Uncatalysed and potassium-catalysed pyrolysis of the cell-wall constituents of biomass and their model compounds

Cell-wall components (cellulose, hemicellulose (oat spelt xylan), lignin (Organosolv)), and model compounds (levoglucosan (an intermediate product of cellulose decomposition) and chlorogenic acid (structurally similar to lignin polymer units)) have been investigated to probe in detail the influence of potassium on their pyrolysis behaviours as well as their uncatalysed decomposition reaction. Cellulose and lignin were pretreated to remove salts and metals by hydrochloric acid, and this dematerialized sample was impregnated with 1% of potassium as potassium acetate. Levoglucosan, xylan and chlorogenic acid were mixed with CHCOOK to introduce 1% K. Characterisation was performed using thermogravimetric analysis (TGA) and differential thermal analysis (DTA). In addition to the TGA pyrolysis, pyrolysis-gas chromatography-mass spectrometry (PY-GC-MS) analysis was introduced to examine reaction products. Potassium-catalysed pyrolysis has a huge influence on the char formation stage and increases the char yields considerably (from 7.7% for raw cellulose to 27.7% for potassium impregnated cellulose; from 5.7% for raw levoglucosan to 20.8% for levoglucosan with CHCOOK added). Major changes in the pyrolytic decomposition pathways were observed for cellulose, levoglucosan and chlorogenic acid. The results for cellulose and levoglucosan are consistent with a base catalysed route in the presence of the potassium salt which promotes complete decomposition of glucosidic units by a heterolytic mechanism and favours its direct depolymerization and fragmentation to low molecular weight components (e.g. acetic acid, formic acid, glyoxal, hydroxyacetaldehyde and acetol). Base catalysed polymerization reactions increase the char yield. Potassium-catalysed lignin pyrolysis is very significant: the temperature of maximum conversion in pyrolysis shifts to lower temperature by 70 K and catalysed polymerization reactions increase the char yield from 37% to 51%. A similar trend is observed for the model compound, chlorogenic acid. The addition of potassium does not produce a dramatic change in the tar product distribution, although its addition to chlorogenic acid promoted the generation of cyclohexane and phenol derivatives. Postulated thermal decomposition schemes for chlorogenic acid are presented. © 2008 Elsevier B.V. All rights reserved.

Coherence imaging by use of a Newton rings sampling function

We show that, with suitable optics in the arm of a Michelson interferometer, orthogonal galvo-scanning mirrors build a sampling function in the form of Newton rings when the two interferometer arms are matched. Using a low-coherence source, one can obtain transversal depth-resolved images. A fast display procedure using a storage oscilloscope was devised based on this method.

Diabetic retinopathy and blockade of the renin–angiotensin system:new data from the DIRECT study programme

The pathogenesis and medical management of diabetic retinopathy is reviewed. The importance of good control of blood glucose and blood pressure remain key elements in the prevention and treatment of diabetic retinopathy, and a number of specific metabolic pathways have been identified that may be useful additional targets for therapeutic intervention. Trial data, however, aimed specifically to answer the questions of optimum medical management are limited, so the DIRECT study of renin-angiotensin blockade using oral candesartan 32 mg daily is a welcome addition to our knowledge. This arose from the promising improvement of retinopathy outcomes in the EUCLID study of lisinopril in type I diabetes. In DIRECT, 5 years of candesartan treatment in type I diabetes reduced the incidence of retinopathy by two or more steps (EDTRS) in severity by 18% (P = 0.0508) and, in a post hoc analysis, reduced the incidence of retinopathy by three-step progression by 35% (P = 0.034). In type I diabetes patients there was no effect on progression of established retinopathy. In contrast, in type II diabetes, 5 years of candesartan treatment resulted in 34% regression of retinopathy (P ≤0.009). Importantly, an overall significant change towards less-severe retinopathy was noted in both type I and II diabetes (P0.03). Although there is still no absolute proof that these effects were specific to RAS blockade, or just an effect of lower blood pressure, it is reasonable to conclude that candesartan has earned a place in the medical management of diabetic retinopathy, to prevent the problem in type I diabetes and to treat the early stages in type II diabetes. © 2010 Macmillan Publishers Limited All rights reserved.

