases being symptomatic. There is a need to further explore the immune evasion properties of the Omicron variant.

Genome Sequencing Reveals a Mixed Picture of SARS-CoV-2 Variant of Concern Circulation in Eastern Uttar Pradesh, India.

Uttar Pradesh is the densely populated state of India and is the sixth highest COVID-19 affected state with 22,904 deaths recorded on November 12, 2021. Whole-genome sequencing (WGS) is being used as a potential approach to investigate genomic evolution of the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) virus. In this study, a total of 87 SARS-CoV-2 genomes-49 genomes from the first wave (March 2020 to February 2021) and 38 genomes from the second wave (March 2021 to July 2021) from Eastern Uttar Pradesh (E-UP) were sequenced and analyzed to understand its evolutionary pattern and variants against publicaly available sequences. The complete genome analysis of SARS-CoV-2 during the first wave in E-UP largely reported transmission of G, GR, and GH clades with specific mutations. In contrast, variants of concerns (VOCs) such as Delta (71.0%) followed by Delta AY.1 (21.05%) and Kappa (7.9%) lineages belong to G clade with prominent signature amino acids were introduced in the second wave. Signature substitution at positions S:L452R, S:P681R, and S:D614G were commonly detected in the Delta, Delta AY.1, and Kappa variants whereas S:T19R and S:T478K were confined to Delta and Delta AY.1 variants only. Vaccine breakthrough infections showed unique mutational changes at position S:D574Y in the case of the Delta variant, whereas position S:T95 was conserved among Kappa variants compared to the Wuhan isolate. During the transition from the first to second waves, a shift in the predominant clade from GH to G clade was observed. The identified spike protein mutations in the SARS-CoV-2 genome could be used as the potential target for vaccine and drug development to combat the effects of the COVID-19 disease.

Fabrication of Conducting Nanochannels Using Accelerator for Fuel Cell Membrane and Removal of Radionuclides: Role of Nanoparticles.

Latent tracks in pure polymer and its nanohybrid are fabricated by irradiating with swift heavy ions (SHI) (Ag+) having 140 MeV energy followed by selective chemical etching of the amorphous path, caused by the irradiation of SHI, to generate nanochannels of size ∼80 nm. Grafting is done within the nanochannels utilizing free radicals generated from the interaction of high-energy ions, followed by tagging of ionic species to make the nanochannels highly ion-conducting. The uniform dispersion of two-dimensional nanoparticles better controls the size and number density of the nanochannels and, thereby, converts them into an effective membrane. The nanoparticle and functionalization induce a piezoelectric ß-phase in the membrane. The functionalized membrane removes the radioactive nuclide like 241Am+3 (α-emitting source) efficiently (∼80% or 0.35 µg/cm2) from its solution/waste. This membrane act as a corrosion inhibitor (92% inhibition efficiency) together with its higher proton conduction (0.13 S/m) ability. The higher ion-exchange capacity, water uptake, ion conduction, and high sorption by the nanohybrid membrane are explored with respect to the extent of functionalization and control over nanochannel dimension. A membrane electrode assembly has been fabricated to construct a complete fuel cell, which exhibits superior power generation (power density of 45 mW/cm2 at a current density of 298 mA/cm2) much higher than that of the standard Nafion, measured in a similar condition. Further, a piezoelectric matrix along with its anticorrosive property, high sorption characteristics, and greater power generation makes this class of material a smart membrane that can be used for many different applications.

Insight into Speciation and Electrochemistry of Uranyl Ions in Deep Eutectic Solvents.

