Preparation of seaweed polysaccharide based hydrophobic composite membranes for the separation of oil/water emulsion and protein.

Agarose is a seaweed-based polysaccharide and is widely used for the separation of nucleic acids in molecular biology. Cross-linked agarose beads are also used as solid-phase matrices in size exclusion chromatography for the separation of proteins. To find the application of agarose for the separation of oil/water emulsion and protein, herein hydrophobic derivative of the seaweed biopolymer [MW (1.27 ± 0.17) × 10 5 g/mol; sulphate content (0.29 ± 0.09) %, gel strength (2242 ± 21) g/cm2] is prepared by reacting the biopolymer with stearic acid and was used to prepare a composite membrane on polyester fabric. The oil and BSA rejection performance of the composite membrane was greater than 98%. The rejection rate increased with the increase in polymer content in the respective membranes for both oil/water and protein separation. The composite membrane showed a stable oil/water emulsion and protein separation performance over a period of six hours. Due to the biodegradable nature of the major components of the membrane, it has the potential for industrial applications.

Studies on neutron spectrum characterization for the Pneumatic Fast Transfer System (PFTS) of KAMINI reactor.

Characterization of neutron energy spectrum along with the determination of sub-cadmium to epithermal neutron flux ratio (f) and the epithermal neutron flux shape factor (α) has been carried out at pneumatic fast transfer system (PFTS) of KAMINI reactor. The facility has been extensively used for the neutron activation analysis (NAA) studies using both k0-NAA and relative method. This paper describes the multi-foil activation method to determine the reaction rates followed by the generation of computed guess spectrum to unfold the neutron spectrum using least square minimization approach.

Vertical distribution, composition profiles, sources and toxicity assessment of PAH residues in the reclaimed mudflat sediments from the adjacent Thane Creek of Mumbai.

A study on vertical distribution of magnetic susceptibility, carcinogenic and endocrine disrupting PAHs was performed in the reclaimed mudflat sediments adjacent to the Thane Creek of Mumbai. The 5-rings PAHs and ΣC-PAHs were more dominant at 120cm depth contributing 52.23% and 60.19% respectively to ∑PAHs. The average ratio values of LMW/HMW PAHs (0.58); Fla/(Fla+Pyr) (0.50); Ant/(Ant+Phe) (0.50); BaA/(Chry+BaA) (0.48); BaP/BghiP (2.06), Phe/Ant (1.03) and BaA/Chr (0.93) indicate that the PAH contamination might have raised due to inefficient combustion and pyrogenic emissions during the open burning of solid waste in the vicinity. This was further supported by the anthropogenic ferri(o)magnetic loading over the last 100years influencing the Creek sediments. The PAHs toxicity estimation was performed by calculating the toxic equivalent quantity (TEQ) value of 8.62ng TEQ/g which was below the safe level (600ng TEQ/g) suggested by the Canadian risk-based soil criterion for protection of human health.

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.

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.

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.

Antibacterial effect of chronic exposure of low concentration ZnO nanoparticles on E. coli.

The toxicity effect due to chronic exposure of ZnO nanoparticles (NPs) was systematically studied by repeatedly treating different lower concentrations of ZnO nanoparticles with culture media of E. coli strain. The chronic exposure of ZnO NPs of concentrations below minimum inhibitory concentration (MIC) exhibited higher toxicity than the single exposure of higher concentrations. Most striking result was 57% inhibition of growth corresponding to chronic exposure of 0.06 mg/mL of ZnO NPs which was two folds more than that exhibited by single exposure of 0.30 mg/mL ZnO NPs. The toxicity of ZnO NPs in E. coli was studied in the light of formation of reactive oxygen species (ROS), measured as malondialdehyde (MDA) equivalent by thiobarbituric acid-ROS (TBARS) assay, and effect of Zn dissolution from ZnO NPs. Higher inhibition of growth for the chronic exposure batches were correlated with higher ROS generation, which subsequently contributed to cause membrane lipid peroxidation, confirmed from observation of cell wall deformation by scanning electron microscopy study and energy dispersive X-ray analysis showed adherence of ZnO NPs on cell wall. The possibility of membrane lipid peroxidation was addressed by revealing in vitro oxidation of oleic acid, which is a monounsaturated fatty acid. Further in this study we have shown that the dissolution of ZnO NPs at pH 7.4 was not significant to cause Zn-induced toxicity.

