Probing the molecular-level control of aluminosilicate dissolution: A sensitive solid-state NMR proxy for reactive surface area

For two suites of volcanic aluminosilicate glasses, the accessible and reactive sites for covalent attachment of the fluorine-containing (3,3,3-trifluoropropyl)dimethylchlorosilane (TFS) probe molecule were measured by quantitative ¹⁹F nuclear magnetic resonance (NMR) spectroscopy. The first set of samples consists of six rhyolitic and dacitic glasses originating from volcanic activity in Iceland and one rhyolitic glass from the Bishop Tuff, CA. Due to differences in the reactive species present on the surfaces of these glasses, variations in the rate of acid-mediated dissolution (pH 4) for samples in this suite cannot be explained by variations in geometric or BET-measured surface area. In contrast, the rates scale directly with the surface density of TFS-reactive sites as measured by solid-state NMR. These data are consistent with the inference that the TFS-reactive M-OH species on the glass surface, which are known to be non-hydrogen-bonded Q³ groups, represent loci accessible to and affected by proton-mediated dissolution. The second suite of samples, originating from a chronosequence in Kozushima, Japan, is comprised of four rhyolites that have been weathered for 1.1, 1.8, 26, and 52 ka. The number of TFS-reactive sites per gram increases with duration of weathering in the laboratory for the “Icelandic” samples and with duration of field weathering for both “Icelandic” and Japanese samples. One hypothesis is consistent with these and published modeling, laboratory, and field observations: over short timescales, dissolution is controlled by fast-dissolving sites, but over long timescales, dissolution is controlled by slower-dissolving sites, the surface density of which is proportional to the number of TFS-reactive Q³ sites. These latter sites are not part of a hydrogen-bonded network on the surface of the glasses, and measurement of their surface site density allows predictions of trends in reactive surface area. The TFS treatment method, which is easily monitored by quantitative ¹⁹F solid-state NMR, therefore provides a chemically specific and quantifiable proxy to understand the nature of how sites on dissolving silicates control dissolution. Furthermore, ²⁷Al NMR techniques are shown here to be useful in identifying clays on the glass surfaces, and these methods are therefore effective for quantifying concentrations of weathering impurities. Our interpretations offer a testable hypothesis for the mechanism of proton-promoted dissolution for low-iron aluminosilicate minerals and glasses and suggest that future investigations of reactive surfaces with high-sensitivity NMR techniques are warranted.     

New chronological and stratigraphical data on the Ivrea amphitheatre (Piedmont, NW Italy)

The Ivrea amphitheatre (IA) in NW Italy has been studied since 1850, on pedostratigraphic and morphological bases. Three stratigraphic groups of glacial sediments were distinguished. Newly recognized stratigraphic boundaries are based on interstadial/interglacial units, palaeosols and lacustrine organic layers interbedded with glacigenic deposits, and on pedostratigraphy. Mapping of morphological features and associated marginal and sub-glacial deposit facies was used to characterize and reconstruct glacial margin fluctuations. Based on the field evidence, the stratigraphical limits recognized at single sites can be interpolated over the whole amphitheatre. Ten stratigraphic units (referred to as alloformations: Afs) were distinguished and mapped. They are related to at least as many glacial episodes ranging in age from the end of the Early Pleistocene to the Late Pleistocene. The youngest three glacial units (Serra Af, Piverone Af and Ivrea Af) and one interstadial level (Alice Superiore Unit between Serra and Piverone Afs) are discussed in detail. Based on biostratigraphical and pedological, as well as sedimentological and morphological data, the Serra Af can be attributed to MIS 6 and Piverone Af to MIS 4. The ¹⁰Be surface exposure ages from two boulders (27.9±3.1, 32.4±4.0 kyr) on the Serra d’Ivrea moraine provide only a minimum age for moraine construction. The alignment of typical ice marginal landforms (moraines and kame terraces) for the more recent unit (Ivrea Af) has allowed recognition of 12 principal stadials during the LGM and Lateglacial; 6 stadials in the amphitheatre and 6 stadials in Dora Baltea Valley, and reconstruction of the nature of the last glacial retreat from the amphitheatre to the cirques. ¹⁰Be exposure ages from three boulders related to Ivrea Af are 13.1±1.0, 17.4±2.6 and 20.8±1.5 ka. The latter two ages indicate that the Dora Baltea Glacier deposited the Ivrea Af in the IA during MIS 2. The ¹⁰Be exposure ages of 14.6±1.2 and 14.0±0.9 ka from a polished bedrock surface some 15 km upstream from the amphitheatre provide a minimum age for ice decay.     