Understanding the speciation of metal ions in heterogeneous hydrogen-bonded deep eutectic solvents (DES) has immense importance for their wide range of applications in green technology, environmental remediation, and nuclear industry. Unfortunately, the fundamental nature of the interaction between DES and actinide ions is almost completely unknown. In the present work, we outline the speciation, solvation mechanism, and redox chemistry of uranyl ion (UO22+) in DES consisting of choline chloride (ChCl) and urea as the hydrogen-bond donor. Electrochemical and spectroscopic techniques along with molecular dynamics (MD) simulations have provided a microscopic insight into the solvation and speciation of the UO22+ ion in DES and also on associated changes in physical composition of the DES. The hydrogen-bonded structure of DES plays an important role in the redox behavior of the UO22+ ion because of its strong complexation with DES components. X-ray absorption spectroscopy and MD simulations showed strong covalent interactions of uranyl ions with the constituents of DES, which led to rearrangement of the hydrogen-bonding network in it without formation of any clusters or aggregations. This, in turn, stabilizes the most unstable pentavalent uranium (UO2+) in the DES. MD analysis also highlights the fact that the number of H-bonds is reduced in the presence of uranyl nitrate irrespective of the presence of water with respect to pristine reline, which suggests high stability of the formed complexed species. The effect of added water up to 20 v/v % on speciation is insignificant for DES, but the presence of water influences the redox chemistry of UO22+ ions considerably. The fundamental findings of the present work would have far reaching consequences on understanding DES, particularly for application in the field of nuclear fuel reprocessing.

Interdiffusion of exchanging counterions in poly(perfluorosulfonic acid) membrane.

The kinetics of forward (Li+/Na+mem <=> Mn+aq) and reverse (Mn+mem <=> Li+/Na+aq) exchanges of metal ions(Mn+ ) Ag+, Cs+, Ba2+, and Eu3+) in the poly(perfluorosulfonic acid) membrane (Nafion-117) equilibrated with a well-stirred aqueous salt solution were experimentally measured using radioactivity tagged counterions. A numerical solution of the Nernst-Planck (N-P) equation for interdiffusion was used to interpret the kinetics of these exchanges. The experimentally measured kinetics of forward and reverse Na+ ion exchanges with Mn+ ions between the membrane and the equilibrating solution were found to be close to that predicted by the N-P equation. The minor differences between the experimental and predicted exchange rate profiles were attributed to change in water content of the poly(perfluorosulfonic acid) membrane in different ionic forms. The kinetics of Li+ ion exchanges with Na+ and Cs+ ions was found to be unusual as the self-diffusion coefficient D(ion)(m) of Li+ ions in the membrane were quite different in the forward and reverse exchanges. The values of D(ion)(m) for Li+ ion, obtained by the N-P equation, were found to be 2 x 10-6 and 0.2 x 10-6 cm2 s-1in Li+mem <=> Na+/Cs+aq and Na+/Cs+mem <=> Li+aq exchanges, respectively. The drastic differences in diffusion mobility of Li+ ions during forward and reverse exchanges was attributed to weak electrostatic interactions of Li+ ions with the fixed exchange sites as indicated by the reported equilibrium constant Kex of the Li+-exchange reaction in Nafion membrane. D(ion)(m) is high in the forward exchange due to minimum retardation in diffusion mobility of Li+ ions by the electrostatic forces in the membrane. In reverse exchange, Li+ diffusion mobility is retarded due to its slow replacement of counterions from the membrane.

Exchanges of uranium(VI) species in amidoxime-functionalized sorbents.

Amidoxime (AO)-functionalized polymer sorbents used in this study were prepared by two different routes involving UV grafting and electron-beam grafting of acrylonitrile (AN) into poly(propylene) fibrous and microporous sheets, and subsequent conversion of AN to AO groups by reacting the precursor sorbent with hydroxylamine. The values of self-diffusion coefficient (D(s)) of UO(2)(2+) in fibrous and sheet AO sorbents were found to be 1.1 x 10(-6) and 2.3 x 10(-10) cm(2) s(-1), respectively. The higher diffusion mobility of UO(2)(2+) in the fibrous AO sorbent was attributed to its higher free volume as observed in scanning electron microscopic studies. The water content was also found to be maximum in AO-fibrous sorbent (165-200 wt %) and minimum in AO-sheet sorbent (70 wt %). In fibrous AO sorbent, the values of D(s) for Na(+) and Sr(2+) were found to be comparable to their self-diffusion coefficients in the aqueous medium. This indicated that the retardation in diffusion mobility of the ions was a minimum in the fibrous AO sorbent. However, D(s) of UO(2)(2+) in the fibrous membrane was found to be significantly lower than that of Sr(2+), which has a self-diffusion coefficient comparable to that of UO(2)(2+) in aqueous medium. This could be attributed to stronger binding of UO(2)(2+) with AO groups as compared to Sr(2+). To understand the parameters affecting the U(VI) sorption from seawater, the U(VI) exchange rates between fibrous AO sorbent (S) and seawater (aq) involving (H(+)/Na(+))(S) right harpoon over left harpoon ([UO(2)(CO(3))(3)](4-))(aq) and (UO(2)(2+))(S) right harpoon over left harpoon ([UO(2)(CO(3))(3)](4-))(aq) systems were experimentally measured. The exchange profiles thus obtained were found to be non-Fickian and much slower than (H(+))(S) right harpoon over left harpoon (UO(2)(2+))(aq) and (UO(2)(2+))(S) right harpoon over left harpoon (UO(2)(2+))(aq) exchanges. This seems to suggest that the reaction kinetics involved in decomplexation of [UO(2)(CO(3))(3)](4-) into UO(2)(2+), which forms a complex with AO groups, is the rate-determining step in sorption of U(VI) from seawater. The kinetics of U(VI) sorption in AO-gel and AO-fibrous sorbents followed the pseudo-second-order rate equation. The density of AO groups in the sorbents and their conditioning were found to influence the U(VI) sorption from seawater.

