Electrochemistry of Hg(II) Salts in Room-Temperature Ionic Liquids

The electrochemistry of HgCl(2) and [Hg(NTf(2))(2)] ([NTf(2)](-) = bis-{(trifluoromethyl)sulfonyl}imide) has been studied in room temperature ionic liquids. It has been found that the cyclic voltammetry of Hg(II) is strongly dependent on a number of factors (e.g., concentration, anions present in the mixture, and nature of the working electrode) and differs from that found in other media. Depending on conditions, the cyclic voltammetry of Hg(II) can give rise to one, two, or four reduction peaks, whereas the reverse oxidative scans show two to four peaks. Diffuse reflectance UV-vis spectroscopy and X-ray powder diffraction have been used to aid the assignment of the voltammetric waves.

Field fluxes and speciation of arsines emanating from soils

The biogeochemical cycle of arsenic (As) has been extensively studied over the past decades because As is an environmentally ubiquitous, nonthreshold carcinogen, which is often elevated in drinking water and food. It has been known for over a century that micro-organisms can volatilize inorganic As salts to arsines (arsine AsH(3), mono-, di-, and trimethylarsines, MeAsH(2), Me(2)AsH, and TMAs, respectively), but this part of the As cycle, with the exception of geothermal environs, has been almost entirely neglected because of a lack of suited field measurement approaches. Here, a validated, robust, and low-level field-deployable method employing arsine chemotrapping was used to quantify and qualify arsines emanating from soil surfaces in the field. Up to 240 mg/ha/y arsines was released from low-level polluted paddy soils (11.3 ± 0.9 mg/kg As), primarily as TMAs, whereas arsine flux below method detection limit was measured from a highly contaminated mine spoil (1359 ± 212 mg/kg As), indicating that soil chemistry is vital in understanding this phenomenon. In microcosm studies, we could show that under reducing conditions, induced by organic matter (OM) amendment, a range of soils varied in their properties, from natural upland peats to highly impacted mine-spoils, could all volatilize arsines. Volatilization rates from 0.5 to 70 µg/kg/y were measured, and AsH(3), MeAsH(2), Me(2)AsH, and TMAs were all identified. Addition of methylated oxidated pentavalent As, namely monomethylarsonic acid (MMAA) and dimethylarsinic acid (DMAA), to soil resulted in elevated yearly rates of volatilization with up to 3.5% of the total As volatilized, suggesting that the initial conversion of inorganic As to MMAA limits the rate of arsine and methylarsines production by soils. The nature of OM amendment altered volatilization quantitatively and qualitatively, and total arsines release from soil showed correlation between the quantity of As and the concentration of dissolved organic carbon (DOC) in the soil porewater. The global flux of arsines emanating from soils was estimated and placed in the context of As atmospheric inputs, with arsines contributing from 0.9 to 2.6% of the global budget.

Molecular layering and local order in thin films of 1-alkyl-3-methylimidazolium ionic liquids using X-ray reflectivity

X-ray reflectivity measurements in air of thin films of 1-alkyl-3-methylimidazolium salts in the liquid, liquid crystalline and solid states supported on Si( 111) are described. The films show Bragg features in both liquid crystalline and solid phases, but only after an initial annealing cycle. Kiessig fringes are observed only for the 1-octadecyl-3-methyl-imidazolium hexafluorophosphate films and, following analysis using Parratt32, a bi-layer model is proposed whereby the molecules are orientated with ionic groups at both salt-air and salt-silicon interfaces.

Efficient, halide free synthesis of new, low cost ionic liquids: 1,3-dialkylimidazolium salts containing methyl- and ethyl-sulfate anions

New low-cost ionic liquids containing methyl- and ethyl-sulfate anions can be easily and efficiently prepared under ambient conditions by the reaction of 1-alkylimidazoles with dimethyl sulfate and diethyl sulfate. The preparation and characterization of a series of 1,3-dialkylimidazolium alkyl sulfate and 1,2,3-trialkylimidazolium alkyl sulfate salts are reported. 1,3-Dialkylimidazolium salts containing at least one non-methyl N-alkyl substituent are liquids at, or below room, temperature. Three salts were crystalline at room temperature, the single crystal X-ray structure of 1,3-dimethylimidazolium methyl sulfate was determined and shows the formation of discrete ribbons comprising of two anion-cation hydrogen-bonded chains linked via intra-chain hydrogen-bonding, but little, or no inter-ribbon hydrogen-bonding. The salts are stable, water soluble, inherently 'chloride-free', display an electrochemical window of greater than 4 V, and can be used as alternatives to the corresponding halide salts in metathesis reactions to prepare other ionic liquids including 1-butyl-3-methylimidazolium hexafluorophosphate.

