Molecular dynamics simulations of simplified sodium borosilicate glasses: the effect of composition on structure and dynamics.

The fusion of valuable material properties has led to the acceptance of sodium borosilicate (NBS) glasses for nuclear waste immobilization. Although popular, the mechanisms associated with these properties are still only partially discovered and need further exploration. Bearing this in mind, the combination of experiments, molecular dynamics (MD) simulations and the Dell, Yuan and Bray model have been used to understand the role of composition variation for structural and physical aspects of vitrified borosilicate glasses. Experiments have been conducted to evaluate the macroscopic glass parameters of density (ρ), glass transition temperature (Tg) and thermal expansion coefficient (TEC). Experimentally observed trends for ρ, Tg and TEC with composition have been found in good agreement with the MD results. MD studies also provide a microscopic understanding of the glass structure and phenomena associated with the change in the glass composition. A detailed view of local structure and medium-range connectivity for the borosilicate glasses has been explored. Owing to a large B4 population, the results showed the abundant presence of BO4-BO4 connections, we hereby omit the generally accepted "B[4] avoidance rule" for glass. The relative propensity for connecting SiO4/BO3/BO4 structural motifs is in line with the predictions made by the Dell, Yuan and Bray model. Furthermore, the effects of composition on the mechanical integrity of NBS glasses, including the elastic nature, plastic distortion, yielding, breaking stress, and brittle fracture, have been explored by MD simulations. In addition, the glass dynamics have been evaluated by diffusion coefficient and the results suggest that Na+ is likely to be more mobile in the case of NBS1 as compared to NBS2 and NBS3 due to significant disruption in the glass network introduced by a larger amount of Na2O network modifier. Also, the diffusivity was reduced with increasing B2O3 due to the altered role of Na+ ions from network modifiers to charge compensators. The combined study of experiments, MD simulations and the Dell, Yuan and Bray model establish the correlation between the microscopic structure and macroscopic properties of NBS glasses with varied composition, which might be of great scientific use for future glasses in various applications including nuclear waste immobilization.

Ligand architectural effect on coordination, bonding, interaction, and selectivity of Am(iii) and Ln(iii) ions with bitopic ligands: synthesis, solvent extraction, and DFT studies.

The isolation of Am(iii) ion from Ln(iii) ions is very crucial for the safe disposal of nuclear wastes and thus, studies are being continuously pursued to accomplish this goal. In view of this, herein, a new conformationally rigid bitopic ligand, N,N,N',N'-tetra(2-ethylhexyl)piperazine-di-methylenecarboxamide (PIPDA) has been synthesized and studied for the separation of Am(iii) from Ln(iii) ions. The effect of structural rigidification on the selectivity of Am(iii) over Ln(iii) was compared with an open chain flexible compound, namely, N,N,N',N'-tetra(2-ethylhexyl)-3,6-(N'',N'''-dibutyl)diaza-octane-1,8-diamide (DADA). Two oxygen atoms of the diamide moiety seem to be responsible for controlling the metal ion extraction ability of PIPDA, whereas two nitrogen atoms of the piperazine moiety most probably dictate the separation factor between the Am(iii) and Eu(iii) ions in PIPDA. In addition, scalar relativistic density functional theory (DFT) in conjunction with Born-Haber thermodynamics was used herein to compliment the experimental selectivity. The experimentally observed preferential selectivity of PIPDA for Am(iii) ion over the Ln(iii) ion was corroborated by the computed extraction free energy, ΔGext. The covalent nature of bonding between the metal ions and the ligand was confirmed by analyzing the Mayer bond order and bond character analysis using the atom in molecule concept. Though the conformational rigidity of PIPDA gives stronger interaction than DADA, it does not offer a significant advantage over DADA in terms of the separation factor. The marginal increase in the separation factor for PIPDA over DADA might be attributed to the piperazine nitrogen and to the ligand architecture during complex formation.

Synthesis and antimicrobial evaluation of ester-linked 1,4-disubstituted 1,2,3-triazoles with a furyl/thienyl moiety.

Twenty ester-linked 1,4-disubstituted 1,2,3-triazoles having a furyl/thienyl moiety have been synthesized from heteroaryl prop-2-yn-1-yl carboxylate and aromatic azides via a Cu(I) catalyzed 1,3-dipolar cycloaddition. All the synthesized compounds were characterized by FTIR, [Formula: see text]H NMR, [Formula: see text]C NMR spectroscopy and HRMS. Synthesized triazoles were tested in vitro for antimicrobial evaluation against Gram-negative bacteria-Escherichia coli, Enterobacter aerogenes and Klebsiella pneumoniae; Gram-positive bacteria-Staphylococcus aureus and two fungal strains-Candida albicans and Aspergillus niger, reflecting moderate to good activity. The structure of compound 6f was also confirmed by X-ray crystallography (CCDC 1469326).