Hybrid organic-inorganic anion-exchange pore-filled membranes for the recovery of nitric acid from highly acidic aqueous waste streams.

Recycling of acid from aqueous waste streams is highly important not only from the environmental point of view but also for developing the sustainable technology. One of the effective ways to recover acid from aqueous waste streams is the anion-exchange membrane based diffusion-dialysis. The work presents the synthesis and characterization of anion-exchange pore-filled membranes for the objective of recovery of high concentration of acid by diffusion dialysis. The membranes were prepared by anchoring the guest organic-inorganic anionic gel in the pores of the host poly(propylene) membrane by in situ UV-initiator induced polymerization of the appropriate monomers along with cross-linker. The removal of nitric acid in the presence of different representative monovalent, divalent and trivalent nitrates and the leakage of these ions through anion exchange membrane have been studied by DD technique for optimizing the chemical composition of the membrane. The nitric acid permeation rate of the membrane with the optimized composition has been found to be considerably faster than the commercial Selemion membrane without sacrificing salt leakage. The performance of the optimized pore-filled anion exchange membranes has been found to be independent of the acid concentration, nature of the anion and substrate and has been observed to be solely dependent on the guest inorganic-organic hybrid anionic gel component. The membranes have been found to be stable and reusable for the acid recovery. Removal of nitric acid as high as 90% from the simulated high level nuclear waste with the optimized grafted pore-filled membrane has been achieved with negligible salt transport.

Change in the Affinity of Ethylene Glycol Methacrylate Phosphate Monomer and Its Polymer Anchored on a Graphene Oxide Platform toward Uranium(VI) and Plutonium(IV) Ions.

The complexation behavior of the carbonyl and phosphoryl ligating groups bearing ethylene glycol methacrylate phosphate (EGMP) monomer and its polymer fixed on a graphene oxide (GO) platform was studied to understand the coordination ability of segregated EGMP units and polymer chains toward UO2(2+) and Pu(4+) ions. The cross-linked poly(EGMP) gel and EGMP dissolved in solution have a similar affinity toward these ions. UV-initiator induced polymerization was used to graft poly(EGMP) on the GO platform utilizing a double bond of EGMP covalently fixed on it. X-ray photoelectron spectroscopy (XPS) of the GO and GO-EGMP was done to confirm covalent attachment of the EGMP via a -C-O-P- link between GO and EGMP. The extent of poly(EGMP) grafting on GO by thermal analyses was found to be 5.88 wt %. The EGMP units fixed on the graphene oxide platform exhibited a remarkable selectivity toward Pu(4+) ions at high HNO3 conc. where coordination is a dominant mode involved in the sorption of ions. The ratio of distribution coefficients of Pu(IV) to U(VI) (DPu(IV)/DU(VI)) followed a trend as cross-linked poly(EGMP) (0.95) < EGMP in solvent methyl isobutyl ketone (1.3) < GO-poly(EGMP) (25) < GO-EGMP (181); the DPu(IV)/DU(VI) values are given in parentheses. The density functional theory computations have been performed for the complexation of UO2(2+) and Pu(4+) ions with the EGMP molecule anchored on GO in the presence of nitrate ions. This computational modeling suggested that Pu(4+) ion formed a strong coordination complex with phosphoryl and carbonyl ligating groups of the GO-EGMP as compared to UO2(2+) ions. Thus, the nonselective EGMP becomes highly selective to Pu(IV) ions when it interacts as a single unit fixed on a GO platform.

