Voltammetric characterization of the ferrocene vertical bar ferrocenium and cobaltocenium vertical bar cobaltocene redox couples in RTILs

Ferrocene, Fc, and cobaltocenium hexafluorophosphate, CcPF(6), have been recommended for use as internal reference redox couples in room-temperature ionic liquids (RTILs), as well as in more conventional aprotic solvents. In this study, the electrochemical behavior of Fc and CcPF(6) is reported in eight commonly used RTILs; [C(2)mim][NTf2], [C(4)mim][NTf2], [C(4)mim][BF4], [C(4)mim][PF6], [C(4)mim][OTf], [C(4)mim][NO3], [C(4)mpyrr][NTf2], and [P-14,P-6.6,P-6][FAP], where [C(n)mim](+) = 1-butyl-3-methylimidazolium, [NTf2](-) = bis(trifluoromethylsulfonyl)imide, [BF4](-) = tetrafluoroborate, [PF6](-) = hexafluorophosphate, [OTf](-) = trifluoromethylsulfonate, [NO3](-) = nitrate, [C(4)mpyrr](+) = N-butyl-N-methylpyrrolidinium, [P-14,P-6,P-6,P-6](+) = tris(ri-hexyl)-tetradecylphosphonium and [FAP](-) = trifluorotris(pentafluoroethyl)phosphate, over a range of concentrations and temperatures. Solubilities and diffusion coefficients, D, of both the charged and neutral species were determined using double potential-step chronoamperometry, and CcPF(6) (36.5-450.0 mM) was found to be Much more Soluble than Fc (27.5-101.8 mM). It was observed that classical Stokes-Einstein diffusional behavior applies for Fc and CcPF(6) in all eight RTILs. Diffusion coefficients of Fc and CcPF(6) were calculated at a range of temperatures, and activation energies calculated. It was also determined that D for Fc and CcPF(6) does not change significantly with concentration. This supports the use of both Fe and CcPF(6) to provide a well-characterized and model redox couple for use as a voltammetric internal potential reference in RTILs contrary to previous literature reports in the former case.

Electrochemical kinetics of Ag vertical bar Ag+ and TMPD vertical bar TMPD+center dot in the room-temperature ionic liquid [C(4)mpyrr][NTf2]; toward optimizing reference electrodes for voltammetry in RTILs

The voltammetry and kinetics of the Ag vertical bar Ag+ system (commonly used as a reference electrode material in both protic/aprotic and RTIL solvents) was studied in the room-temperature ionic liquid N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [C(4)mpyrr][NTf2] on a 10 mu m diameter Pt electrode. For the three silver salts investigated (AgOTf, AgNTf2, and AgNO3, where OTf- = trifluoromethanesulfonate, NTf2- = bis(trifluoromethylsulfonyl)imide, and NO3- = nitrate), the voltammetry gave rise to a redox couple characteristic of a

Postglacial vegetation and climate dynamics in the Seymour-Belize Inlet Complex, central coastal British Columbia, Canada: palynological evidence from Tiny Lake.

A pollen-based study from Tiny Lake in the Seymour-Belize Inlet Complex of central coastal British Columbia, Canada, permits an evaluation of the dynamic response of coastal temperate rainforests to postglacial climate change. Open Pinus parklands grew at the site during the early Lateglacial when the climate was cool and dry, but more humid conditions in the later phases of the Lateglacial permitted mesophytic conifers to colonise the region. Early Holocene conditions were warmer than present and a successional mosaic of Tsuga heterophylla and Alnus occurred at Tiny Lake. Climate cooling and moistening at 8740?±?70 14C a BP initiated the development of closed, late successional T. heterophylla–Cupressaceae forests, which achieved modern character after 6860?±?50 14C a BP, when a temperate and very wet climate became established. The onset of early Holocene climate cooling and moistening at Tiny Lake may have preceded change at more southern locations, including within the Seymour-Belize Inlet Complex, on a meso- to synoptic scale. This would suggest that an early Holocene intensification of the Aleutian Low pressure system was an important influence on forest dynamics in the Seymour-Belize Inlet Complex and that the study region was located near the southern extent of immediate influence of this semi-permanent air mass.

