From geometry to dynamics of microstructure: using boundary lengths to quantify boundary misorientations and anisotropy

The microstructure of a quartzite experimentally deformed and partially recrystallised at 900 °C, 1.2 GPa confining pressure and strain rate 10⁻⁶/s was investigated using orientation contrast and electron backscatter diffraction (EBSD). Boundaries between misoriented domains (grains or subgrains) were determined by image analysis of orientation contrast images. In each domain, EBSD measurements gave the complete quartz lattice orientation and enabled calculation of misorientation angles across every domain boundary. Results are analysed in terms of the boundary density, which for any range of misorientations is the boundary length for that range divided by image area. This allows a more direct comparison of misorientation statistics between different parts of a sample than does a treatment in terms of boundary number.The strain in the quartzite sample is heterogeneous. A 100×150 μm low-strain partially recrystallised subarea C was compared with a high-strain completely recrystallised subarea E. The density of high-angle (>10°) boundaries in E is roughly double that in C, reflecting the greater degree of recrystallisation. Low-angle boundaries in C and E are produced by subgrain rotation. In the low-angle range 0–10° boundary densities in both C and E show an exponential decrease with increasing misorientation. The densities scale with exp(−θ/λ) where λ is approximately 2° in C and 1° in E; in other words, E has a comparative dearth of boundaries in the 8–10° range. We explain this dearth in terms of mobile high-angle boundaries sweeping through and consuming low-angle boundaries as the latter increase misorientation through time. In E, the density of high-angle boundaries is larger than in C, so this sweeping would have been more efficient and could explain the relative paucity of 8–10° boundaries.The boundary density can be generalised to a directional property that gives the degree of anisotropy of the boundary network and its preferred orientation. Despite the imposed strain, the analysed samples show that boundaries are not, on average, strongly aligned. This is a function of the strong sinuosity of high-angle boundaries, caused by grain boundary migration. Low-angle boundaries might be expected, on average, to be aligned in relation to imposed strain but this is not found.Boundary densities and their generalisation in terms of directional properties provide objective measures of microstructure. In this study the patterns they show are interpreted in terms of combined subgrain rotation and migration recrystallisation, but it may be that other microstructural processes give distinctive patterns when analysed in this fashion.     

A mathematical model of concentrate solids content for the wet drum magnetic separator

Low concentrate density from wet drum magnetic separators in dense medium circuits can cause operating difficulties due to inability to obtain the required circulating medium density and, indirectly, high medium solids losses. The literature is almost silent on the processes controlling concentrate density. However, the common name for the region through which concentrate is discharged—the squeeze pan gap—implies that some extrusion process is thought to be at work. There is no model of magnetics recovery in a wet drum magnetic separator, which includes as inputs all significant machine and operating variables.A series of trials, in both factorial experiments and in single variable experiments, was done using a purpose built rig which featured a small industrial scale (700 mm lip length, 900 mm diameter) wet drum magnetic separator. A substantial data set of 191 trials was generated in this work. The results of the factorial experiments were used to identify the variables having a significant effect on magnetics recovery.It is proposed, based both on the experimental observations of the present work and on observations reported in the literature, that the process controlling magnetic separator concentrate density is one of drainage. Such a process should be able to be defined by an initial moisture, a drainage rate and a drainage time, the latter being defined by the volumetric flowrate and the volume within the drainage zone. The magnetics can be characterised by an experimentally derived ultimate drainage moisture. A model based on these concepts and containing adjustable parameters was developed. This model was then fitted to a randomly chosen 80% of the data, and validated by application to the remaining 20%. The model is shown to be a good fit to data over concentrate solids content values from 40% solids to 80% solids and for both magnetite and ferrosilicon feeds.     

A statistical approach to evaluating distance metrics and analog assignments for pollen records

The modern analog technique typically uses a distance metric to determine the dissimilarity between fossil and modern biological assemblages. Despite this quantitative approach, interpretation of distance metrics is usually qualitative and rules for selection of analogs tend to be ad hoc. We present a statistical tool, the receiver operating characteristic (ROC) curve, which provides a framework for identifying analogs from distance metrics. If modern assemblages are placed into groups (e.g., biomes), this method can (1) evaluate the ability of different distance metrics to distinguish among groups, (2) objectively identify thresholds of the distance metric for determining analogs, and (3) compute a likelihood ratio and a Bayesian probability that a modern group is an analog for an unknown (fossil) assemblage. Applied to a set of 1689 modern pollen assemblages from eastern North America classified into eight biomes, ROC analysis confirmed that the squared-chord distance (SCD) outperforms most other distance metrics. The optimal threshold increased when more dissimilar biomes were compared. The probability of an analog vs no-analog result (a likelihood ratio) increased sharply when SCD decreased below the optimal threshold, indicating a nonlinear relationship between SCD and the probability of analog. Probabilities of analog computed for a postglacial pollen record at Tannersville Bog (Pennsylvania, USA) identified transitions between biomes and periods of no analog.     

