Microcolumn studies of dye adsorption onto manganese oxides modified diatomite

The method described here cannot fully replace the analysis of large columns by small test columns (microcolumns). The procedure, however, is suitable for speeding up the determination of adsorption parameters of dye onto the adsorbent and for speeding up the initial screening of a large adsorbent collection that can be tedious if a several adsorbents and adsorption conditions must be tested. The performance of methylene blue (MB), a basic dye, Cibacron reactive black (RB) and Cibacron reactive yellow (RY) was predicted in this way and the influence of initial dye concentration and other adsorption conditions on the adsorption behaviour were demonstrated.

Safe fabrication of sharp gold tips for light emission in scanning tunnelling microscopy

Gold is the optimal tip metal for light emission in scanning tunnelling microscopy (LESTM) under ambient conditions. Sharp Au-tips of similar to 10nm radius were produced reliably using a safe, two-step etching method in 20% (w/w) CaCl2 solution. Previous CaCl2-based methods have tended to produce blunter tips, while other etching techniques that do produce sharp Au-tips, do so with the use of toxic or hazardous electrolytes. The tips are characterised using scanning electron microscopy and their efficacy in LESTM is evidenced by high-resolution, simultaneous topographic and photon mapping of Au(1 1 1)- and polycrystalline Au-surfaces. Spectra of the optical emission exhibit only one or two peaks with etched tips in contrast to the more complex spectra typical of cut tips; this feature, together with the highly symmetric geometry of the tips, facilitates a definitive analysis of the light emission process. (c) 2007 Elsevier B. V.. All rights reserved.

Deep weathering of calcareous sedimentary rock and the redistribution of iron and manganese in soil and saprolite

Iron and Mn redistribute in soil and saprolite during weathering. The geological weathering fronts ofcalcareous sedimentary rock were investigated by examining the bulk density, porosity, and distribution ofCa, Fe, and Mn. Core samples were taken ofsoil, saprolite, and bedrock material from both summit (HHMS-4B) and sideslope (HHMS-5A) positions on an interbedded Nolichucky shale and Maryville limestone landform in Solid Waste Storage Area 6 (SWSA-6). This is a low-level radioactive solids waste disposal site on the Dept. ofEnergy (DOE) Oak Ridge Reservation in Roane County Tennessee. This work was initiated because data about the properties of highly weathered sedimentary rock on this site were limited. The core samples were analyzed for pH, calcium carbonate equivalence (CCE), hydroxylamine-extractable (HA) Mn, and dithionite-citrate (CBD)-extractable Fe and Mn. Low pH values occurred from the soil surface down to the depth of the oxidized and leached saprolite in both cores. The CCE and HA-extractable Mn results were also influenced by the weathering that has occurred in these zones. Extractable Mn oxide was higher at a lower depth in the oxidized and leached saprolite compared with the Fe oxide, which was higher in the overlying soil solum. Amounts of Mn oxides were higher in the sideslope core (HHMS-5A) than in the summit core (HHMS-4B). Iron was more abundant in the deeper weathered summit core, but the highest value, 39.4 g kg-1, was found at 1.8 to 2.4 m in the sideslope core. The zone encompassing the oxidized and partially leached saprolite down to the unoxidized and unleached bedrock had higher densities and larger quantities of CaCO3 than the soil solum and oxidized and leached saprolite. The overlying soil and oxidized and leached saprolite had lower pH and CCE values and were higher in Fe and Mn oxides than the oxidized and unleached saprolite. The distribution of Fe and Mn is important when evaluating soil and saprolite for hazardous waste disposal site assessment.

Adsorption Characteristics of Reactive Dyes in Columns of Activated Carbon

Abstract: Adsorption behaviour of reactive dyes in fixed-bed adsorber was evaluated in this work. The characteristics of mass transfer zone (MTZ), where adsorption in column occurs, were affected by carbon bed depth and influent dye concentration. The working lifetime (t(x)) of MTZ, the height of mass transfer zone (HMTZ), the rate of mass transfer zone (RMTZ), and the column capacity at exhaustion (q(column)) were estimated for the removal of remazol reactive yellow and remazol reactive black by carbon adsorber. The results showed that column capacity calculated at 90% of column exhaustion was lower than carbon capacity obtained from equilibrium studies. This indicated that the capacity of activated carbon was not fully utilized in the fixed-bed adsorber. The bed-depth service time model (BDST) was applied for analysis of reactive yellow adsorption in the column. The adsorption capacity of reactive yellow calculated at 50% breakthrough point (No) was found to be 0.1 kg kg(-1) and this value is equivalent to about 14% of the available carbon capacity. The results of this study indicated the applicability of fixed-bed adsorber for removing remazol reactive yellow from solution. (C) 2008 Elsevier B.V. All rights reserved.

Ionic liquids are not always green: hydrolysis of 1-butyl-3-methylimidazolium hexafluorophosphate

1-Butyl-3-methylimidazolium fluoride hydrate has been identified crystallographically as a decomposition product created during purification of the hydrophobic ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate. This highlights the need to treat ionic liquids much as one would any other research chemical with potentially hazardous properties, unknown toxicity and/or stability, particularly when searching for 'green solvents'.

