Electrochemistry in Room-Temperature Ionic Liquids: Potential Windows at Mercury Electrodes

The cathodic and anodic: potential limit of eleven different ionic liquids were determined at a mercury hemisphere electrode. Ionic liquids containing the phosphonium cation (tri(n-hexyl)tetradecylphosphonium, [P-14.6,P-6.6](+)) give the largest potential window, especially When Coupled to a trifluorotris(pentafluoroethyl)- [FAP](-). or bis(trifluoromethanesulfonyl)imide, [NTf2](-), anion.

Electrochemical Determination of Manganese Solubility in Mercury via Amalgamation and Stripping in the Room Temperature Ionic Liquid n-Hexyltriethylammonium Bis(trifluoromethanesulfonyl)imide, [N-6,N-2,N-2,N-2][NTf2]

The solubility of manganese in mercury was determined electrochemically via amalgamation and stripping in the room temperature ionic liquid n-hexyltriethylammonium bis(trifluoromethanesulfonyl)imide, [N-6,N-2,N-2,N-2][NTf2]. A hemispherical mercury electrode was made by electrodepositing mercury onto a planar platinum microelectrode. Cyclic voltammetry of Mn2+ in [N-6,N-2,N-2,N-2][NTf2] at the mercury microhemisphere electrode was investigated at temperatures of 298, 303 and 313 K. The solubility of Mn in Hg was determined on the basis of the charge under the reduction peak (Mn2+ --> Mn-0) and the corresponding reoxidation.

Bis(trifluoromethyl)mercury(II) complexes with purine and 3,5-dimethyl-4 '-amino-triazole as ligands, [Hg(CF3)(2)(Pur)](4) and [Hg(CF3)(2)(Dat)](2)

Colourless single crystals of [Hg(CF3)(2)(Pur)](4) and [Hg(CF3)(2)(Dat)](2) were obtained from aqueous and etheric solutions of the respective components Purine, (imidazo[4,5-d]pyrimidine, Pur), 3,5-dimethyl-4 '-amino-triazole (Dat) and bis(trifluoromethyl)mercury(II), Hg(CF3)(2). [Hg(CF3)(2)(Pur)](4) crystallizes with the tetragonal system (P-4, Z = 8, a = 1486.8(2), c = 1026.2(l) pm, R-all = 0.0657) with tetrameric molecules consisting of four purine molecules bridged by slightly bent Hg(CF3)2 molecules forming a cage with the CF3 ligands surrounding this cage. The two modifications of [Hg(Dat)(CF3)2]2 (1: 170 K, triclinic, P-1, Z = 2, a 814.9(2), b = 845.4(2), c = 968.4(3) pm, alpha = 106.55(2)degrees, beta= 103.41(2)degrees, gamma = 110.79(2)degrees, R-all = 0.1189; II: monoclinic, P2(1)/c, Z = 8, a = 879.8(2), b = 1731.0(3), c = 1593.9(3) pm, beta = 106.89(2)degrees, R-all = 0.1199) both contain dimeric molecules that are stacked parallel to one crystal axis to strands which are arranged in a parallel fashion in I and rotated against each other in 11 by 110 degrees. In both, the tetrameric [Hg(CF3)(2)(Pur)](4) and the dimeric [Hg(CF3)(2)(Dat)](2) the Hg(CF3)(2) molecules are slightly bent (around 167 and 170 degrees) and rather weakly attached to the N-donor ligands Pur and Dat with Hg-N distances around 272 pm, although in both cases the Hg atoms bridge between two ligand molecules.

Affinity of divalent mercury towards nitrogen donor ligands

As with gold, relativistic effects are important in the chemistry of mercury Together with the closed-shell d(10) configuration of Hg2+ they account for the special bonding schemes as preferred linear coordination with highly covalent contributions to chemical bonding or special affinities to nitrogen and sulfur that are so prominent in mercuric chemistry This research report summarizes recent research on coordination compounds with halogen, oxygen and, especially, nitrogen as direct bonding partners of di-valent mercury and their competition with each other. In a rather systematic way N-donor ligands with one, two and more than two nitrogen atoms have been inspected in order to elucidate the influences that lead to the special bonding schemes of Hg-II-N compounds.

Ammonium mercury(II) dichloride nitrate, (NH4)(2)HgCl2(NO3)(2)

The title compound, (NH4)(2)HgCl2 (NO3)(2), is a double salt of HgCl2 and NH4NO3 and can also be written as `HgCl2.2NH(4)NO(3)'. The structure contains HgCl2 units which are connected by nitrate groups, through long links of ca. 2.90 Angstrom, to give chains running along [010]. All atoms apart from the two oxygen atoms are located on a mirror plane perpendicular to the b axis. The coordination around mercury is a distorted hexagonal bipyramid.

