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.     

Experimental partitioning of trace elements into schreibersite with applications to IIG iron meteorites

Some of the defining characteristics of the IIG iron meteorite group are their high bulk P contents and massive, coarse schreibersite, which have been calculated to make up roughly 11–14 wt% of each specimen. In this study, we produced two data sets to investigate the formation of schreibersites in IIG irons: measurements of trace elements in the IIG iron meteorite Twannberg and experimental determinations of trace element partitioning into schreibersite. The schreibersite‐bearing experiments were conducted with schreibersite in equilibrium with a P‐rich melt and with bulk Ni contents ranging from 0 to 40 wt%. The partitioning behavior for the 20 elements measured in this study did not vary with Ni content. Comparison of the Twannberg measurements with the experimental results required a correction factor to account for the fact that the experiments were conducted in a simplified system that did not contain a solid metal phase. Previously determined solid metal/P‐rich melt partition coefficients were applied to infer schreibersite/solid metal partitioning behavior from the experiments, and once this correction was applied, the two data sets showed broad similarities between the schreibersite/solid metal distribution of elements. However, there were also differences noted, in particular between the Ni and P contents of the solid metal relative to the schreibersite inferred from the experiments compared to that measured in the Twannberg sample. These differences support previous interpretations that subsolidus schreibersite evolution has strongly influenced the Ni and P content now present in the solid metal phase of IIG irons. Quantitative attempts to match the IIG solid metal composition to that of late‐stage IIAB irons through subsolidus schreibersite growth were not successful, but qualitatively, this study corroborates the striking similarities between the IIAB and IIG groups, which are highly suggestive of a possible genetic link between the groups as has been previously proposed.     

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.     

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.     

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.

     

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.