Industrial applications of ionic liquids

The potential to use Ionic Liquids (ILs) as novel solvents or fluids for a diverse range of applications has become increasingly rent as researchers in academia and try respond to challenges from atmospheric emissions and disposal of many common solvents by evaluating novel reaction media. The intrinsic non-volatile nature of ILs provides an opportunity to reduce, or even completely eliminate, hazardous and toxic emissions to the atmosphere, thus providing the promise for significant environmental benefits. In synthesis and catalysis, ILs have been used as solvents (or solvents and catalysts), with the greatest current effort on using the ILs as alternatives to VOCs. In contrast, electrochemical studies hove utills'ed the fact that ILs are liquid rather than solids to provide liquid electrolytes without needing to odd an additional solvent. is overview appraiso an appraisal of potential to use ILs in industrial applications, illustrating some areas where practical uses are being developed, and how, throuqh understanding ionic liquids in a conceptuo level, new opportunities ore continuing to evolve.

Ionic Liquid-Based Routes to Conversion or Reuse of Recycled Ammonium Perchlorate

New, potentially green, and efficient synthetic routes for the remediation and/or re-use of perchlorate-based energetic materials have been developed. Four simple organic imidazolium- and phosphonium-based perchlorate salts/ionic liquids have been synthesized by simple, inexpensive, and nonhazardous methods, using ammonium perchlorate as the perchlorate source. By appropriate choice of the cation, perchlorate can be incorporated into an ionic liquid which serves as its own electrolyte for the electrochemical reduction of the perchlorate anion, allowing for the regeneration of the chloride-based parent ionic liquid. The electrochemical degradation of the hazardous perchlorate ion and its conversion to harmless chloride during electrolysis was studied using IR and Cl-35 NMR spectroscopies.

Adsorption mechanisms of removing heavy metals and dyes from aqueous solution using date pits solid adsorbent

A potential usefulness of raw date pits as an inexpensive solid adsorbent for methylene blue (MB), copper ion (Cu2+), and cadmium ion (Cd2+) has been demonstrated in this work. This work was conducted to provide fundamental information from the study of equilibrium adsorption isotherms and to investigate the adsorption mechanisms in the adsorption of MB, Cu2+, and Cd2+ onto raw date pits. The fit of two models, namely Langmuir and Freundlich models, to experimental data obtained from the adsorption isotherms was checked. The adsorption capacities of the raw date pits towards MB and both Cu2+ and Cd2+ ions obtained from Langmuir and Freundlich models were found to be 277.8, 35.9, and 39.5 mg g(-1), respectively. Surface functional groups on the raw date pits surface substantially influence the adsorption characteristics of MB, Cu2+, and Cd2+ onto the raw date pits. The Fourier transform infrared spectroscopy (FTIR) studies show clear differences in both absorbances and shapes of the bands and in their locations before and after solute adsorption. Two mechanisms were observed for MB adsorption, hydrogen bonding and electrostatic attraction, while other mechanisms were observed for Cu2+ and Cd2+. For Cu2+, binding two cellulose/lignin units together is the predominant mechanism. For Cd2+. the predominant mechanism is by binding itself using two hydroxyl groups in the cellulose/lignin unit. (C) 2009 Elsevier B.V. All rights reserved.

Green photochemistry: photo-Friedel-Crafts acylations of 1,4-naphthoquinone in room temperature ionic liquids

The photo-Friedel-Crafts acylation of 1,4-naphthoquinone with various aldehydes was investigated in a series of room temperature ionic liquids. High conversions and selectivities were achieved in [C(2)mim](+)-based ionic liquids with the highest isolated yields found in [C(2)mim][NTf2]. The developed procedure allowed for a replacement of hazardous solvents such as benzene and acetonitrile which are commonly used for this transformation.

Site formation processes in caves: the Holocene sediments of the Haua Fteah, Cyrenaica, Libya.

Caves have yielded some of the most globally important archaeological sequences, but often their interpretation has suffered from assumptions about cave sedimentary processes. Caves contain distinctive sedimentary environments: this has major implications for the understanding of contained archaeological materials. This paper describes and analyses the Holocene sediments in the Haua Fteah, a sequence regarded as essentially continuous by the original excavator. 50 years after it was first excavated, the Haua’s Epipalaeolithic to post-Classical chronological range and rich finds make it still the key Holocene archaeological site in North Africa. The reassessment shows, however, that the sequence is strongly discontinuous and this has major implications for the reinterpretation of the site, as the highlyresolved archaeological record is thus likely to reflect a series of brief occupations, rather than continuous human activity. As with many caves, the sedimentary record in the Haua Fteah is an extremely sensitive indicator of environments and processes in the wider landscape. Secure understanding of sedimentary process, from analysis of the highly individual records found in caves, is essential for full understanding of their contained archaeology.