Potential of Vetiveria zizanoides L. Nash for phytoremediation of plutonium ((239)Pu): Chelate assisted uptake and translocation.

Plants have demonstrated a great potential to remove toxic elements from soils and solutions and been successfully used for phytoremediation of important radionuclides. Uptake potential of vetiver plants (V. zizanoides) for the remediation of (239)Pu in hydroponic and soil conditions was studied in the present work. High efficiency of V. zizanoides for the removal of (239)Pu was recorded with 66.2% being removed from the hydroponic solution after 30 days. However, remediation of (239)Pu from soil was limited. Remediation of (239)Pu from soil was increased with the addition of chelating agents citric acid (CA) and diethylenetriaminepentaacetic acid (DTPA). Accumulation of (239)Pu was recorded higher in roots than shoots, however its translocation from roots to shoots increased in the presence of chelators in hydroponic as well as soil conditions. DTPA was found more effective than CA showing higher translocation index (TI). Increase in TI was observed 8 and 6 times in the solution and soil respectively when plants were exposed to (239)Pu-DTPA in comparison to only (239)Pu. The present study demonstrates that V. zizanoides plant is a potential plant for phytoremediation of (239)Pu.

Seasonal trends in organochlorine pesticide residues in raw bovine milk from rural areas of Haryana, India.

Seasonal trends in organochlorine pesticides residues namely, 1,2,3,4,5,6-hexachlorocyclohexane (HCH) isomers, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane (DDT) and its metabolites and endosulfan stereo isomers were investigated in raw bovine milk samples from rural areas of Ambala, Gurgaon and Hisar districts of the state of Haryana for winter, summer, and post-monsoon seasons. Highest concentration of HCH and DDT was found in 43 % and 53 % milk samples, respectively in post-monsoon season whereas highest values of endosulfan was reported in 36 % samples during winter season. During the study period only 2 % milk samples exceeded the maximum residue limit recommended by WHO for ΣHCH, 1 % samples each for α-HCH and γ-HCH, 9 % samples for ß-HCH as recommended by PFAA and 30 % samples for ΣDDT as prescribed by FAO. No statistical difference in the mean concentration of ∑HCH and ∑Endosulfan could be observed in any of the three districts. However, ∑DDT concentration showed marked difference [F(2, 25) = 12.42, p = 0.00018)] among the three districts.

Regioselective synthesis and antimicrobial studies of ester linked 1,4-disubstituted 1,2,3-bistriazoles.

A series of 1,4-disubstituted 1,2,3-bistriazoles was synthesized via click chemistry by cycloaddition of various bisalkynes with benzyl/2-phenylethyl azide. Synthesized triazoles were characterized by IR, (1)H NMR, (13)C NMR and mass spectral techniques. All the compounds were evaluated for antibacterial/antifungal activities and found to possess moderate to good antimicrobial activities. Further the docking study for the most active compound against DNA Gyrase was also carried out.

Organochlorine pesticide residues in drinking water in the rural areas of Haryana, India.

Drinking water samples collected from rural areas of three districts of Haryana during pre-monsoon and post-monsoon periods were analysed for the presence of organochlorine pesticide residues. The main source of drinking water in rural areas, i.e. groundwater in Ambala and Gurgaon districts and surface water supply in Hisar district, was found to be contaminated with isomers of HCH and endosulfan and metabolites of DDT, whereas dieldrin remained below detection limits. During the study period, the mean values observed for total HCH, DDT and endosulfan were 87.6, 848.2, and 27.4 ng/L and 99.8, 275.3 and 164.2 ng/L, respectively, for Ambala and Gurgaon districts. In the case of Hisar district, the values were 78.5, 115.9, and 53.0 ng/L, respectively. During the study period, 37% of the samples exceeded the total pesticide level of 500 ng/L indicated in the EECD directive for drinking water. Seasonal variations of pesticide residues were also observed during the study period.

Organochlorine pesticide residues in human blood samples collected from Haryana, India and the changing pattern.

Blood samples were collected during August 1992 and August 2002 from various hospitals of Haryana state and analyzed for the presence of HCH and DDT residues and the change in concentration of pesticide residues was calculated in terms of % reduction. The study revealed that the mean residue levels of total HCH in human blood samples have declined by 87.6% while those of total DDT have decreased by 98.9% during a gap of 10 years. The obtained results reveal that during 1992 p,p'-DDT was the major component with the mean value of 6.125 mg/L followed by p,p'-DDE, γ-HCH, α-HCH and ß-HCH while in 2002, ß-HCH and p,p'-DDE were comparable with mean value of 0.053 and 0.052 mg/L, respectively followed by p,p'-DDT, α-HCH and p,p'-DDD.

