Generation of homologous porphyrins under simulated geochemical conditions

Crude oils generally contain at least one symmetrical homologous series of porphyrins, which is usually centered at m/e 476 (DPEP) or m/e 478 (etioporphyrin). Simulated geochemical conditions in the present study resulted in decarboxylations and alkylations which ultimately led to the synthesis of homologous porphyrins from a single porphyrin. In several series of closed tube experiments, mesoporphyrin IX dimethylester (MPDME) was mixed with a variety of constituents including benzene, acetic acid, propionic acid, water and clay; the experiments were performed at temperatures between 135°C and 400°C at time intervals up to 80 days. Dealkylation, alkylation, hydrolysis, decarboxylation and metallation products were observed. An unsymmetrical homologous series of porphyrins was produced from MPDME. The dominant mass was m/e 478 (corresponding to a double deoarboxylation). Dealkylation products in multiples of 14 amu below the m/e 478 peak comprised the other members of the series. Cu-MPDME also produced homologous porphyrins. These, however, exhibited symmetry about the dominant members, similar to the symmetry found for the porphyrins of most petroleums and oil shales.     

Grassroots social innovations and food localisation: An investigation of the Local Food programme in England

This paper seeks to orientate research on local food networks more firmly towards ideas of grassroots and social niche innovations. Drawing on recent conceptual ideas from strategic niche management, this paper provides an exploratory analysis of attempts to spread grassroots social innovations through the Big Lottery Local Food programme run by the Royal Society of Wildlife Trusts in England. This £ 59.8 million programme aims to distribute grants to a variety of food-related projects and to make locally grown food more accessible and affordable to local communities. Insights into 29 funded projects, of varying length and scale of operation, are provided through over 150 telephone and personal interviews. While the Local Food programme is undoubtedly about bringing small, often neglected pieces of land into production and increasing access to affordable food, results show that the programme is also very much seen as a vehicle for building community capacity through facilitating community cohesion, healthy eating, educational enhancement and integrating disadvantaged groups into mainstream society and economy. The paper concludes with some reflections on the extent to which the concept of grassroots social innovations, as a form of niche innovation, can help understand the ability of local food networks to develop the capacity of communities to respond to locally identified problems and to effect more widespread, sustainable change.     

Topographically moderated soil water seasons impact vegetation dynamics in semiarid mountain catchments: Illustrations from the Dry Creek Experimental Watershed,Idaho, USA

Water stored in soils, in part, controls vegetation productivity and the duration of growing seasons in wildland ecosystems. Soil water is the dynamic product of precipitation, evapotranspiration and soil properties, all of which vary across complex terrain making it challenging to decipher the specific controls that soil water has on growing season dynamics. We assess how soil water use by plants varies across elevations and aspects in the Dry Creek Experimental Watershed in southwest Idaho, USA, a mountainous, semiarid catchment that spans low elevation rain to high elevation snow regimes. We compare trends in soil water and soil temperature with corresponding trends in insolation, precipitation and vegetation productivity, and we observe trends in the timing, rate and duration of soil water extraction by plants across ranges in elevation and aspect. The initiation of growth-supporting conditions, indicated by soil warming, occurs 58 days earlier at lower, compared with higher, elevations. However, growth-supporting conditions also end earlier at lower elevations due to the onset of soil water depletion 29 days earlier than at higher elevations. A corresponding shift in peak NDVI timing occurs 61 days earlier at lower elevations. Differences in timing also occur with aspect, with most threshold timings varying by 14–30 days for paired north- and south-facing sites at similar elevations. While net primary productivity nearly doubles at higher elevations, the duration of the warm-wet period of active water use does not vary systematically with elevation. Instead, the greater ecosystem productivity is related to increased soil water storage capacity, which supports faster soil water use and growth rates near the summer solstice and peak insolation. Larger soil water storage does not appear to extend the duration of the growing season, but rather supports higher growing season intensity when wet-warm soil conditions align with high insolation. These observations highlight the influence of soil water storage capacity in dictating ecological function in these semiarid steppe climatic regimes.     

A deeper look at the colors of the saturnian irregular satellites

We have performed broadband color photometry of the twelve brightest irregular satellites of Saturn with the goal of understanding their surface composition, as well as their physical relationship. We find that the satellites have a wide variety of different surface colors, from the negative spectral slopes of the two retrograde satellites S IX Phoebe (S^′=−2.5±0.4) and S XXV Mundilfari (S^′=−5.0±1.9) to the fairly red slope of S XXII Ijiraq (S^′=19.5±0.9). We further find that there exist a correlation between dynamical families and spectral slope, with the prograde clusters, the Gallic and Inuit, showing tight clustering in colors among most of their members. The retrograde objects are dynamically and physically more dispersed, but some internal structure is apparent.     