Investigating the Mechanism and Electrode Kinetics of the Oxygen vertical bar Superoxide (O-2 vertical bar O-2(center dot-)) Couple in Various Room-Temperature Ionic Liquids at Gold and Platinum Electrodes in the Temperature Range 298-318 K

The reduction of oxygen was studied over a range of temperatures (298-318 K) in n-hexyltriethylammonium bis(trifluoromethanesulfonyl)imide, [N-6,N-2,N-2,N-2][NTf2], and 1-butyl-2,3-methylimidazolium bis(trifluoromethanesulfonyl)imide, [C(4)dmim][NTf2] on both gold and platinum microdisk electrodes, and the mechanism and electrode kinetics of the reaction investigated. Three different models were used to simulate the CVs, based on a simple electron transfer ('E'), an electron transfer coupled with a reversible homogeneous chemical step ('ECrev') and an electron transfer followed by adsorption of the reduction product ('EC(ads)'), and where appropriate, best fit parameters deduced, including the heterogeneous rate constant, formal electrode potential, transfer coefficient, and homogeneous rate constants for the ECrev mechanism, and adsorption/desorption rate constants for the EC(ads) mechanism. It was concluded from the good simulation fits on gold that a simple E process operates for the reduction of oxygen in [N-6,N-2,N-2,N-2][NTf2], and an ECrev process for [C(4)dmim][NTf2], with the chemical step involving the reversible formation of the O-2(center dot-)center dot center dot center dot [C(4)dmim](+) ion-pair. The E mechanism was found to loosely describe the reduction of oxygen in [N-6,N-2,N-2,N-2][NTf2] on platinum as the simulation fits were reasonable although not perfect, especially for the reverse wave. The electrochemical kinetics are slower on Pt, and observed broadening of the oxidation peak is likely due to the adsorption of superoxide on the electrode surface in a process more complex than simple Langmuirian. In [C(4)dmim][NTf2] the O-2(center dot-) predominantly ion-pairs with the solvent rather than adsorbs on the surface, and an ECrev quantitatively describes the reduction of oxygen on Pt also.

Vegetation and climate c. 12 300-9000 cal. yr BP at Andoya, NW Norway

Owing to proximity of the North Atlantic Stream and the shelf, the And circle divide ya biota are assumed to have responded rapidly to climatic changes taking place after the Weichselian glaciation. Palynological, macrofossil, loss-on-ignition, tephra and C-14 data from three sites at the northern part of the island of And circle divide ya were studied. The period 12 300-11 950 cal. yr BP was characterized by polar desert vegetation, and 11 950-11 050 cal. yr BP by a moisture-demanding predominantly low-arctic Oxyria vegetation. During the period 11 050-10 650 cal. yr BP, there was a climatic amelioration towards a sub-arctic climate and heaths dominated by Empetrum. After 10 650 cal. yr BP the Oxyria vegetation disappeared. As early as about 10 800 cal. yr BP the bryozoan Cristatella mucedo indicated a climate sufficient for Betula woodland. However, tree birch did not establish until 10 420-10 250 cal. yr BP, indicating a time-lag for the formation of Betula ecotypes adapted to the oceanic climate of And circle divide ya. From about 10 150 to 9400 cal. yr BP the summers were dry and warm. There was a change towards moister, though comparatively warm, climatic conditions about 9400 cal. yr BP. The present data are compared with evidence from marine sediments and the deglaciation history in the region. It is suggested that during most of the period 11 500-10 250 cal. yr BP a similar situation as in present southern Greenland existed, with birch woodland in the inner fjords near the ice sheet and low-arctic heath vegetation along the outer coast.

Subwavelength resolution for horizontal and vertical polarization by coupled arrays of oblate nanoellipsoids

A structure comprising a coupled pair of two-dimensional arrays of oblate plasmonic nanoellipsoids in a dielectric host medium is proposed as a superlens in the optical domain for both horizontal and vertical polarizations. By means of simulations it is demonstrated that a structure formed by silver nanoellipsoids is capable of restoring subwavelength features of the object for both polarizations at distances larger than half wavelength. The bandwidth of subwavelength resolution is in all cases very large (above 13%). (C) 2009 Optical Society of America

Efficacy of sod removal in regenerating fen vegetation for the conservation of the marsh fritillary butterfly Euphydryas aurinia, Montiaghs Moss Nature Reserve, County Antrim, Northern Ireland.