Correction: Mechanism unravelling for highly efficient and selective 99TcO4 - sequestration utilising crown ether based solvent system from nuclear liquid waste: experimental and computational investigations.

[This corrects the article DOI: 10.1039/D1RA07738D.].

Mechanism unravelling for highly efficient and selective 99TcO4 - sequestration utilising crown ether based solvent system from nuclear liquid waste: experimental and computational investigations.

Selective and efficient separation of pertechnetate (TcO4 -) from nuclear waste is desirable for the safe and secure management of radioactive waste. Here, we have projected dibenzo-18-crown-6 ether (DB18C6) in a highly polar nitrobenzene medium for enhancing the removal efficiency of 99Tc from reprocessing plant low level waste (LLW). An effort was made to determine the stoichiometry of metal-ligand complex by slope ratio method, revealing that one ligand (DB18C6) binds with one TcO4 - moiety. Optimum ligand concentration for 99Tc extraction was evaluated. Relevant interference of the anions was studied systematically. The effect of solution pH was analysed on the extraction efficiency of 99Tc. A kinetic study was carried out for maximum extraction of metal ions. A quantitative stripping study was also achieved for metal ions with a suitable stripping solution. After evaluation of all essential parameters, selectivity and feasibility studies were finally carried out with actual low level reprocessing plant waste to demonstrate a laboratory scale process for effective separation of TcO4 - ions. Density functional theory (DFT) calculations were carried out to understand the nature of the complexation of TcO4 - ion with DB18C6 in different solvents systems and to elucidate the key aspect behind ionic selectivity and enhanced the 99Tc extraction efficiency of DB18C6 in the studied diluent systems. The ΔE and ΔG values for different modeled complexation reactions were evaluated systematically. From the calculated free energy of complexation of TcO4 - with DB18C6, it was observed that the consideration of explicit solvent plays a vital role in predicting the experimental selectivity.

Changing patterns of organochlorine pesticide residues in raw bovine milk from Haryana, India.

Bovine milk samples were collected and analyzed during 1992 and 1998 from rural areas of 14 different districts of Haryana state for the presence of HCH and DDT residues. The study revealed that the mean residues of ΣHCH in raw bovine milk have declined by 67.5% while mean levels of ΣDDT have decreased by 92.8% during six years gap. The obtained results reveal that during 1992 p,p'-DDT was the main component followed by p,p'-DDD, α-HCH and ß-HCH while in 1998, p,p'-DDE and ß-HCH followed by p,p'-DDT were relatively more as compared to other isomers and metabolites of these pesticides.

Suitability assessment of dumpsite soil biocover to reduce methane emission from landfills under interactive influence of nutrients.

Biocovers are known for their role as key facilitator to reduce landfill methane (CH4) emission on improving microbial methane bio-oxidation. Methanotrophs existing in the aerobic zone of dumped wastes are the only known biological sinks for CH4 being emitted from the lower anaerobic section of landfill sites and even from the atmosphere. However, their efficacy remains under the influence of landfill environment and biocover characteristics. Therefore, the present study was executed to explore the suitability and efficacy of dumpsite soil as biocover to achieve enhanced methane bio-oxidation under the interactive influence of nutrients, carbon source, and environmental factors using statistical-mathematical models. The Placket-Burman design (PBD) was employed to identify the significant factors out of 07 tested factors having considerable impact on CH4 bio-oxidation. The normal plot and Student's t test of PBD indicated that ammonical nitrogen (NH4+-N), nitrate nitrogen (NO3--N), methane (CH4), and copper (Cu) concentration were found significant. A three-level Box-Behnken design (BBD) was further applied to optimize the significant factors identified from PBD. The BBD results revealed that interactive interaction of CH4 with NH4+-N and NO3--N affected the CH4 bio-oxidation significantly. The sequential statistical approach predicted that maximum CH4 bio-oxidation of 27.32 µg CH4 h-1 could be achieved with CH4 (35%), NO3--N (250 µg g-1), NH4+-N (25 µg g-1), and Cu (50 mg g-1) concentration. Conclusively, waste dumpsite soil could be a good alternative over conventional soil cover to improve CH4 bio-oxidation and lessen the emission of greenhouse gas from waste sector.

Achieving highly efficient and selective cesium extraction using 1,3-di-octyloxycalix[4]arene-crown-6 in n-octanol based solvent system: experimental and DFT investigation.

