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Ionic liquids (ILs), solvents composed entirely of paired ions, have been used in a variety of process chemistry and renewable energy applications. Imidazolium-based ILs effectively dissolve biomass and represent a remarkable platform for biomass pretreatment. Although efficient, imidazolium cations are expensive and thus limited in their large-scale industrial deployment. To replace imidazolium-based ILs with those derived from renewable sources, we synthesized a series of tertiary amine-based ILs from aromatic aldehydes derived from lignin and hemicellulose, the major byproducts of lignocellulosic biofuel production. Compositional analysis of switchgrass pretreated with ILs derived from vanillin, p-anisaldehyde, and furfural confirmed their efficacy. Enzymatic hydrolysis of pretreated switchgrass allowed for direct comparison of sugar yields and lignin removal between biomass-derived ILs and 1-ethyl-3-methylimidazolium acetate. Although the rate of cellulose hydrolysis for switchgrass pretreated with biomassderived ILs was slightly slower than that of 1-ethyl-3-methylimidazolium acetate, 90-95% glucose and 70-75% xylose yields were obtained for these samples after 72-h incubation. Molecular modeling was used to compare IL solvent parameters with experimentally obtained compositional analysis data. Effective pretreatment of lignocellulose was further investigated by powder X-ray diffraction and glycome profiling of switchgrass cell walls. These studies showed different cellulose structural changes and differences in hemicellulose epitopes between switchgrass pretreatments with the aforementioned ILs. Our concept of deriving ILs from lignocellulosic biomass shows significant potential for the realization of a "closed-loop" process for future lignocellulosic biorefineries and has far-reaching economic impacts for other IL-based process technology currently using ILs synthesized from petroleum sources. renewable chemicals | bioenergy | lignocellulose conversion | saccharification | green chemistry

We consider BF-type topological field theory coupled to non-dynamical particle and string sources on spacetime manifolds of the form IR 1 × M 3 , where M 3 is a 3-manifold without boundary. Canonical quantization of the theory is carried out in the Hamiltonian formalism and explicit solutions of the Schrödinger equation are obtained. We show that the Hilbert space is finite dimensional and the physical states carry a one-dimensional projective representation of the local gauge symmetries. When M 3 is homologically nontrivial the wavefunctions in addition carry a multi-dimensional projective representation, in terms of the linking matrix of the homology cycles of M 3 , of the discrete group of large gauge transformations. The wavefunctions also carry a one-dimensional representation of the non-trivial linking of the particle trajectories and string surfaces in M 3 . This topological field theory therefore provides a phenomenological generalization of anyons to (3 + 1) dimensions where the holonomies representing fractional statistics arise from the adiabatic transport of particles around strings. We also discuss a duality between large gauge transformations and these linking operations around the homology cycles of M 3 , and show that this canonical quantum field theory provides novel quantum representations of the cohomology of M 3 and its associated motion group. *

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F, Cl and Br contents of tholeiitic volcanic glasses dredged along the Mid-Atlantic Ridge from 53° to 28° N, including the transect over the Azores Plateau, are reported. The halogen variations parallel those of 87 Sr/ 86 Sr, La/Sm or other incompatible elements of varying volatility. The latitudinal halogen variation pattern is not obliterated if only Mg-rich lavas are considered. Variations in extent of low-pressure fractional crystallization or partial melting conditions do not appear to be the primary cause of the halogen variations. Instead, mantle-derived heterogeneities in halogens, with major enrichments in the mantle beneath the Azores, are suggested. The Azores platform is not only a ‘hotspot’ but also a ‘wetspot’, which may explain the unusually intense Azores volcanic activity. The magnitude of the halogen and incompatible element enrichments beneath the Azores appear strongly dependent on the size of these anions and cations, but independent of relative volatility at low pressure. The large anions Cl and Br behave similarly to large cations Rb, Cs and Ba, and the smaller anion F similarly to Sr and P. Processes involving crystal and liquid (fluid and/or melt), CO 2 rather than H 2 O dominated, seem to have produced these largescale mantle heterogeneities. Geochemical ‘anomalies’ beneath the Azores are no longer apparent for coherent element pair ratios of similar ionic size. Values of such ‘unfractionated’ coherent trace element ratios provide an indication of the mantle composition and its nature before fractionation event (s) which produced the inferred isotopic and trace element heterogeneities apparently present beneath the North Atlantic. The relative trace element composition of this precursor mantle does not resemble that of carbonaceous chondrites except for refractory trace element pairs of similar ionic size. It is strongly depleted in halogens, and to a lesser extent in large alkali ions Rb and Cs relative to refractory Ba. These relative depletions are comparable within a factor of 5 to Ganapathy & Anders’s estimates for the bulk Earth, with the exception of Cs. There is also evidence for removal of phosphorus into the iron core during its formation. With the exception of San Miguel, alkali basalts from the Azores Islands appear to have been derived from the same mantle source as tholeiitic basalts from the ridge transect over the Azores Platform but by half as much degree of partial melting. The Azores subaerial basalts seem to have been partly degassed in Cl, Br and F, in decreasing order of intensity. A working model involving metasomatism from release of fluids at phase transformation during convective mantle overturns is proposed to explain the formation of mantle plumes or diapirs enriched in larger relative to smaller halogen and other incompatible trace elements. The model is ad hoc and needs testing. However, any other dynamical model accounting for the 400 -1000 km long gradients in incompatible trace elements, halogens and radiogenic isotopes along the Mid-Atlantic Ridge should, at some stage, require either (1) some variable extent of mixing or (2) differential migration of liquid relative to crystals followed by re-equilibration (or both), as a diffusion controlled mechanism over such large distances is clearly ruled out, given the age of the Earth.