A study of methods to estimate debris flow velocity

Debris flow velocities are commonly back-calculated from superelevation events which require subjective estimates of radii of curvature of bends in the debris flow channel or predicted using flow equations that require the selection of appropriate rheological models and material property inputs. This research investigated difficulties associated with the use of these conventional velocity estimation methods. Radii of curvature estimates were found to vary with the extent of the channel investigated and with the scale of the media used, and back-calculated velocities varied among different investigated locations along a channel. Distinct populations of Bingham properties were found to exist between those measured by laboratory tests and those back-calculated from field data; thus, laboratory-obtained values would not be representative of field-scale debris flow behavior. To avoid these difficulties with conventional methods, a new preliminary velocity estimation method is presented that statistically relates flow velocity to the channel slope and the flow depth. This method presents ranges of reasonable velocity predictions based on 30 previously measured velocities.     

Natural Resource Access Rights and Wrongs: Nontimber Forest Products Gathering in Urban Environments

This article uses research about non-timber forest products (NTFP) gathering in Seattle, Washington, USA to examine how people gain access to natural resources in urban environments. Our analysis focuses on gathering in three spaces: parks, yards, and public rights of way. We present a framework for conceptualizing access, and highlight cognitive mechanisms of access associated with foragers’ internal moral judgments about harvesting. Key findings are: (1) internal moral calculations about whether it is right or wrong to harvest a particular NTFP in a particular place are an important but previously unacknowledged mechanism governing resource access; and (2) these calculations may help prevent over-harvesting of NTFPs, which are common pool resources, in urban environments where social and environmental conditions lend themselves to a de facto situation of open access. Our findings suggest that voluntary codes of conduct may be the best way to manage NTFP access in cities.     

Landslide deposits as stratigraphical markers for a sequence‐based glacial stratigraphy: a case study of a Younger Dryas system in the Eastern Alps

Detailed ¹⁰Be and ¹⁴C dating and supporting pollen analysis of Alpine Lateglacial glacial and landslide deposits in the Hohen Tauern Mountains (Austria) constrain a sequence‐based stratigraphy comprising a major landslide (13.0±1.1 ka) overlain by till and termino‐lateral moraines of an advancing (12.6±1.0 ka) and retreating (11.3±0.8 ka) glacier in turn overlain by a minor landslide (10.8±1.1 ka). These results define glacier activity during the Younger Dryas age Egesen stadial bracketed by landslide activities during the Bølling‐Allerød interstadial and the Preboreal. In contrast to recent studies on Holocene glaciation in the Alps, no traces of any Holocene glacier advance bigger than during the Little Ice Age are documented. Furthermore, this study demonstrates the advantages of using an allostratigraphical approach based on unconformity‐bounded sedimentary units as a tool for glacial stratigraphy in formerly glaciated mountain regions, rather than a stratigraphy based on either isolated morphological features or lithostratigraphical characteristics.     

Learning across levels of governance: Expert advice and the adoption of carbon dioxide emissions reduction targets in the UK

This paper is concerned with environmental governance and policy formation in the area of climate change. Specifically, it examines a decision by the UK Government in 2003 to adopt a demanding, long-term CO₂ emissions reduction target, following the advice of one of its longest standing environmental advisory bodies, the Royal Commission on Environmental Pollution. It explores the origins of the Commission's recommendation and the reasons for its relatively rapid uptake in public policy. It argues that in both cases, a complex mix of structural and contingent, cognitive and non-cognitive factors can be identified, operating at different levels of governance. Finally, the paper reflects on what we might learn from this particular case about policy processes and the role of knowledge and expert advice within them.     

Becoming Reading Group: reflections on assembling a collegiate,caring collective

ABSTRACT

In neoliberalising universities, collegial and collective practices such as reading groups are often positioned by students, staff and managers as less important than meeting individual KPIs (such as producing research publications, seeking research grants, or meeting the increasing demands of producing quality teaching outcomes.) However, reading groups can be vital for cultivating caring collectives and spaces of collegiality. In this paper we use assemblage thinking to explore 25 years of a Geography reading group at the University of Newcastle. The paper addresses two questions: what does reading together do and make possible; and how might we think about the labours of reading together as a way of building caring collectives. The paper draws on reflections from 24 past and present members of reading group to explore how these kinds of academic practices nourish our working lives.     