Abatement and Allocation in the Pilot Phase of the EU ETS

We use historical industrial emissions data to assess the level of abatement and over-allocation that took place across European countries during the pilot phase (2005–2007) of the European Union Emission Trading Scheme. Using a dynamic panel data model, we estimate the counter factual (business-as-usual) emissions scenario for EU member states. Comparing this baseline to allocated and verified emissions, we find that both over-allocation and abatement occurred, along with under-allocation and emissions inflation. Over the three trading years of the pilot phase we find over-allocation of approximately 280 million EUAs and total abatement of 247 Mt CO2. However, we calculate that emissions inflation of approximately 73 Mt CO2 also occurred, possibly due to uncertainty about future policy design features.

Abatement technologies for road surface run-off

Heavy metals, primarily zinc, copper, lead, and chromium, and Polycyclic Aromatic Hydrocarbons (PAHs) are the main hazardous constituents of road runoff. The main sources of these contaminants are vehicle emission, mostly through wear and leakage, although erosion of the road surface and de-icing salts are also recognised pollution sources. The bioavailability of these toxic compounds, and more importantly their potential biomagnification along food chains, could affect aquatic communities persistently exposed to road runoff. Several internationally approved abatement technologies are available for the management of road runoff on new motorway schemes. Recent studies conducted in Cork and Dublin, Ireland demonstrated the efficacy of infiltration trenches as abatement technologies in the removal of both heavy metals and PAHs prior to discharge; the technology was however inefficient in mitigating first flush events. Gully traps with sedimentation chambers, another technology investigated, demonstrated to have a substantially lower removal potential but appeared to be more effective in attenuating surges of contaminants attributed to first flush events. Consequently the employment of combined abatement techniques could efficiently minimise deviations from required effluent concentrations. The studies determined a relatively stationary accumulation of heavy metals and PAHs in sediments close to the point of discharge with a rapid decline in concentration in nearby downstream sediments (<50m). Further, Microtox® Solid Phase testing reported a negligible impact on assemblages exposed to contaminated sediments for all sites investigated. This paper describes pollutant loading from road runoff and mitigation measures from a freshwater deterioration in a water quality perspective. The results and analysis of field samples collected adjacent to a number of roads and motorways in Ireland is also presented. Finally sustainable drainage systems, abatement techniques and technologies available for onsite treatment of runoff are presented to improve and mitigate impacts of vehicular transport on the environment.

Abatement of nitrous oxide over natural and iron modified natural zeolites

The natural zeolite obtained from the Sivas-Yavu region in Turkey and iron modified forms were studied for the decomposition of N2O and selective catalytic reduction of N2O with NH3. The natural and iron modified zeolites were characterised by XRD, SEM, H-2-TPR, NH3-TPD and low temperature nitrogen sorption. The effect iron loading, precursor and valency on the catalytic performance of catalysts were studied. The catalytic activity of the zeolites increased up to about 7.0 wt.% Fe. Above this value, the activity decreased as a result of a reduction in the surface area and pore volume of the zeolite. The highest catalytic activity was observed using catalysts prepared with FeCl2 due to the formation of more reducible iron species in the zeolites. When FeSO4 was used as the iron precursor, sulphate remained on the surface even after extensive washing resulting in a decrease in the N2O decomposition activity and a shift the N2O reduction temperature to higher values. Since the natural and iron exchanged natural zeolites prepared using FeCl2 have comparable activity with synthetic zeolites, the offer a promising alternative catalyst for the abatement of N2O, particularly for the selective reduction of N2O with NH3. (C) 2011 Elsevier B.V. All rights reserved.

The molecular form of mercury in biota:identification of novel mercury peptide complexes in plants

The molecular structure of a variety of novel mercury-phytochelatin complexes was evidenced in rice plants exposed to inorganic mercury (Hg2+) using RP-HPLC with simultaneous detection via ICP-MS and ES-MS.

Investigation into mercury bound to biothiols:structural identification using ESI-ion-trap MS and introduction of a method for their HPLC separation with simultaneous detection by ICP-MS and ESI-MS

Mercury in plants or animal tissue is supposed to occur in the form of complexes formed with biologically relevant thiols (biothiols), rather than as free cation. We describe a technique for the separation and molecular identification of mercury and methylmercury complexes derived from their reactions with cysteine (Cys) and glutathione (GS): Hg(Cys)(2), Hg(GS)(2), MeHgCys, MeHgGS. Complexes were characterised by electrospray mass spectrometry (MS) equipped with an ion trap and the fragmentation pattern of MeHgCys was explained by using MP2 and B3LYP calculations, showing the importance of mercury-amine interactions in the gas phase. Chromatographic baseline separation was performed within 10 min with formic acid as the mobile phase on a reversed-phase column. Detection was done by online simultaneous coupling of ES-MS and inductively coupled plasma MS. When the mercury complexes were spiked in real samples (plant extracts), no perturbation of the separation and detection conditions was observed, suggesting that this method is capable of detecting mercury biothiol complexes in plants.