Sorption of As(III) and As(V) on chemically synthesized manganese dioxide.

Sorption of As(III) and As(V) on manganese dioxide was studied by batch equilibration method using (76)As radioactive tracer. Manganese dioxide was prepared by two different methods viz. reacting (a) KMnO(4) solution with MnSO(4) solution, and (b) KMnO(4) solution with concentrated hydrochloric acid. Manganese dioxide was characterized by zeta potential measurement, surface area measurement, thermogravimetry (TG), differential thermal analysis (DTA) and X-ray diffraction (XRD) techniques. Point of zero charge (PZC) for manganese dioxide was between pH 3 and 4. Radioactive tracer ((76)As) was prepared by neutron irradiation of arsenious oxide in self serve facility of CIRUS reactor followed by conversion to As(III) and As(V), by appropriate chemical methods. Sorption of As(III) and As(V) were studied separately, between pH 1 to 11, using (i) freshly prepared, (ii) air-dried and (iii) aged manganese dioxide. Sorption of As(III) and As(V) on freshly prepared as well as aged manganese dioxide, from both the methods was greater than 98% between pH 1 to 9 and decreased above pH 9. Percentage sorption was comparable for manganese dioxide prepared by both the methods in different batches. Sorption capacity was ∼2 mg g(-1) for both As(III) and As(V). Arsenic was desorbed from the manganese dioxide by 0.1 M sodium hydroxide and oxidation state of desorbed arsenic was determined by solvent extraction method. It was found that the desorbed arsenic was present in As(V) oxidation state, independent of the initial oxidation states. This simple and direct chemical evidence, establishing that As(III) is converted to As(V) by manganese dioxide, is reported for the first time. Sorption of As(III) and As(V) on manganese dioxide did not cause an increase in manganese concentration above solubility limit confirming that Mn(2+), formed during oxidation of As(III) to As(V), was re-adsorbed.

Matrix elimination ion chromatography method for the determination of trace levels of anionic impurities in high purity cesium iodide.

In the present study an ion chromatographic method based on matrix elimination has been developed for the determination of anionic impurities in high purity cesium iodide crystals. The presence of impurities has a detrimental effect on the characteristics of detectors based on cesium iodide crystals. In particular, oxygen-containing anions inhibit the resolving power of scintillators and decrease the optical absorption. The quantitative determination of anions (fluoride, chloride, bromide, nitrate, phosphate, and sulphate) simultaneously in the high-purity cesium iodide crystals has not been carried out before. The large concentration of iodide poses a challenge in the determination of anions (especially phosphate and sulphate); hence, matrix elimination is accomplished by adopting a sample pretreatment technique. The method is validated for linearity, accuracy, and precision. The limit of detection for different anions is in the range of 0.3-3 µg/g, and the relative standard deviation is in the range of 4-6% for the overall method.

Studies on antibacterial activity of ZnO nanoparticles by ROS induced lipid peroxidation.

Recent studies indicated the role of ROS toward antibacterial activity. In our study we report ROS mediated membrane lipid oxidation of Escherichia coli treated with ZnO nanoparticles (NPs) as supported by detection and spectrophotometric measurement of malondialdehyde (MDA) by TBARS (thiobarbituric acid-reactive species) assay. The antibacterial effects of ZnO NPs were studied by measuring the growth curve of E. coli, which showed concentration dependent bacteriostatic and bacteriocidal effects of ZnO NPs. The antibacterial effects were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Further, antibacterial effect of ZnO NPs was found to decrease by introducing histidine to the culture medium treated with ZnO NPs. The ROS scavenging action of histidine was confirmed by treating histidine to the batch of Escherichia coli+ZnO NPs at the end of the lag phase of the growth curve (Set-I) and during inoculation (Set-II). A moderate bacteriostatic effect (lag in the E. coli growth) was observed in Set-II batch while Set-I showed no bacteriostatic effect. From these evidences we confirmed that the antibacterial effect of bare as well as TG capped ZnO NPs were due to membrane lipid peroxidation caused by the ROS generated during ZnO NPs interaction in culture medium.