The use of the lichen genus Rhizocarpon in lichenometric dating with special reference to Holocene glacial events

Lichenometry is one of the most widely used methods of dating the surface age of substrata including rock surfaces, boulders, walls, and archaeological remains and has been particularly important in dating late Holocene glacial events. Yellow-green species of the crustose genus Rhizocarpon have been the most useful lichens in lichenometry because of their low growth rates and longevity. This review describes: (1) the biology of the genus Rhizocarpon, (2) growth rates and longevity, (3) environmental growth effects, (4) methods of estimating lichen age, (5) the methodology of lichenometry, (6) applications to dating glacial events, and (7) future research. Lichenometry depends on many assumptions, most critically that if the lag time before colonisation of a substratum is known and lichen age can be estimated, then a minimum surface age date can be obtained by measuring the size of the largest Rhizocarpon thallus. Lichen age can be estimated by calibrating thallus size against surfaces of known age (‘indirect lichenometry’), by constructing a growth rate-size curve from direct measurement of growth (‘direct lichenometry’), using radio-carbon (RC) dating, or from lichen ‘growth rings’. Future research should include a more rigorous investigation of the assumptions of lichenometry, especially whether the largest thallus present at a site is a good indicator of substratum age, and further studies on the establishment, development, growth, senescence, and mortality of Rhizocarpon lichens.

Estimating direct and indirect effects of foreign direct investment on firm productivity in the presence of interactions between firms

We implement a method to estimate the direct effects of foreign-ownership on foreign firms' productivity and the indirect effects (or spillovers) from the presence of foreign-owned firms on other foreign and domestic firms' productivity in a unifying framework, taking interactions between firms into account. To do so, we relax a fundamental assumption made in empirical studies examining a direct causal effect of foreign ownership on firm productivity, namely that of no interactions between firms. Based on our approach, we are able to combine direct and indirect effects of foreign ownership and calculate the total effect of foreign firms on local productivity. Our results show that all these effects vary with the level of foreign presence within a cluster, an important finding for the academic literature and policy debate on the benefits of attracting foreign owned firms.

Supercritical water gasification of RDF and its components over RuO2/γ-Al2O3 catalyst:new insights into RuO2 catalytic reaction mechanisms

Five samples including a composite refuse derived fuel (RDF) and four combustible components of municipal solid wastes (MSW) have been reacted under supercritical water conditions in a batch reactor. The reactions have been carried out at 450 °C for 60 min reaction time, with or without 20 wt% RuO2/gamma-alumina catalyst. The reactivities of the samples depended on their compositions; with the plastic-rich samples, RDF and mixed waste plastics (MWP), giving similar product yields and compositions, while the biogenic samples including mixed waste wood (MWW) and textile waste (TXT) also gave similar reaction products. The use of the heterogeneous ruthenium-based catalyst gave carbon gasification efficiencies (CGE) of up to 99 wt%, which was up by at least 83% compared to the non-catalytic tests. In the presence of RuO2 catalyst, methane, hydrogen and carbon dioxide became the dominant gas products for all five samples. The higher heating values (HHV) of the gas products increased at least two-fold in the presence of the catalyst compared to non-catalytic tests. Results show that the ruthenium-based catalyst was active in feedstock steam reforming, methanation and possible direct hydrogenolysis of C-C bonds. This work provides new insights into the catalytic mechanisms of RuO2 during SCWG of carbonaceous materials, along with the possibility of producing high yields of methane from MSW fractions.

A note on the propagation of quantized vortex rings through a quantum turbulence tangle:energy transport or energy dissipation?

We investigate quantum vortex ring dynamics at scales smaller than the inter-vortex spacing in quantum turbulence. Through geometrical arguments and high-resolution numerical simulations, we examine the validity of simple estimates for the mean free path and the structure of vortex rings post-reconnection. We find that a large proportion of vortex rings remain coherent objects where approximately 75% of their energy is preserved. This leads us to consider the effectiveness of energy transport in turbulent tangles. Moreover, we show that in low density tangles, appropriate for the ultra-quantum regime, ring emission cannot be ruled out as an important mechanism for energy dissipation. However at higher vortex line densities, typically associated with the quasi-classical regime, loop emission is expected to make a negligible contribution to energy dissipation, even allowing for the fact that our work shows rings can survive multiple reconnection events. Hence the Kelvin wave cascade seems the most plausible mechanism leading to energy dissipation