Desorption kinetics of radiocesium from subsurface sediments at Hanford Site, USA

The desorption of ¹³⁷Cs⁺ was investigated on sediments from the United States Hanford site. Pristine sediments and ones that were contaminated by the accidental release of alkaline ¹³⁷Cs⁺-containing high level nuclear wastes (HLW, 2 × 10⁶ to 6 × 10⁷ pCi ¹³⁷Cs⁺/g) were studied. The desorption of ¹³⁷Cs⁺ was measured in Na⁺, K⁺, Rb⁺, and NH₄⁺electrolytes of variable concentration and pH, and in presence of a strong Cs⁺-specific sorbent (self-assembled monolayer on a mesoporous support, SAMMS). ¹³⁷Cs⁺ desorption from the HLW-contaminated Hanford sediments exhibited two distinct phases: an initial instantaneous release followed by a slow kinetic process. The extent of ¹³⁷Cs⁺ desorption increased with increasing electrolyte concentration and followed a trend of Rb⁺ ≥ K⁺ > Na⁺ at circumneutral pH. This trend followed the respective selectivities of these cations for the sediment. The extent and rate of ¹³⁷Cs⁺ desorption was influenced by surface armoring, intraparticle diffusion, and the collapse of edge-interlayer sites in solutions containing K⁺, Rb⁺, or NH₄⁺. Scanning electron microscopic analysis revealed HLW-induced precipitation of secondary aluminosilicates on the edges and basal planes of micaceous minerals that were primary Cs⁺ sorbents. The removal of these precipitates by acidified ammonium oxalate extraction significantly increased the long-term desorption rate and extent. X-ray microprobe analyses of Cs⁺-sorbed micas showed that the ¹³⁷Cs⁺ distributed not only on mica edges, but also within internal channels parallel to the basal plane, implying intraparticle diffusive migration of ¹³⁷Cs⁺. Controlled desorption experiments using Cs⁺-spiked pristine sediment indicated that the ¹³⁷Cs⁺ diffusion rate was fast in Na⁺-electrolyte, but much slower in the presence of K⁺ or Rb⁺, suggesting an effect of edge-interlayer collapse. An intraparticle diffusion model coupled with a two-site cation exchange model was used to interpret the experimental results. Model simulations suggested that about 40% of total sorbed ¹³⁷Cs⁺ was exchangeable, including equilibrium and kinetic desorbable pools. At pH 3, this ratio increased to 60-80%. The remainder of the sorbed ¹³⁷Cs⁺ was fixed or desorbed at much slower rate than our experiments could detect.     

Recent Rapid Regional Climate Warming on the Antarctic Peninsula

The Intergovernmental Panel on Climate Change (IPCC) confirmed that mean global warming was 0.6 ± 0.2 °C during the 20th century and cited anthropogenic increases in greenhouse gases as the likely cause of temperature rise in the last 50 years. But this mean value conceals the substantial complexity of observed climate change, which is seasonally- and diurnally-biased, decadally-variable and geographically patchy. In particular, over the last 50 years three high-latitude areas have undergone recent rapid regional (RRR) warming, which was substantially more rapid than the global mean. However, each RRR warming occupies a different climatic regime and may have an entirely different underlying cause. We discuss the significance of RRR warming in one area, the Antarctic Peninsula. Here warming was much more rapid than in the rest of Antarctica where it was not significantly different to the global mean. We highlight climate proxies that appear to show that RRR warming on the Antarctic Peninsula is unprecedented over the last two millennia, and so unlikely to be a natural mode of variability. So while the station records do not indicate a ubiquitous polar amplification of global warming, the RRR warming on the Antarctic Peninsula might be a regional amplification of such warming. This, however, remains unproven since we cannot yet be sure what mechanism leads to such an amplification. We discuss several possible candidate mechanisms: changing oceanographic or changing atmospheric circulation, or a regional air-sea-ice feedback amplifying greenhouse warming. We can show that atmospheric warming and reduction in sea-ice duration coincide in a small area on the west of the Antarctic Peninsula, but here we cannot yet distinguish cause and effect. Thus for the present we cannot determine which process is the probable cause of RRR warming on the Antarctic Peninsula and until the mechanism initiating and sustaining the RRR warming is understood, and is convincingly reproduced in climate models, we lack a sound basis for predicting climate change in this region over the coming century.     

