Combining advanced NMR techniques with ultrahigh resolution mass spectrometry: A new strategy for molecular scale characterization of macromolecular components of soil and sedimentary organic matter

Molecular level characterization of complex biopolymers in nature is a key element to understanding the composition of natural organic matter (NOM) and fossil organic matter formation, such as kerogen and coal. Characterization of such geopolymers is difficult due to their heterogeneity and insolubility in common aqueous or organic solvents. Here, a strategy for extracting a representative sample is presented using the combined techniques of nuclear magnetic resonance (NMR) and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) for chemical analysis and characterization of NOM. A variety of NOM samples (wood, kerogen, bitumen, whole sediments) are shown as examples for implementing the strategy, which include solvent extractions using pyridine. For most samples, the extracts are confirmed to be chemically representative of the insoluble solid, by comparing the liquids NMR spectrum of the extract to that of the whole, unfractionated NOM utilizing high resolution magic angle spinning (HRMAS) NMR. To assist in unambiguous peak assignment, a technique for post acquisition spectral denoising, using wavelet transformation (WT), is also employed on the 1D and 2D NMR spectra. The findings from the NMR data lay a foundation for the subsequent electrospray ionization FTICR-MS analysis of the pyridine extracts, since this instrument has the limitation of only analyzing liquid samples. The FTICR-MS analyses can, therefore, be used to molecularly represent the structural components of the NOM. Various compositional insights have been obtained on these samples, indicating the efficacy of the analytical techniques used.     

Spatial dimensions of New Zealand's environmental management

New Zealand's regional council boundaries drawn as part of the 1989 local government reforms privilege integrated catchment management. This privilege is now challenged by calls to both fragment and amalgamate councils and centralise decision‐making but with little analytic assessment of the spatial differentiation to support them. The spatial underpinnings of these calls were explored using a case study that assessed the spatial dimensions of environment management. Analysis of the Land Environments and River Environment Classification databases and councils' planning documents highlights challenges local governments face in applying integrated natural resource management within single purpose jurisdictions and implications for wider sustainable development policy.     

Influence of seepage undercutting on the stability of root‐reinforced streambanks

Several mechanisms contribute to streambank failure including fluvial toe undercutting, reduced soil shear strength by increased soil pore‐water pressure, and seepage erosion. Recent research has suggested that seepage erosion of noncohesive soil layers undercutting the banks may play an equivalent role in streambank failure to increased soil pore‐water pressure. However, this past research has primarily been limited to laboratory studies of non‐vegetated banks. The objective of this research was to utilize the Bank Stability and Toe Erosion Model (BSTEM) in order to determine the importance of seepage undercutting relative to bank shear strength, bank angle, soil pore‐water pressure, and root reinforcement. The BSTEM simulated two streambanks: Little Topashaw Creek and Goodwin Creek in northern Mississippi. Simulations included three bank angles (70° to 90°), four pore‐water pressure distributions (unsaturated, two partially saturated cases, and fully saturated), six distances of undercutting (0 to 40 cm), and 13 different vegetation conditions (root cohesions from 0·0 to 15·0 kPa). A relative sensitivity analysis suggested that BSTEM was approximately three to four times more sensitive to water table position than root cohesion or depth of seepage undercutting. Seepage undercutting becomes a prominent bank failure mechanism on unsaturated to partially saturated streambanks with root reinforcement, even with undercutting distances as small as 20 cm. Consideration of seepage undercutting is less important under conditions of partially to fully saturated soil pore‐water conditions. The distance at which instability by undercutting became equivalent to instability by increased soil pore‐water pressure decreased as root reinforcement increased, with values typically ranging between 20 and 40 cm at Little Topashaw Creek and between 20 and 55 cm at Goodwin Creek. This research depicts the baseline conditions at which seepage undercutting of vegetated streambanks needs to be considered for bank stability analyses. Copyright © 2008 John Wiley & Sons, Ltd.     

How ready is ready? Measuring physical preparedness for severe storms

This paper investigates use of inventories, or checklists of activities, as an emergency management tool to motivate preparedness action in individuals. It develops the inventory concept to provide the foundation for a more targeted approach to storm preparation communication and community engagement. It also examines the potential efficacy of alternatives to paper-based checklists, such as web or smartphone applications. Academic and grey literature was reviewed to collect activities for a storm inventory for emergency agencies to measure individual preparedness and for individuals to measure their preparation progress. The resulting master list was refined for application and tested for useability in a pilot study of semi-structured interviews in a storm-susceptible community in Queensland, Australia. Also, clustering items by type of preparedness activity reveal where strengths and weaknesses exist in individual preparedness. For instance, preparation for leaving and safety planning were shown to be the areas of weakest activity in the pilot sample, while preparation of the house for a storm was the strongest area. In addition, behaviour change literature shows potential for effective use of an inventory-based smartphone application in motivating preparation activity. Data collected by a storm preparedness smartphone application could show where a communication or engagement program for targeted communities should be focused. It is supported by health literature that identifies preferences of individuals to make progress on complex tasks in stages, the value of lists to achievement of goals and demonstrated increase in uptake of activities prompted by smartphone applications over web or paper-based diaries.