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.

Boroaluminosilicate glasses: novel sorbents for separation of Th and U.

Boroaluminosilicate glass having a specific composition could be successfully used for the selective uptake of thorium from a mixture containing uranium by controlling the solution pH only. Single ion uptake studies showed that the uptake of uranium and thorium was maximum at pH of 4.5 and 7.5, respectively. But uptake studies using mixtures with uranium and thorium showed that irrespective of the pH, the uptake of thorium was higher than that of uranium.

Study of seleniferous soils using instrumental neutron activation analysis.

Soil samples from the seleniferous region of Punjab State in India were analyzed by instrumental neutron activation analysis (INAA) using reactor neutrons and high resolution γ-ray spectrometry. Samples were collected from three different depths namely surface, root and geological bed zones. Concentrations of 15 elements including selenium and arsenic were determined by relative method. For comparison purposes, soil samples collected from a non-seleniferous region were also analyzed.

Voltammetric determination of trace levels of Hg in ayurvedic medicine and in cobalt-containing samples using a carbon paste electrode.

An analytical method has been described for the determination of mercury using a carbon paste electrode. Conditions for the preparation of the carbon paste electrode were optimized for low background current in order to use it for the determination of ultra trace levels of mercury. The carbon paste electrode was found to be a good electrode material for the determination of mercury. The optimized pH for the determination was in the range of 2.5 to 3.5. The three sigma detection limit of mercury was obtained as 0.095 µg L(-1). Method has been modified for determination of mercury in cobalt sulfate samples.

Covalent immobilization of protein onto a functionalized hydrogenated diamond-like carbon substrate.

Hydrogenated diamond-like carbon (HDLC) has an atomically smooth surface that can be deposited on high-surface area substrata and functionalized with reactive chemical groups, providing an ideal substrate for protein immobilization. A synthetic sequence is described involving deposition and hydrogenation of DLC followed by chemical functionalization. These functional groups are reacted with amines on proteins causing covalent immobilization on contact. Raman measurements confirm the presence of these surface functional groups, and Fourier transform infrared spectroscopy (FTIR) confirms covalent protein immobilization. Atomic force microscopy (AFM) of immobilized proteins is reproducible because proteins do not move as a result of interactions with the AFM probe-tip, thus providing an advantage over mica substrata typically used in AFM studies of protein. HDLC offers many of the same technical advantages as oxidized graphene but also allows for coating large surface areas of biomaterials relevant to the fabrication of medical/biosensor devices.

Heavy metal bioaccumulation in selected medicinal plants collected from Khetri copper mines and comparison with those collected from fertile soil in Haridwar, India.

Heavy metal distribution in medicinal plants is gaining importance not only as an alternative medicine, but also for possible concern due to effects of metal toxicity. The present study has been focused on emphasizing the heavy metal status and bioaccumulation factors of V, Mn, Fe, Co, Cu, Zn, Se (essential metals) and Cr, Ni, Cd, As and Pb (potentially toxic metals) in medicinal plants grown under two different environmental conditions e.g., near to Khetri copper mine and those in fertile soils of Haridwar, both in India, using Instrumental Neutron Activation Analysis (relative method) and Atomic Absorption Spectrometry. The copper levels in the medicinal plants from Khetri were found to be 3-4 folds higher (31.6-76.5 mg kg(-1)) than those from Haridwar samples (7.40-15.3 mg kg(-1)), which is correlated with very high copper levels (763 mg kg(-1)) in Khetri soil. Among various heavy metals, Cr (2.60-5.92 mg kg(-1)), Cd (1.47-2.97 mg kg(-1)) and Pb (3.97-6.63 mg kg(-1)) are also higher in concentration in the medicinal plants from Khetri. The essential metals like Mn (36.4-69.3 mg kg(-1)), Fe (192-601 mg kg(-1)), Zn (24.9-49.9 mg kg(-1)) and Se (0.13-0.91 mg kg(-1)) and potentially toxic metals like Ni (3.09-9.01 mg kg(-1)) and As (0.41-2.09 mg kg(-1)) did not show much variations in concentration in the medicinal plants from both Khetri and Haridwar. The medicinal plants from Khetri, e.g., Ocimum sanctum, Cassia fistula, Withania somnifera and Azadirachta Indica were found rich in Ca and Mg contents while Aloe barbadensis showed moderately high Ca and Mg. Higher levels of Ca-Mg were found to correlate with Zn (except Azadirachta Indica). The bioaccumulation factors (BAFS) of the heavy metals were estimated to understand the soil-to-plant transfer pattern of the heavy metals. Significantly lower BAF values of Cu and Cr were found in the medicinal plants from Khetri, indicating majority fraction of these metals are precipitated and were immobilized species unsuitable for plant uptake. Overall, Withania somnifera (Ashwagandha) showed very high metal bioaccumulation.