Stratigraphy and palynostratigraphy, Karoo Supergroup (Permian and Triassic), mid-Zambezi Valley, southern Zambia

The Karoo Supergroup outcropst in the mid-Zambezi Valley, southern Zambia. It is underlain by the Sinakumbe Group of Ordovician to Devonian age. The Lower Karoo Group (Late Carboniferous to Permian age) consists of the basal Siankondobo Sandstone Formation, which comprises three facies, overlain by the Gwembe Coal Formation with its economically important coal deposits, in turn overlain by the Madumabisa Mudstone Formation which consists of lacustrine mudstone, calcilutite, sandstone, and concretionary calcareous beds. The Upper Karoo Group (Triassic to Early Jurassic) is sub-divided into the coarsely arenaceous Escarpment Grit, overlain by the fining upwards Interbedded Sandstone and Mudstone, Red Sandstone; and Batoka Basalt Formations.Palynomorph assemblages suggest that the Siankondobo Sandstone Formation is Late Carboniferous (Gzhelian) to Early Permian (Asselian to Early Sakmarian) in age, the Gwembe Coal Formation Early Permian (Artinskian to Kungurian), the Madumabisa Mudstone Late Permian (Tatarian), and the Interbedded Sandstone and Mudstone Early or Middle Triassic (Late Scythian or Anisian). The marked quantitative variations in the assemblages are due partly to age differences, but they also reflect vegetational differences resulting from different paleoclimates and different facies.The low thermal maturity of the formations (Thermal Alteration Index 2) suggests that the rocks are oil prone. However, the general scarcity of amorphous kerogen, such as the alga Botryococcus sp., and the low proportion of exinous material, indicates a low potential for liquid hydrocarbons. Gas may have been generated, particularly in the coal seams of the Gwembe Coal Formation, that are more deeply buried.     

Nitrogen flow and the interaction of Boston harbor with Massachusetts Bay

This paper summarizes evidence that most of the considerable nitrogen loading (～8, 470 mmol total N m^?2 yr^?1) to Boston Harbor (Massachusetts, USA) is expelled to shallow shelf waters of Massachusetts Bay, where it strongly influences ecological dynamics. Examination of nitrogen concentrations in the harbor, compared with loading, indicated that removal processes are active in the harbor. Comparison to other estuarine systems showed that the harbor’s nitrogen concentrations are consistent with its loading, if they are corrected for tidal flushing effects on the water residence time. Furthermore, extensive measurements of sediment denitrification confirmed that rates of N₂ gas loss are high in an absolute sense (～600–800 mmol N m^?2 yr^?1) but nonetheless remove only a small portion (<10%) of the annual land-derived nitrogen loading. Burial in sediments apparently removes only about 2% of the N input, implying export to offshore environments as the major removal process (～88–90% of N input). Western Massachusetts Bay receiving waters were examined for a signature of export from the harbor. Data consistently show a gradient of decreasing nitrogen concentrations from the harbor to about 10–20 km into the bay. In many cases, plots of nitrogen concentrations versus salinity show nearly conservative mixing character, which implies virtual export. Seasonally, the data suggest most of the export from the harbor in winter is as dissolved inorganic forms (NH₄ ⁺, NO₃ ^?, NO₂ ^?). In summer, export is dominated by the outflow of organic nitrogen forms. Chlorophyll export is evident as well, suggesting that the nutritional coupling of the harbor and bay in summer involves organic fertilization of the bay’s surface water. Finally, high-resolution studies over different stages of the tidal cycle help refine understanding of the advection of chlorophyll and stimulation of in situ chlorophyll growth at the seaward edge of the tidal excursion into the bay.     

The Development of Laser Ablation ICP-MS and Calibration Strategies: Examples from the Analysis of Trace Elements in Volcanic Glass Shards and Sulfide Minerals

This contribution presents a review of the recent developments in laser ablation inductively coupled plasma-mass spectrometry. We describe the important developments which have occurred in the laser systems used, leading to a spatial resolution of around 20 (im, and give an overview of the major instrument developments which have affected the geological applications of laser ablation ICP-MS. We describe the calibration of laser ablation for the analysis of trace elements in two different matrices: volcanic glass shards and sulfide minerals. We show how single glass shards can be analysed using the National Institute of Standards and Technology (NIST) glass certified reference materials for calibration and demonstrate the effect of using single spot analyses compared to rastering of the calibration sample. We show the importance of inter-shard variation and demonstrate that averaged single shard analyses produce data which compare well with bulk analyses. The calibration of the laser system for sulfide mineral analysis is discussed and two different strategies are proposed, one using spiked pressed powder pellets of sulfides and the other metal reference materials. We present conclusions and recommendations for the calibration of laser ablation ICP-MS instruments.