The efficacy of ‘sod removal’ as a fenland restoration technique was tested using an experimental approach at Montiaghs Moss Nature Reserve, Northern Ireland, from 2006 to 2008. The site suffered from rank growth of purple moor-grass Molinia caerulea which was out-competing herbaceous species. Soil was removed up to a depth of 15 cm completely denuding vegetation in the experimental plot exposing bare peat. By July 2007, 15.2% of sod-removal areas were revegetated; by October 2008 cover had risen to 64.6%. Of this cover, purple moor-grass accounted for only 9-11% compared to 78- 79% on control plots. Cover of other rank-forming grass species was also significantly reduced. Sod removal significantly increased the cover of species characteristic of fenlands including sedges Carex spp., rushes Juncus spp., marsh pennywort Hydrocotyle vulgaris and lesser spearwort Ranunculus flammula. It seems likely that sod removal, which lowered the surface of the peat, restored minerotrophic conditions and exposed the historical seed bank stimulating regeneration of some fenland specialists and pioneer species; this resulted in significantly higher species richness on sod removal plots than control plots two years after treatment. There was no demonstrable effect of sod removal on abundance of devil’s-bit scabious Succisa pratensis, the larval food plant of the Annex II listed marsh fritillary butterfly Euphydryas aurinia. We recommend that consideration should be given to artificially seeding devil’s-bit scabious soon after sod removal treatment to promote early recolonisation and to increase plant abundance on the site.

Computer simulations of seasonal outbreak and diurnal vertical migration of cyanobacteria

Algal blooms caused by cyanobacteria are characterized by two features with different time scales: one is seasonal outbreak and collapse of a bloom and the other is diurnal vertical migration. Our two-component mathematical model can simulate both phenomena, in which the state variables are nutrients and cyanobacteria. The model is a set of one-dimensional reaction-advection-diffusion equations, and temporal changes of these two variables are regulated by the following five factors: (1) annual variation of light intensity, (2) diurnal variation of light intensity, (3) annual variation of water temperature, (4) thermal stratification within a water column and (5) the buoyancy regulation mechanism. The seasonal change of cyanobacteria biomass is mainly controlled by factors, (1), (3) and (4), among which annual variations of light intensity and water temperature directly affect the maximum growth rate of cyanobacteria. The latter also contributes to formation of the thermocline during the summer season. Thermal stratification causes a reduction in vertical diffusion and largely prevents mixing of both nutrients and cyanobacteria between the epilimnion and the hypolimnion. Meanwhile, the other two factors, (2) and (5), play a significant role in diurnal vertical migration of cyanobacteria. A key mechanism of vertical migration is buoyancy regulation due to gas-vesicle synthesis and ballast formation, by which a quick reversal between floating and sinking becomes possible within a water column. The mechanism of bloom formation controlled by these five factors is integrated into the one-dimensional model consisting of two reaction-advection-diffusion equations.

Weakly nonlinear vertical dust grain oscillations in dusty plasma crystals in the presence of a magnetic field

The weakly nonlinear regime of transverse paramagnetic dust grain oscillations in dusty (complex) plasma crystals is discussed. The nonlinearity, which is related to the sheath electric/magnetic field(s) and to the intergrain (electrostatic/magnetic dipole) interactions, is shown to lead to the generation of phase harmonics and, in the case of propagating transverse dust-lattice modes, to the modulational instability of the carrier wave due to self-interaction. The stability profile depends explicitly on the form of the electric and magnetic fields in the plasma sheath. The long term evolution of the modulated wave packet, which is described by a nonlinear Schrodinger-type equation, may lead to propagating localized envelope structures whose exact forms are presented and discussed. Explicit suggestions for experimental investigations are put forward. (C) 2004 American Institute of Physics.