     

Contrasting rainfall generated debris flows from adjacent watersheds at Forest Falls, southern California, USA

Debris flows are widespread and common in many steeply sloping areas of southern California. The San Bernardino Mountains community of Forest Falls is probably subject to the most frequently documented debris flows in southern California. Debris flows at Forest Falls are generated during short-duration high-intensity rains that mobilize surface material. Except for debris flows on two consecutive days in November 1965, all the documented historic debris flows have occurred during high-intensity summer rainfall, locally referred to as ‘monsoon’ or ‘cloudburst’ rains. Velocities of the moving debris range from about 5 km/h to about 90 km/h. Velocity of a moving flow appears to be essentially a function of the water content of the flow. Low velocity debris flows are characterized by steep snouts that, when stopped, have only small amounts of water draining from the flow. In marked contrast are high-velocity debris flows whose deposits more resemble fluvial deposits. In the Forest Falls area two adjacent drainage basins, Snow Creek and Rattlesnake Creek, have considerably different histories of debris flows. Snow Creek basin, with an area about three times as large as Rattlesnake Creek basin, has a well developed debris flow channel with broad levees. Most of the debris flows in Snow Creek have greater water content and attain higher velocities than those of Rattlesnake Creek. Most debris flows are in relative equilibrium with the geometry of the channel morphology. Exceptionally high-velocity flows, however, overshoot the channel walls at particularly tight channel curves. After overshooting the channel, the flows degrade the adjacent levee surface and remove trees and structures in the immediate path, before spreading out with decreasing velocity. As the velocity decreases the clasts in the debris flows pulverize the up-slope side of the trees and often imbed clasts in them. Debris flows in Rattlesnake Creek are relatively slow moving and commonly stop in the channel. After the channel is blocked, subsequent debris flows cut a new channel upstream from the blockage that results in the deposition of new debris-flow deposits on the lower part of the fan. Shifting the location of debris flows on the Rattlesnake Creek fan tends to prevent trees from becoming mature. Dense growths of conifer seedlings sprout in the spring on the late summer debris flow deposits. This repeated process results in stands of even-aged trees whose age records the age of the debris flows.     

Partnering between a geography department and a community initiative to provide a wind resource assessment for the Blueskin Bay region,Otago, New Zealand

This paper explores the partnership between a community group and a geography department to assess the wind energy potential of the Blueskin Bay region in southern New Zealand. The partnership has provided opportunities for research and is of strategic importance. Year‐long wind observations and numerical modelling have revealed that the hills surrounding Blueskin Bay show potential for wind energy generation. Despite challenges for both parties, the university–community partnership has allowed a successful research platform to be established.     

The evolution of the terrestrial-terminating Irish Sea glacier during the last glaciation

Here we reconstruct the last advance to maximum limits and retreat of the Irish Sea Glacier (ISG), the only land-terminating ice lobe of the western British Irish Ice Sheet. A series of reverse bedrock slopes rendered proglacial lakes endemic, forming time-transgressive moraine- and bedrock-dammed basins that evolved with ice marginal retreat. Combining, for the first time on glacial sediments, optically stimulated luminescence (OSL) bleaching profiles for cobbles with single grain and small aliquot OSL measurements on sands, has produced a coherent chronology from these heterogeneously bleached samples. This chronology constrains what is globally an early build-up of ice during late Marine Isotope Stage 3 and Greenland Stadial (GS) 5, with ice margins reaching south Lancashire by 30 ± 1.2 ka, followed by a 120-km advance at 28.3 ± 1.4 ka reaching its 26.5 ± 1.1 ka maximum extent during GS-3. Early retreat during GS-3 reflects piracy of ice sources shared with the Irish-Sea Ice Stream (ISIS), starving the ISG. With ISG retreat, an opportunistic readvance of Welsh ice during GS-2 rode over the ISG moraines occupying the space vacated, with ice margins oscillating within a substantial glacial over-deepening. Our geomorphological chronosequence shows a glacial system forced by climate but mediated by piracy of ice sources shared with the ISIS, changing flow regimes and fronting environments.     