Carbon flow in an upland grassland: effect of liming on the flux of recently photosynthesized carbon to rhizosphere soil

The effect of liming on the flow of recently photosynthesized carbon to rhizosphere soil was studied using (CO2)-C-13 pulse labelling, in an upland grassland ecosystem in Scotland. The use of C-13 enabled detection, in the field, of the effect of a 4-year liming period of selected soil plots on C allocation from plant biomass to soil, in comparison with unlimed plots. Photosynthetic rates and carbon turnover were higher in plants grown in limed soils than in those from unlimed plots. Higher delta(13)C% values were detected in shoots from limed plants than in those from unlimed plants in samples clipped within 15 days of the end of pulse labelling. Analysis of the aboveground plant production corresponding to the 4-year period of liming indicated that the standing biomass was higher in plots that received lime. Lower delta(13)C% values in limed roots compared with unlimed roots were found, whereas no significant difference was detected between soil samples. Extrapolation of our results indicated that more C has been lost through the soil than has been gained via photosynthetic assimilation because of pasture liming in Scotland during the period 1990-1998. However, the uncertainty associated with such extrapolation based on this single study is high and these estimates are provided only to set our findings in the broader context of national soil carbon emissions.

Low pressure carbon dioxide solubility in lithium-ion batteries based electrolytes as a function of temperature. Measurement and prediction

We present in this study the effect of nature and concentration of lithium salt, such as the lithium hexafluorophosphate, LiPF6; lithium tris(pentafluoroethane)-trifluorurophosphate LiFAP; lithium bis(trifluoromethylsulfonyl)imide, LiTFSI, on the CO2 solubility in four electrolytes for lithium ion batteries based on pure solvent that include ethylene carbonate (EC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), as well as, in the EC:DMC, EC:EMC and EC:DEC (50:50) wt.% binary mixtures as a function of temperature from (283 to 353) K and atmospheric pressure. Based on experimental solubility values, the Henry’s law constant of the carbon dioxide in these solutions with the presence or absence of lithium salt was then deduced and compared with reported values from the literature, as well as with those predicted by using COSMO-RS methodology within COSMOThermX software. From this study, it appears that the addition of 1 mol · dm-3 LiPF6 salt in alkylcarbonate solvents decreases their CO2 capture capacity. By using the same experimental conditions, an opposite CO2 solubility trend was generally observed in the case of the addition of LiFAP or LiTFSI salts in these solutions. Additionally, in all solutions investigated during this work, the CO2 solubility is greater in electrolytes containing the LiFAP salt, followed by those based on the LiTFSI case. The precision and accuracy of the experimental data reported therein, which are close to (1 and 15)%, respectively. From the variation of the Henry’s law constant with temperature, the partial molar thermodynamic functions of dissolution such as the standard Gibbs energy, the enthalpy, and the entropy, as well as the mixing enthalpy of the solvent with CO2 in its hypothetical liquid state were calculated. Finally, a quantitative analysis of the CO2 solubility evolution was carried out in the EC:DMC (50:50) wt.% binary mixture as the function of the LiPF6 or LiTFSI concentration in solution to elucidate how ionic species modify the CO2 solubility in alkylcarbonates-based Li-ion electrolytes by investigating the salting effects at T = 298.15 K and atmospheric pressure.

Comparative study on transport properties for LiFAP and LiPF6 in alkyl-carbonates as electrolytes through conductivity, viscosity and NMR self-diffusion measurements