Spatialities of ageing: The co-construction and co-evolution of old age and space

This editorial introduction to the themed issue is divided into four parts. We begin with outlining five reasons for more sustained attention to ageing and old age in human geography and go onto discuss two major challenges for geographical inquiry into ageing and later life. One of these is examining embodiment in ways that keep both its social/cultural aspects and its biological/physiological dimensions in sharp focus; the other concerns the challenge of considering time, or rather spatiotemporality, in all its facets. With regard to the latter we argue that the life-course concept can be helpful in this regard, especially if attention is paid to transitions as well as to slow, difficult-to-identify forms of change and if life-courses are understood in terms of folds. Thinking in these terms opens up a perspective according to which ageing and space can be analysed as entwined becomings. We conclude by positioning the contributions in this issue vis-à-vis the perspective developed in this piece.     

Climatic Influences on Autochthonous and Allochthonous Phytoplankton Blooms in a Subtropical Estuary, St. Lucie Estuary, Florida, USA

The St. Lucie Estuary, located on the southeast coast of Florida, provides an example of a subtropical ecosystem where seasonal changes in temperature are modest, but summer storms alter rainfall regimes and external inputs to the estuary from the watershed and Atlantic Ocean. The focus of this study was the response of the phytoplankton community to spatial and temporal shifts in salinity, nutrient concentration, watershed discharges, and water residence times, within the context of temporal patterns in rainfall. From a temporal perspective, both drought and flood conditions negatively impacted phytoplankton biomass potential. Prolonged drought periods were associated with reduced nutrient loads and phytoplankton inputs from the watershed and increased influence of water exchange with the Atlantic Ocean, all of which restrict biomass potential. Conversely, under flood conditions, nutrient loads were elevated, but high freshwater flushing rates in the estuary diminished water residence times and increase salinity variation, thereby restricting the buildup of phytoplankton biomass. An exception to the latter pattern was a large incursion of a cyanobacteria bloom from Lake Okeechobee via the St. Lucie Canal observed in the summer of 2005. From a spatial perspective, regional differences in water residence times, sources of watershed inputs, and the proximity to the Atlantic Ocean influenced the composition and biomass of the phytoplankton community. Long water residence times in the North Fork region of the St. Lucie Estuary provided an environment conducive to the development of blooms of autochthonous origin. Conversely, shorter residence times in the mid-estuary limit autochthonous increases in biomass, but allochthonous sources of biomass can result in bloom concentrations of phytoplankton.     

Food Web Structure of the Alaskan Nearshore Shelf and Estuarine Lagoons of the Beaufort Sea

The eastern Alaska Beaufort Sea coast is characterized by numerous shallow (2–5 m) estuarine lagoons, fed by streams and small rivers that drain northward from the Brooks Range through the arctic coastal plain, and bounded seaward by barrier islands and shoals. Millions of birds from six continents nest and forage during the summer period in this region using the river deltas, lagoons, and shoreline along with several species of anadromous and marine fish. We examined biogeochemical processes linking the benthic community to the overall food web structure of these poorly studied but pristine estuaries, which are largely covered by 1.8 m of ice for 10 months annually. In summer, these lagoons are relatively warm with brackish salinities (5–10°C, S = 10–25) compared to more open coastal waters (0–5°C, S > 27). The stable isotopic composition of organic materials in sediments (i.e., benthic particulate organic matter) and water column suspended particulate organic matter from both streams and lagoons are largely indistinguishable and reflect strong terrestrial contributions, based upon δ¹³C and δ¹⁵N values (−25.6‰ to −27.4‰ and 1.4‰ to 3.3‰, respectively). By comparison, shifts toward more heavy isotope-enriched organic materials reflecting marine influence are observed on the adjacent coastal shelf (−24.8‰ to −25.4‰ and 3.4‰ to 5.3‰, respectively). The isotopic composition of lagoon fauna is consistent with a food web dominated by omnivorous detritovores strongly dependent on microbial processing of terrestrial sources of carbon. Biomagnification of ¹⁵N in benthic organisms indicate that the benthic food web in lagoons support up to four trophic levels, with carnivorous gastropod predators and benthic fishes (δ¹⁵N values up to 14.4‰) at the apex.