Nutrient limitation of the macroalgaEnteromorpha intestinalis collected along a resource gradient in a highly eutrophic estuary

We conducted a laboratory experiment to quantify nutrient (nitrogen and phosphorus) limitation of macroalgae collected along a gradient in water column nutrient availability in Upper Newport Bay estuary, a relatively nutrient-rich system in southern California, United States. We collectedEnteromorpha intestinalis and water for use in the experiment from five sites ranging from the lower end of the estuary to the head. Initial algal tissue N and P concentrations and molar N∶P ratios—as well as water column NO₃ and total Kjeldahl nitrogen (TKN)—increased along a spatial gradient from the lower end toward the head. Water column soluble reactive phosphorus (SRP) varied among sites as well but did not follow a pattem of increasing from the seaward end toward the head. Algae from each site were assigned to one of four experimental treatments: control (C), nitrogen enrichment (+N), phosphorus enrichment (+P), and nitrogen and phosphorus enrichment (+N+P). Each week for 3 wk we replaced the water in each unit with the appropriate treatment water to mimic a poorly flushed estuary. After 3 wk, the degree of nutrient limitation ofE. intestinalis varied spatially with distance from the head of the estuary. Growth ofE. intestinalis collected from several sites increased with N enrichment alone and increased further when P was added in combination with N This indicated that N was limiting and that when N was sufficient, P became limiting. Sites from whichE. intestinalis exhibited nutrient limitation spanned the range of background water column NO₃ (12.9±0.4 to 55.2±2.1 μM) and SRP (0.8±0.0 to 2.9±0.2 μM) concentrations. Algae that were N limited had initial tissue N levels ranging from 1.18±0.03 to 2.81±0.08% dry weight and molar N∶P ratios ranging from 16.75±0.39 to 26.40±1.98.     

A spatial and statistical analysis of the impact of transformation of raster cost surfaces on the variation of least-cost paths

Planners who are involved in locational decision-making often use raster-based geographic information systems to quantify the value of land in terms of suitability or cost for a certain use. From a computational point of view, this process can be seen as a transformation of one or more sets of values associated with a grid of cells into another set of such values through a function reflecting one or more criteria. While it is generally anticipated that different transformations lead to different ‘best’ locations, little has been known on how such differences arise (or do not arise). The paper attempts to answer this question in the context of path planning through a series of computational experiments using a number of random landscape grids with a variety of spatial and nonspatial structures. In the experiments, we generated least-cost paths on a number of cost grids transformed from the landscape grids using a variety of transformation parameters and analyzed the locations and (weighted) lengths of those paths. Results show that the same pair of terminal cells may well be connected by different least-cost paths on different cost grids though derived from the same landscape grid and that the variation among those paths is affected by how given values are distributed in the landscape grid as well as by how derived values are distributed in the cost grids. Most significantly, the variation tends to be smaller when the landscape grid contains more distinct patches of cells potentially attracting or distracting cost-saving passage or when the cost grid contains a smaller number of low-cost cells.     

Experimental insights into the formation of high-Mg basaltic andesites in the trans-Mexican volcanic belt

High-Mg basaltic andesites and andesites occur in the central trans-Mexican volcanic belt, and their primitive geochemical characteristics suggest equilibration with mantle peridotite. These lavas may represent slab melts that reequilibrated with overlying peridotite or hydrous partial melts of a peridotite source. Here, we experimentally map the liquidus mineralogy for a high-Mg basaltic andesite (9.6 wt% MgO, 54.4 wt% SiO₂, Mg# = 75.3) as a function of temperature and H₂O content over a range of mantle wedge pressures. Our results permit equilibration of this composition with a harzburgite residue at relatively high water contents (>7 wt%) and low temperatures (1,080–1,150°C) at 11–14 kbar. However, in contrast to the high Ni contents characteristic of olivine phenocrysts in many such samples from central Mexico, those of olivine phenocrysts in our sample are more typical of mantle melts that have fractionated a small amount of olivine. To account for this and the possibility that the refractory mantle source may have had olivine more Fo-rich than Fo₉₀, we numerically evaluated alternative equilibration conditions, using our starting bulk composition adjusted to be in equilibrium with Fo₉₂ olivine. This shifts equilibration conditions to higher temperatures (1,180–1,250°C) at mantle wedge pressures (11–15 kbar) for H₂O contents (>3 wt%) comparable to those analyzed in olivine-hosted melt inclusions from this region. Comparison with geodynamic models shows that final equilibration occurred shallower than the peak temperature of the mantle wedge, suggesting that basaltic melts from the hottest part of the wedge reequilibrated with shallower mantle as they approached the Moho.