We present in this work a comparative study on density and transport properties, such as the conductivity (sigma), viscosity (eta) and self-diffusion coefficients (D), for electrolytes based on the lithium hexafluorophosphate, LiPF6; or on the lithium tris(pentafluoroethane)-trifluorophosphate, LiFAP dissolved in a binary mixture of ethylene carbonate (EC) and dimethylcarbonate (DMC) (50:50 wt%). For each electrolyte, the temperature dependence on transport properties over a temperature range from 10 to 80 degrees C and 20 to 70 degrees C for viscosity and conductivity, respectively, exhibits a non-Arrhenius behavior. However, this dependence is correctly correlated by using the Vogel-Tamman-Fulcher (VTF) type fitting equation. In each case, the best-fit parameters, such as the pseudo activation energy and ideal glass transition temperature were then extracted. The self-diffusion coefficients (D) of the Li+ cation and PF6- or FAP(-) anions species, in each studied electrolyte, were then independently determined by observing Li-3, F-19 and P-31 nuclei with the pulsed-gradient spin-echo (PGSE) NMR technique over the same temperature range from 20 to 80 degrees C. Results show that even if the diffusion of the lithium cation is quite similar in both electrolytes, the anions diffusion differs notably. In the case of the LiPF6-based electrolyte, for example at T approximate to 75 degrees C (high temperature), the self-diffusion coefficients of Li+ cations in solution (D (Li+)approximate to 5 x 10(-19) m(2) s(-1)) is 1.6 times smaller than that of PF6- anions (D (PF6-) = 8.5 x 10(-19) m(2) s(-1)), whereas in the case of the LiFAP-based electrolyte, FAP(-) anions diffuse at same rate as the Li+ cations (D (FAP(-)) = 5 x 10(-1) m(2) s(-1)). Based on these experimental results, the transport mobility of ions were then investigated through Stokes-Einstein and Nernst-Einstein equations to determine the transport number of lithium t(Li)(+), effective radius of solvated Li+ and of PF6- and FAP(-) anions, and the degree of dissociation of these lithium salts in the selected EC/DMC (50:50 wt%) mixture over a the temperature range from 20 to 80 degrees C. This study demonstrates the conflicting nature of the requirements and the advantage of the well-balanced properties as ionic mobility and dissociation constant of the selected electrolytes. (C) 2013 Elsevier Ltd. All rights reserved.

Uranium halide complexes in ionic liquids: an electrochemical and structural study

The electrochemistry of the salts, [emim](2)[UBr6] and [emim](2)[UO2Br4] ([emim] = 1-ethyl-3-methylimidazolium), has been investigated in both a basic and an acidic bromoaluminate(III) ionic liquid. In the basic ionic liquid, the hexabromo salt undergoes a one-electron reversible reduction process at a stationary glassy carbon disc electrode, while the tetrabromodioxo salt was reduced to a uranium(IV) species by an irreversible two-electron process with the simultaneous transfer of oxide to the ionic liquid. On the other hand, dissolution of either of the salts in an acidic bromoaluminate( III) ionic liquid resulted in the formation of the same electroactive species. The solid state structures of the uranium chloride salts, [emim](2)[UCl6] and [emim](2)[UO2Cl4], have previously been reported, but have now been re-evaluated using a new statistical model developed in our group, to determine the presence or absence of weak hydrogen bonding interactions in the crystalline state.

Olefin / Paraffin separation using Task-Specific Materials based on Ionic Liquids: Advances in Gas Processing

In this work, 1-hexene was extracted from its mixtures with n-hexane in varying ratios using a task specific ionic liquid. Herein, the ionic liquid (IL) 1-butyl-3-methylimidazolium nitrate, [BMIM][NO3], was used and examined with and without the addition of a metal salt. The impact of water on both selectivity and distribution coefficient was also tested. Four potential metal salts were investigated, the results of which demonstrate that the dissolution of transition-metal salts in the IL improves the separation of 1-hexene from n-hexane through metal-olefin complexation. Additionally, the presence of water in IL solutions containing metal salt enhances this selectivity. Finally, UNIFAC was used to correlate the experimental LLE data with good accuracy.

Land use history of Village Bay, Hirta, St Kilda World Heritage Site:A palynological investigation of plaggen soils

This paper presents findings based on a palynological investigation of artificially accreting (plaggen) soils from the settlement of Village Bay, Hirta, in the St Kilda archipelago, which was perhaps the most distant and inhospitable outpost of sustained human habitation in the British Isles. The soils were developed principally through the addition of turf ash and seabird waste, although some ash may have been derived from upland peats. It is assumed that the woodland pollen signal (much lower in the soils than in an upland peat site nearby) represents off-island sources. Corylus avellana-type pollen (frequent in upland sites), along with Potentilla-type, may provide markers in the Village Bay profiles for the addition of ashed hillside turf, and possibly peat, to the plaggen soils. Cereal-type pollen is well represented through the profiles and is often strongly associated with the record for Chrysanthemum segetum (corn marigold), a frequent indicator of arable land. The Brassicaceae signal may partly reflect the cultivation of cabbages; Chelidonium majus (greater celandine) may have been grown for medicinal use. Soil mixing has rendered radiocarbon dating meaningless at this site, but the establishment of a change in cultivation regime before AD 1830 may have been identified from the patterns of pollen concentration and preservation in the profiles. © 2008 Elsevier B.V. All rights reserved.

