Unusual isotope effect in the reaction of chlorosilylene with trimethylsilane-1-d: Absolute rate studies and quantum chemical and Rice–Ramsperger–Kassel–Marcus calculations provide strong evidence for the involvement of an intermediate complex

Time-resolved studies of chlorosilylene, ClSiH, generated by the 193 nm laser flash photolysis of 1-chloro-1- silacyclopent-3-ene, have been carried out to obtain rate constants for its bimolecular reaction with trimethylsilane-1-d, Me3SiD, in the gas phase. The reaction was studied at total pressures up to 100 Torr (with and without added SF6) over the temperature range of 295−407 K. The rate constants were found to be pressure independent and gave the following Arrhenius equation: log[(k/(cm3 molecule−1 s−1)] = (−13.22 ± 0.15) + [(13.20 ± 1.00) kJ mol−1]/(RT ln 10). When compared with previously published kinetic data for the reaction of ClSiH with Me3SiH, kinetic isotope effects, kD/kH, in the range from 7.4 (297 K) to 6.4 (407 K) were obtained. These far exceed values of 0.4−0.5 estimated for a single-step insertion process. Quantum chemical calculations (G3MP2B3 level) confirm not only the involvement of an intermediate complex, but also the existence of a low-energy internal isomerization pathway which can scramble the D and H atom labels. By means of Rice−Ramsperger−Kassel−Marcus modeling and a necessary (but small) refinement of the energy surface, we have shown that this mechanism can reproduce closely the experimental isotope effects. These findings provide the first experimental evidence for the isomerization pathway and thereby offer the most concrete evidence to date for the existence of intermediate complexes in the insertion reactions of silylenes.

Oxygen isotope ratios in the shell of Mytilus edulis: archives of glacier meltwater in Greenland?

Melting of the Greenland Ice Sheet (GrIS) is accelerating and will contribute significantly to global sea level rise during the 21st century. Instrumental data on GrIS melting only cover the last few decades, and proxy data extending our knowledge into the past are vital for validating models predicting the influence of ongoing climate change. We investigated a potential meltwater proxy in Godthåbsfjord (West Greenland), where glacier meltwater causes seasonal excursions with lower oxygen isotope water (δ18Ow) values and salinity. The blue mussel (Mytilus edulis) potentially records these variations, because it precipitates its shell calcite in oxygen isotopic equilibrium with ambient seawater. As M. edulis shells are known to occur in raised shorelines and archaeological shell middens from previous Holocene warm periods, this species may be ideal in reconstructing past meltwater dynamics. We investigate its potential as a palaeo-meltwater proxy. First, we confirmed that M. edulis shell calcite oxygen isotope (δ18Oc) values are in equilibrium with ambient water and generally reflect meltwater conditions. Subsequently we investigated if this species recorded the full range of δ18Ow values occurring during the years 2007 to 2010. Results show that δ18Ow values were not recorded at very low salinities (< ~ 19), because the mussels appear to cease growing. This implies that Mytilus edulis δ18Oc values are suitable in reconstructing past meltwater amounts in most cases, but care has to be taken that shells are collected not too close to a glacier, but rather in the mid-region or mouth of the fjord. The focus of future research will expand on the geographical and temporal range of the shell measurements by sampling mussels in other fjords in Greenland along a south–north gradient, and by sampling shells from raised shorelines and archaeological shell middens from prehistoric settlements in Greenland.

The speliothem record of climate variability in Southern Arabia.

Uranium-series dated stalagmites from Oman indicate that pluvial conditions prevailed from 6.3 to 10.5, 78 to 82, 120 to 130, 180 to 200 and 300 to 330 kyr B.P.; all of these periods coincide with peak interglacials. Oxygen (δ18O) and hydrogen (δD) isotope ratios of speleothem calcite and fluid inclusions reveal the source of moisture and provide information on the amount of precipitation, respectively. δ18O and δD values of stalagmites deposited during peak interglacials vary between −8 and −4 ‰ (VPDB) and −53 and −20‰ (Vienna Standard Mean Ocean Water [VSMOW]) respectively, whereas modern stalagmites range from −2.6 to −1.1‰ in δ18O (VPDB) and −7.6 and −3.3‰ in δD (VSMOW), respectively. The growth and isotopic records indicate that during peak interglacial periods, the limit of the monsoon rainfall was shifted far north of its present location and each pluvial period was coinciding with an interglacial stage of the marine oxygen isotope record.

Will greenhouse gas-induced warming over the next 50 years lead to higher frequency and greater intensity of hurricanes?