Biosorption of Pb2+ from aqueous solutions by Moringa oleifera bark: equilibrium and kinetic studies.

Biosorption of Pb(2+) from aqueous solution by biomass prepared from Moringa oleifera bark (MOB), an agricultural solid waste has been studied. Parameters that influence the biosorption such as pH, biosorbent dose, contact time and concentration of metal ion were investigated. The experimental equilibrium adsorption data were tested by four widely used two-parameter equations, the Langmuir, Freundlich, Dubinin-Radushkevich (D-R) and Temkin isotherms. Results indicated that the data of Pb(2+) adsorption onto MOB were best fit by the Freundlich model. The adsorption capacity (Q(m)) calculated from the Langmuir isotherm was 34.6mgPb(2+)g(-1) at an initial pH of 5.0. Adsorption kinetics data were analyzed using the pseudo-first-, pseudo-second-order equations and intraparticle diffusion models. The results indicated that the adsorption kinetic data were best described by pseudo-second-order model. Infrared (IR) spectral analysis revealed that the lead ions were chelated to hydroxyl and/or carboxyl functional groups present on the surface of MOB. Biosorbent was effective in removing lead in the presence of common metal ions like Na(+), K(+), Ca(2+) and Mg(2+) present in water. Desorption studies were carried out with dilute hydrochloric acid for quantitative recovery of the metal ion as well as to regenerate the adsorbent. Based on the results obtained such as good uptake capacity, rapid kinetics, and its low cost, M. oleifera bark appears to be a promising biosorbent material for the removal of heavy metal ions from wastewater/effluents.

Membrane optode for uranium(VI) ions preconcentration and quantification based on a synergistic combination of 4-(2-thiazolylazo)-resorcinol with 8-hydroxyquinaldine.

A membrane optode was developed utilizing the 8-hydroxyquinaldine (HQ) facilitated preconcentration of UO(2)(2+) ions and subsequent colored complex formation of UO(2)(2+) with 4-(2-thiazolylazo)-resorcinol (TAR) in optode matrix. The composition of the membrane optode was optimized by scanning several extractants immobilized in different plasticized polymer matrices. It was observed that the chelating agent HQ along with an indicator TAR immobilized in the tri-(2-ethylhexyl)phosphate (TEHP) plasticized cellulose triacetate matrix (CTA) was best suited as an optode for the UO(2)(2+) ions in aqueous samples. On sorption of UO(2)(2+) in the optode matrix, TAR changes color of the optode from yellow to magenta having a maximum absorbance (lambda(max)) at 546 nm. The uptake of UO(2)(2+) ions in the optode was found to be pH dependent and was maximum (>90%) at pH above 3. The acetate buffer (0.1 mol L(-1) sodium acetate + 0.1 mol L(-1) acetic acid) was found to be necessary for the stable response. The optimum equilibration time for the optode (2 cm x 1 cm) was found to be 30 min in 10 mL aqueous sample containing acetate buffer (pH 4.75). The equilibration time was found to increase with increase in aqueous sample volume. The optode response was found to be linear in the UO(2)(2+) ions concentration range of 0.01-0.11 micromol L(-1) in tap water as well as aqueous solutions containing 0.1 mol L(-1) NaCl or NaNO(3). The tolerance to the presence of several cations and anions in the determination of UO(2)(2+) ion was studied. It was observed that the optode in the presence of buffer can tolerate presence of large amounts of interfering cations (Ce(4+), V(4+), Eu(3+), Al(3+), Fe(3+), Ni(2+), Cd(2+), Co(2+), Pb(2+), Hg(2+), Cu(2+) and Th(4+) ions) without hindering the sorption of UO(2)(2+) ions in the optode matrix. The present work indicated that 50 ppb UO(2)(2+) ions in 100 mL sample can easily be quantified using this optode. The optode was found to be fully reversible, can readily be regenerated by equilibrating it with 0.1 mol L(-1) HNO(3) and reusable up to three cycles. The applicability of the developed optode in real samples was studied by determining uranium in the ground water samples spiked with a known quantity of UO(2)(2+) ions.