An arsenic-accumulating, hypertolerant brassica, Isatis capadocica

Isatis capadocica, a brassica collected from Iranian arsenic-contaminated mine spoils and control populations, was examined to determine arsenate tolerance, metabolism and accumulation. I. cappadocica exhibited arsenate hypertolerance in both mine and nonmine populations, actively growing at concentrations of > 1 mm arsenate in hydroponic solution. I. cappadocica had an ability to accumulate high concentrations of arsenic in its shoots, in excess of 100 mg kg(-1) DW, with a shoot : root transfer ratio of > 1. The ability to accumulate arsenic was exhibited in both hydroponics and contaminated soils. Tolerance in this species was not achieved through suppression of high-affinity phosphate/arsenate root transport, in contrast to other monocotyledons and dicotyledons. A high percentage (> 50%) of arsenic in the tissues was phytochelatin complexed; however, it is argued that this is a constitutive, rather than an adaptive, mechanism of tolerance.

A single-component multidrug transporter of the major facilitator superfamily is part of a network that protects Escherichia coli from bile salt stress

Resistance to high concentrations of bile salts in the human intestinal tract is vital for the survival of enteric bacteria such as Escherichia coli. Although the tripartite AcrAB-TolC efflux system plays a significant role in this resistance, it is purported that other efflux pumps must also be involved. We provide evidence from a comprehensive suite of experiments performed at two different pH values (7.2 and 6.0) that reflect pH conditions that E. coli may encounter in human gut that MdtM, a single-component multidrug resistance transporter of the major facilitator superfamily, functions in bile salt resistance in E. coli by catalysing secondary active transport of bile salts out of the cell cytoplasm. Furthermore, assays performed on a chromosomal ΔacrB mutant transformed with multicopy plasmid encoding MdtM suggested a functional synergism between the single-component MdtM transporter and the tripartite AcrAB-TolC system that results in a multiplicative effect on resistance. Substrate binding experiments performed on purified MdtM demonstrated that the transporter binds to cholate and deoxycholate with micromolar affinity, and transport assays performed on inverted vesicles confirmed the capacity of MdtM to catalyse electrogenic bile salt/H(+) antiport.

Just a matter of time: Fungi and roots significantly and rapidly aggregate soil over four decades along the Tagliamento River, NE Italy

Fluvial islands are emergent landforms which form at the interface between the permanently inundated areas of the river channel and the more stable areas of the floodplain as a result of interactions between physical river processes, wood and riparian vegetation. These highly dynamical systems are ideal to study soil structure development in the short to medium term, a process in which soil biota and plants play a substantial role. We investigated soil structure development on islands along a 40 year chronosequence within a 3 km island-braided reach of the Tagliamento River, Northeastern Italy. We used several parameters to capture different aspects of the soil structure, and measured biotic (e.g., fungal and plant root parameters) and abiotic (e.g. organic carbon) factors expected to determine the structure. We estimated models relating soil structure to its determinants, and, in order to confer statistical robustness to our results, we explicitly took into account spatial autocorrelation, which is present due to the space for time substitution inherent in the study of chronosequences and may have confounded results of previous studies. We found that, despite the eroding forces from the hydrological and geomorphological dynamics to which the system is subject, all soil structure variables significantly, and in some case greatly increased with site age. We interpret this as a macroscopic proxy for the major direct and indirect binding effects exerted by root variables and extraradical hyphae of arbuscular mycorrhizal fungi (AMF). Key soil structure parameters such as percentage of water stable aggregates (WSA) can double from the time the island landform is initiated (mean WSA = 30%) to the full 40 years (mean WSA = 64%) covered by our chronosequence. The study demonstrates the fundamental role of soil biota and plant roots in aggregating soils even in a system in which intense short to medium term physical disturbances are common.

Pro-fragrant ionic liquids with stable hemiacetal motifs: water-triggered release of fragrances

Stable liquid and solid salts in the form of elusive hemiacetals, appended with fragrant alcohols, have been synthesised as pro-fragrances, and the controlled release of these fragrances, triggered by water, is demonstrated