The use of a high resolution atmospheric model at T106 resolution, for studying the influence of greenhouse warming on tropical storm climatology, is investigated. The same method for identifying the storms has been used as in a previous study by Bengtsson et al. The sea surface temperature anomalies have been taken from a previous transient climate change experiment, obtained with a low resolution ocean-atmosphere coupled model. The global distribution of the storms, at the time when the CO2 concentration in the atmosphere had doubled, agrees in geographical position and seasonal variability with that of the present climate, but the number of storms is significantly reduced, particularly at the Southern Hemisphere. The main reason to this, appear to be connected to changes in the large scale circulation, such as a weaker Hadley circulation and stronger upper air westerlies. The low level vorticity in the hurricane genesis regions is generally reduced compared to the present climate, while the vertical tropospheric wind shear is somewhat increased. Most tropical storm regions indicate reduced surface windspeeds and a slightly weaker hydrological cycle.

A dramatic isotope effect in the reaction of ClSiH with trimethylsilane-1-d: experimental evidence for intermediate complexes in silylene Si-H(D) insertion reactions

A kinetic isotope effect (kD/kH) of 7.4 has been found for the reaction of chlorosilylene with trimethysilane (Me3SiD vs Me3SiH). Such a value can be accounted for by theoretical modelling, but only if an internal rearrangement of the initially form complex is included in the mechanism. This provides the first concrete evidence for such complexes.

Stable isotope and modelling evidence for CO2 as a driver of glacial–interglacial vegetation shifts in southern Africa

Atmospheric CO2 concentration is hypothesized to influence vegetation distribution via tree–grass competition, with higher CO2 concentrations favouring trees. The stable carbon isotope (δ13C) signature of vegetation is influenced by the relative importance of C4 plants (including most tropical grasses) and C3 plants (including nearly all trees), and the degree of stomatal closure – a response to aridity – in C3 plants. Compound-specific δ13C analyses of leaf-wax biomarkers in sediment cores of an offshore South Atlantic transect are used here as a record of vegetation changes in subequatorial Africa. These data suggest a large increase in C3 relative to C4 plant dominance after the Last Glacial Maximum. Using a process-based biogeography model that explicitly simulates 13C discrimination, it is shown that precipitation and temperature changes cannot explain the observed shift in δ13C values. The physiological effect of increasing CO2 concentration is decisive, altering the C3/C4 balance and bringing the simulated and observed δ13C values into line. It is concluded that CO2 concentration itself was a key agent of vegetation change in tropical southern Africa during the last glacial–interglacial transition. Two additional inferences follow. First, long-term variations in terrestrial δ13Cvalues are not simply a proxy for regional rainfall, as has sometimes been assumed. Although precipitation and temperature changes have had major effects on vegetation in many regions of the world during the period between the Last Glacial Maximum and recent times, CO2 effects must also be taken into account, especially when reconstructing changes in climate between glacial and interglacial states. Second, rising CO2 concentration today is likely to be influencing tree–grass competition in a similar way, and thus contributing to the "woody thickening" observed in savannas worldwide. This second inference points to the importance of experiments to determine how vegetation composition in savannas is likely to be influenced by the continuing rise of CO2 concentration.

Focusing the kaleidoscope: investigating the newly formed role of 'Academic Lead’ at a research-led University

Now, more than ever, higher education institutions are reflecting on the need for flexible leadership models to help adapt to the fast changing academic environment. Rapid shifts in the sector are contributing to a kaleidoscopic ‘supercomplexity’ of challenges, structures, processes and value frameworks for academics who lead and for those who are led. How are institutions’ leadership structures and roles developing in response to these changes? And how do these responses affect academic staff in relation to their identity, status and career trajectory? This paper reports on a Leadership Foundation funded research project exploring the ways in which one UK institution has implemented a new ‘distributed’ leadership model. Crucially, the project examines the impact of the model on both those who are leaders and those being led.

Marine Isotope Stage 9 environments of fluvial deposits at Hackney, north London, UK

Middle Pleistocene deposits at Hackney, north London comprise a thick unit of organic sands and silts occupying a channel near the confluence of the River Thames in south-eastern England and its left-bank tributary the River Lea. They represent a short time interval, perhaps no more than a few years, within a late Middle Pleistocene interglacial. The organic sediments are overlain by unfossiliferous sands and gravels indicating deposition on the floodplain of a braided river under cool or cold climatic conditions. The fossil plant, insect, mollusc and vertebrate remains from the interglacial deposits all indicate climatic conditions with summers warmer than the present in SE England, and winters with a similar thermal climate. The biostratigraphic evidence suggests that the time period represented by the organic unit is part of MIS 9, although the geochronological evidence for such an age is inconclusive. The palaeontological evidence strongly suggests that this temperate stage was warmer than the succeeding temperate stage MIS 7 or the Holocene, and approaching the Ipswichian (MISs 5e) in its warmth. The multidisciplinary description of the Hackney deposits is one of the first to reconstruct terrestrial conditions in Marine Isotope Stage 9 in Western Europe.