Chemically selective polymer substrate based direct isotope dilution alpha spectrometry of Pu.

Quantification of actinides in the complex environmental, biological, process and waste streams samples requires multiple steps like selective preconcentration and matrix elimination, solid source preparations generally by evaporation or electrodeposition, and finally alpha spectrometry. To minimize the sample manipulation steps, a membrane based isotope dilution alpha spectrometry method was developed for the determination of plutonium concentrations in the complex aqueous solutions. The advantages of this method are that it is Pu(IV) selective at 3M HNO3, high preconcentration factor can be achieved, and obviates the need of solid source preparation. For this, a thin phosphate-sulfate bifunctional polymer layer was anchored on the surface of microporous poly(ethersulfone) membrane by UV induced surface grafting. The thickness of the bifunctional layer on one surface of the poly(ethersulfone) membrane was optimized. The thickness, physical and chemical structures of the bifunctional layer were studied by secondary ionization mass spectrometry (SIMS), scanning electron microscopy (SEM) and SEM-EDS (energy-dispersive spectroscopy). The optimized membrane was used for preconcentration of Pu(IV) from aqueous solutions having 3-4M HNO3, followed by direct quantification of the preconcentrated Pu(IV) by isotope dilution alpha spectrometry using (238)Pu spike. The chemical recovery efficiency of Pu(IV) was found to be 86±3% below Pu(IV) loading capacity (1.08 µg in 2×1 cm(2)) of the membrane sample. The experiments with single representative actinides indicated that Am(III) did not sorb to significant extent (7%) but U(VI) sorbed with 78±3% efficiency from the solutions having 3M HNO3 concentration. However, Pu(IV) chemical recovery in the membrane remained unaffected from the solution containing 1:1000 wt. proportion of Pu(IV) to U(VI). Pu concentrations in the (U, Pu)C samples and in the irradiated fuel dissolver solutions were determined. The results thus obtained were found to be in good agreement with those obtained by conventional alpha spectrometry, biamperometry and thermal ionization mass spectrometry.

Understanding nitric acid-induced changes in the arrangement of monomeric and polymeric methacryloyl diglycolamides on their affinity toward f-element ions.

Assembled diglycolamides (DGAs) have a strong affinity toward f-element ions at high nitric acid concentrations. Small angle X-ray scattering studies revealed that nitric acid concentration dependent changes occur in the geometrical arrangement of the DGA units of monomeric methacryloyl-DGA and the corresponding polymeric DGA. Cylindrical aggregates of methacryloyl-DGA were formed in 10:1 n-dodecane:1-decanol (added for solubility reasons) upon equilibration with nitric acid. The lengths and diameters of the cylindrical methacryloyl-DGA aggregates increased on varying the nitric acid concentration from 3 to 4 mol L(-1). This resulted in an increase of the distribution coefficient (D) of Eu(3+) ions from 72 to 197. The physical structure of cross-linked (10 mol %) poly(methacryloyl-DGA) reorganized distinctly upon equilibration with nitric acid. In this case, also the DEu(3+) values increased significantly from 147 mL g(-1) at 1 mol L(-1) HNO3 to ∼4000 mL g(-1) at 4 mol L(-1) HNO3. Hydrogen bonds between the outer sphere of Eu(3+)/Am(3+)/Pu(4+) nitrate and DGA units provide stabilization in the hydrophobic environment. This results in enhancement of their extraction upon increasing nitric acid concentration both in the organic phase as well as in the polymer matrix. Though monomeric and polymeric methacryloyl-DGA are different in their physical assembling, the normalized DI values for a same f-element ion upon varying HNO3 concentrations show remarkably similar patterns in both forms. In addition, the unusual stoichiometry deduced from the slopes of the log D vs log[HNO3] curves at fixed nitrate concentration seems to suggest that the normal extraction mechanism may not be operating in the hydrogen bonded DGA assemblies.

