Testing isotherm models and recovering empirical relationships for adsorption in microporous carbons using virtual carbon models and grand canonical Monte Carlo simulations

Using the plausible model of activated carbon proposed by Harris and co-workers and grand canonical Monte Carlo simulations, we study the applicability of standard methods for describing adsorption data on microporous carbons widely used in adsorption science. Two carbon structures are studied, one with a small distribution of micropores in the range up to 1 nm, and the other with micropores covering a wide range of porosity. For both structures, adsorption isotherms of noble gases (from Ne to Xe), carbon tetrachloride and benzene are simulated. The data obtained are considered in terms of Dubinin-Radushkevich plots. Moreover, for benzene and carbon tetrachloride the temperature invariance of the characteristic curve is also studied. We show that using simulated data some empirical relationships obtained from experiment can be successfully recovered. Next we test the applicability of Dubinin's related models including the Dubinin-Izotova, Dubinin-Radushkevich-Stoeckli, and Jaroniec-Choma equations. The results obtained demonstrate the limits and applications of the models studied in the field of carbon porosity characterization.

Prowess, the Nine Worthies and the Hundred Years War: the Prologues to the Chroniques of Jean Froissart and Enguerrand de Monstrelet

An analysis of the evolution of the image of chivalry in the successive redactions of the Prologue to Froissart's Chroniques, focussing on the figures of the Nine Worthies as models of behaviour for young noblemen. This is then compared and contrasted with the prologue written by his continuator, Enguerrand de Monstrelet, whose work betrays a shift in sensibilities that expresses itself, inter alia, by a near-total absence of the Worthies in his Chronique. Close textual analysis suggests that the two choniclers shared a comparable sense of disillusion, though expressed in different ways.

Determination of Holocene cave temperatures from Kr and Xe concentrations in stalagmite fluid inclusions

From the concentrations of dissolved atmospheric noble gases in water, a so-called “noble gas temperature” (NGT) can be determined that corresponds to the temperature of the water when it was last in contact with the atmosphere. Here we demonstrate that the NGT concept is applicable to water inclusions in cave stalagmites, and yields NGTs that are in good agreement with the ambient air temperatures in the caves. We analysed samples from two Holocene and one undated stalagmite. The three stalagmites originate from three caves located in different climatic regions having modern mean annual air temperatures of 27 °C, 12 °C and 8 °C, respectively. In about half of the samples analysed Kr and Xe concentrations originated entirely from the two well-defined noble gas components air-saturated water and atmospheric air, which allowed NGTs to be determined successfully from Kr and Xe concentrations. One stalagmite seems to be particularly suitable for NGT determination, as almost all of its samples yielded the modern cave temperature. Notably, this stalagmite contains a high proportion of primary water inclusions, which seem to preserve the temperature-dependent signature well in their Kr and Xe concentrations. In future work on stalagmites detailed microscopic inspection of the fluid inclusions prior to noble gas analysis is therefore likely to be crucial in increasing the number of successful NGT determinations.

Case study part 1: how to calculate appropriate deterministic long-term toxicity to exposure rates (TERs) for birds and mammals

In the European Union, first-tier assessment of the long-term risk to birds and mammals from pesticides is based on calculation of a deterministic long-term toxicity/exposure ratio(TERlt). The ratio is developed from generic herbivores and insectivores and applied to all species. This paper describes two case studies that implement proposed improvements to the way long-term risk is assessed. These refined methods require calculation of a TER for each of five identified phases of reproduction (phase-specific TERs) and use of adjusted No Observed Effect Levels (NOELs)to incorporate variation in species sensitivity to pesticides. They also involve progressive refinement of the exposure estimate so that it applies to particular species, rather than generic indicators, and relates spraying date to onset of reproduction. The effect of using these new methods on the assessment of risk is described. Each refinement did not necessarily alter the calculated TER value in a way that was either predictable or consistent across both case studies. However, use of adjusted NOELs always reduced TERs, and relating spraying date to onset of reproduction increased most phase-specific TERs. The case studies suggested that the current first-tier TERlt assessment may underestimate risk in some circumstances and that phase-specific assessments can help identify appropriate risk-reduction measures. The way in which deterministic phase-specific assessments can currently be implemented to enhance first-tier assessment is outlined.

Case study part 2: probabilistic modelling of long-term effects of pesticides on individual breeding success in birds and mammals

Abstract: Long-term exposure of skylarks to a fictitious insecticide and of wood mice to a fictitious fungicide were modelled probabilistically in a Monte Carlo simulation. Within the same simulation the consequences of exposure to pesticides on reproductive success were modelled using the toxicity-exposure-linking rules developed by R.S. Bennet et al. (2005) and the interspecies extrapolation factors suggested by R. Luttik et al.(2005). We built models to reflect a range of scenarios and as a result were able to show how exposure to pesticide might alter the number of individuals engaged in any given phase of the breeding cycle at any given time and predict the numbers of new adults at the season’s end.