Antarctic dry valleys: Microclimate zonation, variable geomorphic processes, and implications for assessing climate change on Mars

The Antarctic Dry Valleys (ADV) are generally classified as a hyper-arid, cold-polar desert. The region has long been considered an important terrestrial analog for Mars because of its generally cold and dry climate and because it contains a suite of landforms at macro-, meso-, and microscales that closely resemble those occurring on the martian surface. The extreme hyperaridity of both Mars and the ADV has focused attention on the importance of salts and brines on soil development, phase transitions from liquid water to water ice, and ultimately, on process geomorphology and landscape evolution at a range of scales on both planets. The ADV can be subdivided into three microclimate zones: a coastal thaw zone, an inland mixed zone, and a stable upland zone; zones are defined on the basis of summertime measurements of atmospheric temperature, soil moisture, and relative humidity. Subtle variations in these climate parameters result in considerable differences in the distribution and morphology of: (1) macroscale features (e.g., slopes and gullies); (2) mesoscale features (e.g., polygons, including ice-wedge, sand-wedge, and sublimation-type polygons, as well as viscous-flow features, including solifluction lobes, gelifluction lobes, and debris-covered glaciers); and (3) microscale features (e.g., rock-weathering processes/features, including salt weathering, wind erosion, and surface pitting). Equilibrium landforms are those features that formed in balance with environmental conditions within fixed microclimate zones. Some equilibrium landforms, such as sublimation polygons, indicate the presence of extensive near-surface ice; identification of similar landforms on Mars may also provide a basis for detecting the location of shallow ice. Landforms that today appear in disequilibrium with local microclimate conditions in the ADV signify past and/or ongoing shifts in climate zonation; understanding these shifts is assisting in the documentation of the climate record for the ADV. A similar type of landform analysis can be applied to the surface of Mars where analogous microclimates and equilibrium landforms occur (1) in a variety of local environments, (2) in different latitudinal bands, and (3) in units of different ages. Documenting the nature and evolution of the ADV microclimate zones and their associated geomorphic processes is helping to provide a quantitative framework for assessing the evolution of climate on Mars.     

Origin of the Blue Ridge escarpment along the passive margin of Eastern North America

The Blue Ridge escarpment is a rugged landform situated within the ancient Appalachian orogen. While similar in some respects to the great escarpments along other passive margins, which have evolved by erosion following rifting, its youthful topographic expression has inspired proposals of Cenozoic tectonic rejuvenation in eastern North America. To better understand the post‐orogenic and post‐rift geomorphic evolution of passive margins, we have examined the origin of this landform using low‐temperature thermochronometry and manipulation of topographic indices. Apatite (U–Th)/He and fission‐track analyses along transects across the escarpment reveal a younging trend towards the coast. This pattern is consistent with other great escarpments and fits with an interpretation of having evolved by prolonged erosion, without the requirement of tectonic rejuvenation. Measured ages are also comparable specifically to those measured along other great escarpments that are as much as 100 Myr younger. This suggests that erosional mechanisms that maintain rugged escarpments in the early post‐rift stages may remain active on ancient passive margins for prolonged periods. The precise erosional evolution of the escarpment is less clear, however, and several end‐member models can explain the data. Our preferred model, which fits with all data, involves a significant degree of erosional escarpment retreat in the Cenozoic. Although this suggests that early onset of topographic stability is not required of passive margin evolution, more data are required to better constrain the details of the escarpment's development.     

Glacier fluctuations in the southern Peruvian Andes during the late‐glacial period,constrained with cosmogenic 3He

The occurrence of pronounced climate reversals during the last glacial termination has long been recognised in palaeoclimate records from both hemispheres and from high to low latitudes. Accurate constraint of both the timing and magnitude of events, such as the Younger Dryas and Antarctic Cold Reversal, is vital in order to test different hypotheses for the causes and propagation of abrupt climate change. However, in contrast to higher‐latitude regions, well‐dated records from the Tropics are rare and the structure of late‐glacial tropical climate remains uncertain. As a step toward addressing this problem, we present an in situ cosmogenic ³He surface exposure chronology from Nevado Coropuna, southern Peru, documenting a significant fluctuation of the ice margin during the late‐glacial period. Ten tightly clustered ages from a pair of moraines located halfway between the modern glacier and the Last Glacial Maximum terminus range from 11.9 to 13.9 ka and give an arithmetic mean age of 12.8 ± 0.7 ka (1σ). These data constitute direct evidence for a readvance, or prolonged stillstand, of glaciers in the arid Andes of southwestern Peru. Copyright © 2011 John Wiley & Sons, Ltd.     

Catastrophic landslides,glacier behaviour and moraine formation – A view from an active plate margin

The influence of large bedrock landslides (“rock avalanches”) on the behaviour of glaciers is incompletely recognised. Here we present an example from an active tectonic margin in South Island, New Zealand where large earthquakes leave a significant imprint on glacial records. We demonstrate that terminal moraines on the western side of the Southern Alps record both ‘ordinary’ (i.e. climate-driven) and landslide-initiated glacial advances. Following consideration of the processes involved in rock avalanche-initiated moraine construction we suggest ways of determining the nature of the advance that built the terminal moraine. The implications of these observations are important in breaking the conventional linkage of individual terminal moraines with climate forcing.