Due to the long half-life of 137Cs (t 1/2 ∼ 30 years), the selective extraction of cesium (Cs) from high level liquid waste is of paramount importance in the back end of the nuclear fuel cycle to avoid long term surveillance of high radiotoxic waste. As 1,3-di-octyloxycalix[4]arene-crown-6 (CC6) is suggested to be a promising candidate for selective Cs extraction, the improvement in the Cs extraction efficiency by CC6 has been investigated through the optimization of the effect of dielectric media on the extraction process. The effects of the feed acid (HNO3, HCl, and HClO4) and the composition of the diluents for the ligand in the organic phase on the extraction efficiency of Cs have been investigated systematically. In 100% n-octanol medium, Cs is found to form a 1 : 1 ion-pair complex with CC6 (0.03 M) providing a very high distribution ratio of D Cs ∼ 22, suggesting n-octanol as the most suitable diluent for Cs extraction. No significant interference of other relevant cations such as Na, Mg and Sr was observed on the D Cs value in the optimized solvent system. Density functional theory (DFT) based calculations have been carried out to elucidate the reason of ionic selectivity and enhanced Cs extraction efficiency of CC6 in the studied diluent systems. In addition to the ionic size-based selectivity of the crown-6 cavity, the polarity of the organic solvent system, the hydration energy of the ion, and the relative reorganization of CC6 upon complexation with Cs are understood to have roles in achieving the enhanced efficiency for the extraction of Cs by the CC6 extractant in nitrobenzene medium.

Surface dose rate variations in planar and curved geometries of 106Ru/106Rh plaque sources for ocular tumors.

PURPOSE: Investigation of surface dose rate variation with respect to the source configuration of 106Ru/106Rh eye plaque. To explore an alternate way to determine activity of brachytherapy plaques. METHODS: The surface dose rates of 106Ru/106Rh plaque developed indigenously were measured by extrapolation chamber. To rule out possibility of any error in the activity distribution and quantity, same source was used in two different configurations namely planar and curved. EBT3 Gafchromic film was used for determination of uniformity in activity. Monte Carlo-based Codes EGSnrc and FLUKA were used to calculate dose rate in tissue, percentage depth dose and for determination of activity. Parameters and correction factors were estimated using simulations. RESULTS: The measured reference absorbed dose rates for planar and curved 106Ru/106Rh eye plaques are found to be 589 ± 29 mGy/h and 560 ± 28 mGy/h, respectively. The difference in the reference absorbed dose rate of curved eye plaque is about ~5% as compared to planar configuration. The FLUKA-calculated dose values are almost independent of cavity length of the extrapolation chamber for both eye plaques. The FLUKA-based dose rates per µCi 106Ru/106Rh are about 17.28 ± 0.08 mGy/h and 16.48 ± 0.06 mGy/h, respectively for planar and curved eye plaques which match well with the measurements. The calculated activities for planar and curved eye plaques are 34.08 µCi and 33.98 µCi, respectively. CONCLUSIONS: Surface dose rates for a prototype 106Ru/106Rh eye plaque with different configurations were estimated using simulations and measured experimentally. An alternate way to determine activity of beta-gamma brachytherapy plaque has been proposed.

Pesticide pollution of River Ghaggar in Haryana, India.

Ghaggar, one of the major rivers of northern India originating in outer Himalayas and flowing through the state of Punjab, Haryana, and Rajasthan, is put to multiple uses. Along its course of 464 km, it receives discharge from various cities and runoff from agricultural lands. Punjab and Haryana are two predominantly agricultural states of India using substantial amounts of agrochemicals, yet there are no reports available in literature on the level of pesticides in the stretch of river Ghaggar through Punjab and Haryana. This is the first report on pesticide pollution of the river Ghaggar in Haryana. Water samples along the 230-km stretch of the river in Haryana were analyzed for the presence of organochlorine insecticide residues. While aldrin and dieldrin were below detection limits, both hexachlorocyclohexane (HCH) and dichlorodiphenyltrichloroethane (DDT) were traceable in all the water samples. High concentration of beta-HCH among SigmaHCH indicates old pollution source whereas predominance of p,p'-DDT among SigmaDDT reflects its recent use in the catchment area of the river. The concentrations of HCH and DDT in all the samples were above the permissible limits prescribed by the European Commission Directive for drinking purposes.

Effect of cyanobacterial exopolysaccharides on salt stress alleviation and seed germination.