A visual strip sensor for determination of iron.

A visual strip has been developed for sensing iron in different aqueous samples like natural water and fruit juices. The sensor has been synthesized by UV-radiation induced graft polymerization of acrylamide monomer in microporous poly(propylene) base. For physical immobilization of iron selective reagent, the in situ polymerization of acrylamide has been carried out in the presence of 1,10-phenanthroline. The loaded strip on interaction with Fe(II) in aqueous solution turned into orange red color and the intensity of the color was found to be directly proportional to the amount of Fe(II) in the aqueous sample. The minimal sensor response with naked eye was found for 50ngmL(-1) of Fe in 15min of interaction. However, as low as 20ngmL(-1) Fe could be quantified using a spectrophotometer. The detection limit calculated using the 3s/S criteria, where 's' is the standard deviation of the absorbance of blank reagent loaded strip and 'S' is the slope of the linear calibration plot, was 1.0ngmL(-1). The strip was applied to measure Fe in a variety of samples such as ground water and fruit juices.

Thin extractive membrane for monitoring actinides in aqueous streams.

Alpha spectrometry and solid state nuclear track detectors (SSNTDs) are used for monitoring ultra-trace amount of alpha emitting actinides in different aqueous streams. However, these techniques have limitations i.e. alpha spectrometry requires a preconcentration step and SSNTDs are not chemically selective. Therefore, a thin polymer inclusion membrane (PIM) supported on silanized glass was developed for preconcentraion and determination of ultra-trace concentration of actinides by α-spectrometry and SSNTDs. PIMs were formed by spin coating on hydrophobic glass slide or solvent casting to form thin and self-supported membranes, respectively. Sorption experiments indicated that uptakes of actinides in the PIM were highly dependent on acidity of solution i.e. Am(III) sorbed up to 0.1 molL(-1) HNO3, U(VI) up to 0.5 molL(-1) HNO3 and Pu(IV) from HNO3 concentration as high as 4 molL(-1). A scheme was developed for selective sorption of target actinide in the PIM by adjusting acidity and oxidation state of actinide. The actinides sorbed in PIMs were quantified by alpha spectrometry and SSNTDs. For SSNTDs, neutron induced fission-fragment tracks and α-particle tracks were registered in Garware polyester and CR-39 for quantifications of natural uranium and α-emitting actinides ((241)Am/(239)Pu/(233)U), respectively. Finally, the membranes were tested to quantify Pu in 4 molL(-1) HNO3 solutions and synthetic urine samples.

Extractive fixed-site polymer sorbent for selective boron removal from natural water.

Water contamination by boron is a widespread environmental problem. The World Health Organization (WHO) recommends maximum boron concentration of 2.4 mg L(-1) for drinking water. The paper presents a simple method for preparation of functionalized sheet sorbent for selective extraction of boron from natural water. The pores of commercially available poly(propylene) membrane were functionalized by room temperature in situ crosslinking of poly(vinylbenzyl chloride) with a cyclic diamine piperazine. The precursor membranes were chemically modified with N-methyl D-glucamine which is selective for boron. Characterization of membrane was carried out using scanning electron microscopy (SEM) and attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR) techniques. The functionalized membrane has been characterized in terms of parameters that influence the sorption of boron from aqueous streams like pH, uptake capacity, contact time, effects of competing ions and reusability. The maximum boron sorption capacity determined experimentally was 28 mg g(-1). The studies showed that trace concentrations of boron were quantitatively removed from water at neutral pH. The developed fixed site polymer sorbent exhibited high sorption capacity and fast kinetics as compared to various sorbents reported in literature. It was successfully applied for the removal of boron from ground water and seawater samples in presence of high concentration of interfering ions.

Synthesis and application of a unified sorbent for simultaneous preconcentration and determination of trace metal pollutants in natural waters.