Chaucer's presence in songes and sonettes

In an elegy to Wyatt published in Tottel’s Miscellany, Surrey claims that Wyatt ‘reft Chaucer the glory of his wit’. This statement, which both lauds and resists Chaucer, is a microcosm of the way Chaucer is treated throughout the Miscellany. In examining the collection’s paradoxical attitude to Chaucer, this essay focuses particularly on the Squire’s Tale, the Franklin’s Tale, Anelida and Arcite, the Legend of Good Women, and several short lyrics. In its interest in courtly love poetry and Petrarch, the Miscellany follows a trajectory in English poetry set by Chaucer. Its courtly verse is saturated with words, phrases, and tropes from his poetry. Rhyme royal, which he introduced into English poetry, is widely used. The Canterbury Tales has been fully assimilated and can be referred to allusively with the same confidence of the audience’s knowledge as is the case when referring to classical myth; in Wyatt’s ‘Myne owne Jhon Poins’, the speaker, disclaiming deceitfulness, says that he cannot ‘say that Pan/ Passeth Appollo in musike manifold:/ Praise syr Topas for a noble tale,/ And scorne the story that the knight tolde’ (lines 48-50). However, Chaucer’s poetry is also downplayed and contested in the Miscellany. ‘Truth’, the only poem of his which appears in the volume, is disingenuously placed in the ‘Uncertain Authors’ section. In addition, some of the most important elements of his work are strongly resisted in the Miscellany, either ignored, dismissed or challenged. These elements include Chaucer’s interest in variety of voice, his sympathetic engagement with women, particularly wronged women, and his interest in female speech and particularly female complaint. The Miscellany, by contrast, is dominated by male-voiced lyrics preoccupied with the pain inflicted on the lover by a lady who is frequently unfeeling, cruel, or faithless. Chaucer’s frequent focus on the cynical seduction and betrayal of female by male is reversed in the Miscellany, and the language and metaphors he uses to express male cruelty (e.g. the word ‘newfangleness’ and images of hooks, nets and traps) are usurped to describe the lady’s cruelty to the suffering lover. On occasion, poems in the Miscellany challenge specific Chaucerian texts; ‘On His Love Named White’ throws down a gauntlet to The Book of the Duchess, while two of Surrey’s poems implicitly take issue with the female falcon’s voice in the Squire’s Tale, giving the deceitful tercelet the opportunity to shout down the falcon’s charges. The essay thus shows that in many respects Tottel’s Miscellany is only superficially Chaucerian, and that it both passively and actively takes issue with Chaucer’s work.

Tropical climates at the Last Glacial Maximum: a new synthesis of terrestrial palaeoclimate data. I. Vegetation, lake-levels and geochemistry.

Palaeodata in synthesis form are needed as benchmarks for the Palaeoclimate Modelling Intercomparison Project (PMIP). Advances since the last synthesis of terrestrial palaeodata from the last glacial maximum (LGM) call for a new evaluation, especially of data from the tropics. Here pollen, plant-macrofossil, lake-level, noble gas (from groundwater) and δ18O (from speleothems) data are compiled for 18±2 ka (14C), 32 °N–33 °S. The reliability of the data was evaluated using explicit criteria and some types of data were re-analysed using consistent methods in order to derive a set of mutually consistent palaeoclimate estimates of mean temperature of the coldest month (MTCO), mean annual temperature (MAT), plant available moisture (PAM) and runoff (P-E). Cold-month temperature (MAT) anomalies from plant data range from −1 to −2 K near sea level in Indonesia and the S Pacific, through −6 to −8 K at many high-elevation sites to −8 to −15 K in S China and the SE USA. MAT anomalies from groundwater or speleothems seem more uniform (−4 to −6 K), but the data are as yet sparse; a clear divergence between MAT and cold-month estimates from the same region is seen only in the SE USA, where cold-air advection is expected to have enhanced cooling in winter. Regression of all cold-month anomalies against site elevation yielded an estimated average cooling of −2.5 to −3 K at modern sea level, increasing to ≈−6 K by 3000 m. However, Neotropical sites showed larger than the average sea-level cooling (−5 to −6 K) and a non-significant elevation effect, whereas W and S Pacific sites showed much less sea-level cooling (−1 K) and a stronger elevation effect. These findings support the inference that tropical sea-surface temperatures (SSTs) were lower than the CLIMAP estimates, but they limit the plausible average tropical sea-surface cooling, and they support the existence of CLIMAP-like geographic patterns in SST anomalies. Trends of PAM and lake levels indicate wet LGM conditions in the W USA, and at the highest elevations, with generally dry conditions elsewhere. These results suggest a colder-than-present ocean surface producing a weaker hydrological cycle, more arid continents, and arguably steeper-than-present terrestrial lapse rates. Such linkages are supported by recent observations on freezing-level height and tropical SSTs; moreover, simulations of “greenhouse” and LGM climates point to several possible feedback processes by which low-level temperature anomalies might be amplified aloft.