Economic transformation in Ghana: where will the path lead?

In the context of the Ghanaian government’s objective of structural transformation with an emphasis on manufacturing, this paper provides a case study of economic transformation in Ghana, exploring patterns of growth, sectoral transformation, and agglomeration. We document and examine why, despite impressive growth and poverty reduction figures, Ghana’s economy has exhibited less transformation than might be expected for a country that has recently achieved middle-income status. Ghana’s reduced share of agriculture in the economy, unlike many successfully transformed countries in Asia and Latin America, has been filled by services, while manufacturing has stagnated and even declined. Likely causes include weak transformation of the agricultural sector and therefore little development of agroprocessing, the emergence of consumption cities and consumption-driven growth, upward pressure on the exchange rate, weak production linkages, and a poor environment for private-sector-led manufacturing.

Inferring animal husbandry strategies in coastal zones through stable isotope analysis: new evidence from the Flemish coastal plain (Belgium, 1st-15th century AD)

In a proof-of-concept study, Britton et al. (2008) demonstrated that the isotopic composition of halophytic plants can be traced in the skeletal tissues of their animal consumers. Here we apply the method to domestic herbivore remains (n = 303) from nine archaeological sites in or near the Flemish coastal plain (Belgium), where, prior to embankments, salt-marshes offered extensive pasture grounds for domestic herbivores. The sites span a period of ∼1500 years (Roman to late medieval period), during which the coastal landscape was progressively transformed from little managed wetlands to a fully embanked polder area. The bulk collagen data show variations between sites and over time, which are consistent with this historical framework and are interpreted as reflecting environmental change and differences in animal management in the coastal plain throughout the late Holocene. The study demonstrates the immense value of faunal stable isotope analysis for characterising coastal husbandry strategies beyond the means of traditional zooarchaeological techniques.

A refined sampling strategy for intra-tooth stable isotope analysis of mammalian enamel

Serial sampling and stable isotope analysis performed along the growth axis of vertebrate tooth enamel records differences attributed to seasonal variation in diet, climate or animal movement. Because several months are required to obtain mature enamel in large mammals, modifications in the isotopic composition of environmental parameters are not instantaneously recorded, and stable isotope analysis of tooth enamel returns a time-averaged signal attenuated in its amplitude relative to the input signal. For convenience, stable isotope profiles are usually determined on the side of the tooth where enamel is thickest. Here we investigate the possibility of improving the time resolution by targeting the side of the tooth where enamel is thinnest. Observation of developing third molars (M3) in sheep shows that the tooth growth rate is not constant but decreases exponentially, while the angle between the first layer of enamel deposited and the enamel–dentine junction increases as a tooth approaches its maximal length. We also noted differences in thickness and geometry of enamel growth between the mesial side (i.e., the side facing the M2) and the buccal side (i.e., the side facing the cheek) of the M3. Carbon and oxygen isotope variations were measured along the M3 teeth from eight sheep raised under controlled conditions. Intra-tooth variability was systematically larger along the mesial side and the difference in amplitude between the two sides was proportional to the time of exposure to the input signal. Although attenuated, the mesial side records variations in the environmental signal more faithfully than the buccal side. This approach can be adapted to other mammals whose teeth show lateral variation in enamel thickness and could potentially be used as an internal check for diagenesis.

A 27 day persistence model of near-Earth solar wind conditions: a long lead-time forecast and a benchmark for dynamical models

Geomagnetic activity has long been known to exhibit approximately 27 day periodicity, resulting from solar wind structures repeating each solar rotation. Thus a very simple near-Earth solar wind forecast is 27 day persistence, wherein the near-Earth solar wind conditions today are assumed to be identical to those 27 days previously. Effective use of such a persistence model as a forecast tool, however, requires the performance and uncertainty to be fully characterized. The first half of this study determines which solar wind parameters can be reliably forecast by persistence and how the forecast skill varies with the solar cycle. The second half of the study shows how persistence can provide a useful benchmark for more sophisticated forecast schemes, namely physics-based numerical models. Point-by-point assessment methods, such as correlation and mean-square error, find persistence skill comparable to numerical models during solar minimum, despite the 27 day lead time of persistence forecasts, versus 2–5 days for numerical schemes. At solar maximum, however, the dynamic nature of the corona means 27 day persistence is no longer a good approximation and skill scores suggest persistence is out-performed by numerical models for almost all solar wind parameters. But point-by-point assessment techniques are not always a reliable indicator of usefulness as a forecast tool. An event-based assessment method, which focusses key solar wind structures, finds persistence to be the most valuable forecast throughout the solar cycle. This reiterates the fact that the means of assessing the “best” forecast model must be specifically tailored to its intended use.