Effectof exopolysaccharides (EPS) produced by a consortium of cyanobacteria on germination of three crops wheat, maize and rice was studied at different salt concentrations. Production of EPS was found to be stimulated by salts, which in turn had a significant Na+ removal capability from aqueous solution. Seed germination, vigor index and mobilization efficiency in all the three crops remarkably improved when cyanobacterial EPS was applied. While germination improved significantly by 13 to 30%, mobilization efficiency increased marginally by 1.03 to 1.1 times and vigor index increased by 1.15 to 2.4 times in these crops in response to EPS under non-saline conditions. Salinity had an inhibitory effect on seed germination of all the species showing 18 to 54% reduction. However, in the presence of EPS, the salt induced inhibition diminished to 13 to 18%. Inhibitory effect of salt on chlorophyll concentration, vigor index and mobilization efficiency of the seedlings was much less in these crops in the presence of EPS, indicating the latter's role in salt stress alleviation.

Vermicomposting of sugar industry waste (press mud) mixed with cow dung employing an epigeic earthworm Eisenia fetida.

In India, millions of tons of press mud (PM) are generated by sugar mills every year. This paper reports the potential of vermitechnology to convert sugar industry waste PM mixed with cow dung (CD) into vermicompost, employing an epigeic earthworm Eisenia fetida. A total of six different reactors were established having different ratios of PM and CD including one control (CD only). The growth and fecundity of E. fetida was monitored for 13 weeks. Maximum growth was recorded in 100% CD, but earthworms grew and reproduced favourably up to 1:1 PM and CD feed composition. However, greater percentages of PM in different reactors significantly affected the growth and fecundity of worms. Vermicomposting resulted in a decrease in carbon concentration and an increase in nitrogen, phosphorus and calcium concentrations of the vermicompost. Investigations indicated that vermicomposting could be an alternative technology for the management of PM into useful fertilizing material, if mixed at maximum 50% with CD.

TALSPEAK process on hollow fiber renewable liquid membrane apropos to the remedial maneuver of high level nuclear waste.

In concurrence with objectives of advanced high level nuclear waste(HLW) management, separation of chemically similar trivalent actinides and lanthanides is accomplished using TALSPEAK (Trivalent Actinide - Lanthanide Separation by Phosphorous reagent Extraction from Aqueous Komplexes) process on hollow fibre renewable liquid membrane (HFRLM). Permeability coefficient(Kf) of metal ions are determined under varying concentrations of diethylene triamine pentacaetic acid (DTPA) and H+ in the feed solution, containing 241Am with other metal impurities usually occurred in the HLW, and di(2-ethylhexyl) phosphoric acid (HDEHP) in liquid membrane and receiving emulsion phase. Optimized process conditions obtained are: 5 ± 0.25 L feed solution: containing 0.05 M DTPA, 1 M lactic acid and metal ions under the agitation of 400 ± 15 rpm, receiving phase: emulsion of 400 ± 15 mL 2 M HNO3 + 100 mL 0.2 M HDEHP/dodecane under stirring at 650 ± 25 rpm. The Kf of metal ions obtained under optimized process conditions are in the order: Am(III)<

Potential of Chromolaena odorata for phytoremediation of (137)Cs from solution and low level nuclear waste.

Potential of Chromolaena odorata plants for remediation of (137)Cs from solutions and low level nuclear waste was evaluated. When plants were exposed to solutions spiked with three different levels of (137)Cs, namely 1 x 10(3) kBqL(-1), 5 x 10(3) kBqL(-1) and 10 x 10(3) kBqL(-1), 89%, 81% and 51% of (137)Cs was found to be remediated in 15 d, respectively. At the lowest Cs activity (1 x 10(3) kBqL(-1)), accumulation of Cs was found to be higher in roots compared to shoots, while at higher Cs activities (5 x 10(3) kBqL(-1) and 10 x 10(3) kBqL(-1)), Cs accumulation was more in shoots than roots. When plants were incubated in low level nuclear waste, 79% of the activity was removed by plants at the end of 15 d. The present study suggests that C. odorata could be used as a potential candidate plant for phytoremediation of (137)Cs.

Ionic transport behavior of BaO containing sodium borosilicate glasses.

The present manuscript describes the preparation, characterization and electrical behavior of sodium borosilicate glasses with varying concentrations of BaO, while maintaining the SiO(2):B(2)O(3):Na(2)O ratios constant for all the samples. The effect of BaO substitution on the ionic conductivity of glasses was studied by ac impedance analyzer, below the glass transition temperature. The diffusion coefficient (D) of each sample has been determined from the values of electrical conductivity and density. The activation energy for sodium ion transport has been calculated from the values of diffusion coefficients at different temperatures. The electrical properties of the modified glass have been explained on the basis of the structural factor.