A flat sheet sorbent with poly(hydroxamic acid) groups anchored on the microporous structure of poly(propylene) membrane was developed and applied for the preconcentration and determination of heavy elements from natural waters. The designing of the sorbent involved UV-irradiation induced graft polymerization of acrylamide using N,N'-methylene-bis-acrylamide (MBA) as the crosslinker on the poly(propylene) base followed by chemical modification of the grafted membrane to generate crosslinked poly(hydroxamic acid) (PHA) groups in its pores. The synthesized PHA-membrane was found to preconcentrate U, V, Cu, Cr, Fe and Pb quantitatively (95%) from aqueous samples over a wide pH range of 4-9. The sorbed trace elements were quantified by direct analysis of the membrane using Energy Dispersive X-ray Fluorescence (EDXRF). To test the applicability of the developed sorbent to real samples, interference effect of common matrix elements like Na, K, Ca and Mg on the uptake of the analytes at sub µg mL(-1) level was studied. The PHA sorbent was found to be immune to interferences from Na, K and Mg up to 1000 µg mL(-1) and Ca up to 100 µg mL(-1) for an analyte concentration of 1 µg mL(-1). The method detection limit for EDXRF measurement was 6-30 ng using a 2 cm × 2 cm sorbent.

Iron-complexed adsorptive membrane for As(V) species in water.

Selective preconcentration of a target analyte in the solid phase is an effective route not only to enhance detection limit of the conventional analytical method but also for elimination of interfering matrix. An adsorptive membrane was developed for selective preconcentration and quantification of ultra-trace (ppb) amounts of As(V) present in a variety of aqueous samples. The precursor membrane was prepared by UV-initiator induced graft polymerization of sulphate and phosphate bearing monomers (1:1 mol proportion) in pores of the host microporous poly(propylene) membrane. Fe(3+) ions were loaded in the precursor membrane to make it selective for As(V) ions. The presence of phosphate functional groups prevent leaching of Fe(3+) ions from the membrane when it comes in contact with solution like seawater having high ionic strength. The optimized membrane was characterized in terms of its physical structure, chemical structure and experimental conditions affecting As(V) uptake in the membrane. The possibility of quantifying total preconcentration of As content was also explored by converting As(III) to As(V). To quantify As(V), the membrane samples were subjected to instrumental neutron activation analysis (INAA). The studies carried in the present work showed that quantification of inorganic arsenic species in natural water samples is easily possible in 2-3 ppb concentration range.

Matrix supported tailored polymer for solid phase extraction of fluoride from variety of aqueous streams.

Fluoride related health hazards (fluorosis) are a major environmental problem in many regions of the world. It affects teeth; skeleton and its accumulation over a long period can lead to changes in the DNA structure. It is thus absolutely essential to bring down the fluoride levels to acceptable limits. Here, we present a new inorganic-organic hybrid polymer sorbent having tailored fixed-sites for fluoride sorption. The matrix supported poly (bis[2-(methacryloyloxy)-ethyl]phosphate) was prepared by photo-initiator induced graft-polymerization in fibrous and microporous (sheet) host poly(propylene) substrates. These substrates were conditioned for selective fluoride sorption by forming thorium complex with phosphate groups on bis[2-methacryloyloxy)-ethyl] phosphate (MEP). These tailored sorbents were studied for their selectivity towards fluoride in aqueous media having different chemical conditions. The fibrous sorbent was found to take up fluoride with a faster rate (15 min for ≈76% sorption) than the sheet sorbent. But, the fluoride loading capacity of sheet sorbent (4,320 mg kg(-1)), was higher than fibrous and any other sorbent reported in the literature so far. The sorbent developed in the present work was found to be reusable after desorption of fluoride using NaOH solution. It was tested for solid phase extraction of fluoride from natural water samples.

Forced and self-excited oscillations of an optomechanical cavity.

We experimentally study forced and self-excited oscillations of an optomechanical cavity, which is formed between a fiber Bragg grating that serves as a static mirror and a freely suspended metallic mechanical resonator that serves as a moving mirror. In the domain of small amplitude mechanical oscillations, we find that the optomechanical coupling is manifested as changes in the effective resonance frequency, damping rate, and cubic nonlinearity of the mechanical resonator. Moreover, self-excited oscillations of the micromechanical mirror are observed above a certain optical power threshold. A comparison between the experimental results and a theoretical model that we have recently derived and analyzed yields a good agreement. The comparison also indicates that the dominant optomechanical coupling mechanism is the heating of the metallic mirror due to optical absorption.