Application of 140La and 24Na as intrinsic radiotracers for investigating catalyst dynamics in FCCUs.

Instrumental neutron activation analysis (INAA) of fluid catalytic cracking (FCC) catalyst samples was carried out with an objective to identify activable elements and evaluate its suitability for use as an intrinsic radiotracer for tracing catalyst itself in Fluid Catalytic Cracking Units (FCCUs) used in petroleum refining. Two catalyst samples obtained from two different refineries were analyzed. Twelve different elements were identified in each catalyst sample and their respective concentrations were determined. From the recorded gamma-ray spectra, it was found that lanthanum-140 ((140)La) and sodium-24 ((24)Na) were the predominantly present and suitable radionuclides that could be used as radiotracers for tracing catalyst in FCCUs. Lanthanum being present in much higher concentration forms the major component of the radiotracer after irradiation. Based on the results of INAA, appropriate quantities of the catalyst samples were irradiated with neutrons to produce the desired amount of activity of lanthanum-140 and sodium-24 to be used as radiotracers for tracing the catalyst itself in a pilot as well as an industrial-scale FCCU. The residence time distribution (RTD) of catalyst was measured and analyzed to determine mean residence time (MRT). The axial dispersion model (ADM) was used to simulate the measured RTD data and investigate the degree of axial mixing. The results of the experiments were used to improve the design of pilot-scale FCCU and optimize the performance of the industrial-scale FCCU.

Evaluation of doses from ionising radiation to non-human species at Trombay, Mumbai, India.

In order to meet the proposed regulatory compliances for the protection of non-human species from the ionising radiation, a comprehensive dose-evaluation process for terrestrial and aquatic biota was worked out at Trombay. During this work, dose rate (external and internal) from ionising radiation to the terrestrial plants and marine organisms (mixed varieties of fish) was evaluated by estimating the concentration of anthropogenic ((137)Cs, (90)Sr) and natural radionuclides ((238)U, (232)Th and (40)K) in environmental matrices, such as soil, vegetation, sea water and sediment. The samples were processed as per the International Atomic Energy Agency protocol for the estimation of naturally occurring and anthropogenic radionuclides. The average values of radiation exposure to the terrestrial plants for (40)K, (90)Sr, (137)Cs, (232)Th and (238)U were 632.8 +/- 40.5, 167.4 +/- 48.2, 691.2 +/- 29.9, 48769 +/- 13203 and 1801 +/- 1495 microGy y(-1), respectively. In the case of marine organisms (fish), the maximum external exposure was 195 microGy y(-1) due to (40)K concentration in bottom sediment, whereas the minimum was 0.004 microGy y(-1) due to (137)Cs in sea water. Internal exposure to fish was maximum (700 microGy y(-1)) due to (40)K, whereas the minimum of 0.12 microGy y(-1) was due to (90)Sr. Considering the dose limit of 10 mGy d(-1) (3.65 Gy y(-1)), proposed by the US Department of Energy, evaluated radiation exposure (external + internal) and dose rate in the present study to the terrestrial plants and marine organisms are orders of magnitude less.