Discrete breather modes associated with vertical dust grain oscillations in dusty plasma crystals

Accounting for the lattice discreteness and the sheath electric field nonlinearity in dusty plasma crystals, it is demonstrated that highly localized structures (discrete breathers) involving vertical (transverse, off-plane) oscillations of charged dust grains may exist in a dust lattice. These structures correspond to either extremely localized bright breather excitations (pulses) or dark excitations composed of dips/voids. Explicit criteria for selecting different breather modes are presented. (C) 2005 American Institute of Physics.

The vegetation and climate history of the last glacial cycle in a new pollen record from Lake Fimon (southern Alpine foreland, N-Italy)

The sediments of Like Fimon N Italy contain the first continuous archive of the Late Pleistocene environmental and climate history of the southern Alpine foreland We present here the detailed palynological record of the interval between Termination II and the List Glacial Maximum The age-depth model is obtained by radiocarbon dating in the uppermost part of the record Downward we con elated major forest expansion and contraction events to isotopic events in the Greenland Ice core records via a stepping-stone approach involving intermediate correlation to isotopic events dated by TIMS U/Th in Alpine and Apennine stalagmites and to pollen records from mime cores of the Iberian margin Modelled ages obtained by Bayesian analysis of deposition are thoroughly consistent with actual ages with maximum offset of +/- 1700 years Sharp expansion of broad-leaved temperate forest and of sudden water table rise mark the onset of the Last Interglacial after a treeless steppe phase at the end of penultimate glaciation This event is actually a two-step process which matches the two step rise observed in the isotopic record of the nearby Antro del Corchia stalagmite respectively dated to 132 5 +/- 2 5 and 129 +/- 1 5 ka At the interglacial decline mixed oak forests were replaced by oceanic mixed forests the latter persisting further for 7 ka till the end of the Eemian succession Warm-temperate woody species are still abundant at the Eemian end corroborating a steep gradient between central Europe and the Alpine divide at the inception of the last glacial After a stadial phase marked by moderate forest decline a new expansion of warm broad leaved forests interrupted by minor events and followed by mixed oceanic forests can be identified with the north-alpine Saint Germain I The spread of beech during the oceanic phase is a valuable circumalpine marker The subsequent stadial-interstadial succession lacking the telocratic oceanic phase is also consistent with the evidence at the north alpine foreland The Middle Wurmian (full glacial) is marked by persistence of mixed forests dominated by conifers but with significant lime and other broad leaved species A major Arboreal Pollen decrease is observed at modelled age of 38 7 +/- 0 5 ka (larch expansion and last occurrence of lime) which his been related to Heinrich Event 4 The evidence of afforestation persisting south of the Alps throughout most of MIS 3 contrasts with a boreal and continental landscape known for the northern alpine foreland pointing to a sharp rainfall boundary at the Alpine divide and to southern air circulation This is in agreement with the Alpine paleoglaciological record and is supported by the pressure and rainfall patterns designed by mesoscale paleoclimate simulations Strenghtening the continental high pressure during the full glacial triggered cyclogenesis in the middle latitude eastern Europe and orographic rainfall in the eastern Alps and the Balkanic mountains thus allowing forests development at current sea level altitudes (C) 2010 Elsevier Ltd All rights reserved

The pace of Holocene vegetation change - testing for synchronous developments

Mid to high latitude forest ecosystems have undergone several major compositional changes during the Holocene. The temporal and spatial patterns of these vegetation changes hold potential information to their causes and triggers. Here we test the hypothesis that the timing of vegetation change was synchronous on a sub-continental scale, which implies a common trigger or a step-like change in climate parameters. Pollen diagrams from selected European regions were statistically divided into assemblage zones and the temporal pattern of the zone boundaries analysed. The results show that the temporal pattern of vegetation change was significantly different from random. Times of change cluster around8.2, 4.8, 3.7, and 1.2 ka, while times of higher than average stability were found around 2.1 and 5.1 ka.Compositional changes linked to the expansion of Corylus avellana and Alnus glutinosa centre around 10.6 and 9.5 ka, respectively. A climatic trigger initiating these changes may have occurred 0.5 to 1 ka earlier, respectively. The synchronous expansion of C. avellana and A. glutinosa exemplify that dispersal is not necessarily followed by population expansion. The partly synchronous, partly random expansion of A. glutinosa in adjacent European regions exemplifies that sudden synchronous population expansions are not species specific traits but vary regionally.