Growth and magnetic properties of MnO2−delta nanowire microspheres

We report the synthesis of MnO2−delta microspheres using hydrothermal and conventional chemical reaction methods. The microspheres of MnO2−delta consist of nanowires having a diameter of 20-50 nm and a length of 2-8 micro m. The value of the oxygen vacancy delta estimated from the x-ray photoelectron spectrum (XPS) is 0.3. The magnetization versus temperature curve indicates a magnetic transition at about 13 K. It is found that a parasitic ferromagnetic component is imposed on the antiferromagnetic structure of MnO2−delta, which might result from distortion of the lattice structure due to oxygen vacancies. The magnetic transition temperature TN is about 10 K lower than that of the bulk MnO2 single crystal

Algorithmic Debugging of Real-World Haskell Programs: Deriving Dependencies from the Cost Centre Stack

Existing algorithmic debuggers for Haskell require a transformation of all modules in a program, even libraries that the user does not want to debug and which may use language features not supported by the debugger. This is a pity, because a promising ap- proach to debugging is therefore not applicable to many real-world programs. We use the cost centre stack from the Glasgow Haskell Compiler profiling environment together with runtime value observations as provided by the Haskell Object Observation Debugger (HOOD) to collect enough information for algorithmic debugging. Program annotations are in suspected modules only. With this technique algorithmic debugging is applicable to a much larger set of Haskell programs. This demonstrates that for functional languages in general a simple stack trace extension is useful to support tasks such as profiling and debugging

Megasequence architecture of Taranaki, Wanganui, and King Country basins and Neogene progradation of two continental margin wedges across western New Zealand.

Taranaki, Wanganui and King Country basins (formerly North Wanganui Basin) have been regarded as discrete basins, but they contain a very similar Neogene sedimentary succession and much of their geological history is held in common. Analysis of the stratigraphic architecture of the fill of each basin reveals the occurrence of four 2nd order megasequences of tectonic origin. The oldest is the early-early Miocene (Otaian Stage) Mahoenui Group/megasequence, followed by the late-early Miocene (Altonian Stage) Mokau Group/megasequence (King Country Basin), both of which correspond to the lower part of the Manganui Formation in Taranaki Basin. The third is the middle to late Miocene Whangamomona Group/megasequence, and the fourth is the latest Miocene-Pleistocene Rangitikei Supergroup/megasequence, both represented in the three basins. Higher order sequences (4th, 5th, 6th), having a eustatic origin, are evident in the Whangamomona and Rangitikei megasequences, particularly those of 5th order with 41 ka periodicity. The distribution of the megasequences are shown in a series of cross-section panels built-up from well -to-well correlations, complemented by time-stratigraphic cross-sections. The base of each megasequence is marked by marine flooding and represents a discrete phase in basin development. For the first megasequence this corresponded to rapid subsidence of the King Country Basin in a compressional setting and basement overthrusting on the Taranaki Fault, with the rapid introduction of terrigenous sediment during transgression. The Mahoenui megasequence accumulated mostly at bathyal depths; no regressive deposits are evident, having been eroded during subsequent uplift. The second (Mokau) megasequence accumulated during reverse movement on the Ohura Fault, formation of the Tarata Thrust Zone, and onlap of the basement block between the Taranaki Fault and the Patea-Tongaporutu-Herangi High (PTH). The Whangamomona megasequence accumulated during extensive reflooding of King Country Basin, onlap of the PTH High and of basement in the Wanganui Basin. This is an assymetrical sequence with a thin transgressive part (Otunui Formation) and a thick regressive part (Mount Messenger to Matemateaonga Formations). It represents the northward progradation of a continental margin wedge with bottom-set, slope-set and top-set components through Wanganui and King Country basins, with minor progradation over the PTH High and into Taranaki Basin. The Rangitikei megasequence is marked by extensive flooding at its base (Tangahoe Mudstone) and reflects the pull-down of the main Wanganui Basin depocentre. This megasequence comprises a second progradational margin wedge, which migrated on two fronts, one northward through Wanganui Basin and into King Country Basin, and a second west of the PTH High, through the Toru Trough and into the Central and Northern Grabens of Taranaki Basin and on to the Western Platform as the Giant Foresets Formation, thereby building up the modern shelf and slope. Fifth and 6th order sequences are well expressed in the shelf deposits (top-sets) of the upper parts of the Whangamomona and Rangitikei megasequences. They typically have a distinctive sequence architecture comprising shellbed (TST), siltstone (HST) and sandstone (RST) beds. Manutahi-1, which was continuously cored, provides calibration of this sequence architecture to wireline log character, thereby enabling shelf deposits to be mapped widely in the subsurface via the wireline data for hydrocarbon exploration holes. Similar characterization of slope-sets and bottom-sets is work ongoing. The higher order (eustatic) sequences profoundly influenced the local reservoir architecture and seal properties of formations, whereas the megasequence progradation has been responsible for the regional hydrocarbon maturation and migration. Major late tilting, uplift and erosion affected all three basins and created a regional high along the eastern Margin of Taranaki Basin, thereby influencing the migration paths of hydrocarbons sourced deeper in the basin and allowing late charge of structural and possibly stratigraphic traps

Megasequence architecture of Taranaki, Wanganui, and King Country basins and Neogene progradation of two continental margin wedges across western New Zealand.

Taranaki, Wanganui and King Country basins (formerly North Wanganui Basin) have been regarded as discrete basins, but they contain a very similar Neogene sedimentary succession and much of their geological history is held in common. Analysis of the stratigraphic architecture of the fill of each basin reveals the occurrence of four 2nd order megasequences of tectonic origin. The oldest is the early-early Miocene (Otaian Stage) Mahoenui Group/megasequence, followed by the late-early Miocene (Altonian Stage) Mokau Group/megasequence (King Country Basin), both of which correspond to the lower part of the Manganui Formation in Taranaki Basin. The third is the middle to late Miocene Whangamomona Group/megasequence, and the fourth is the latest Miocene-Pleistocene Rangitikei Supergroup/megasequence, both represented in the three basins. Higher order sequences (4th, 5th, 6th), having a eustatic origin, are evident in the Whangamomona and Rangitikei megasequences, particularly those of 5th order with 41 ka periodicity. The distribution of the megasequences are shown in a series of cross-section panels built-up from well -to-well correlations, complemented by time-stratigraphic cross-sections. The base of each megasequence is marked by marine flooding and represents a discrete phase in basin development. For the first megasequence this corresponded to rapid subsidence of the King Country Basin in a compressional setting and basement overthrusting on the Taranaki Fault, with the rapid introduction of terrigenous sediment during transgression. The Mahoenui megasequence accumulated mostly at bathyal depths; no regressive deposits are evident, having been eroded during subsequent uplift. The second (Mokau) megasequence accumulated during reverse movement on the Ohura Fault, formation of the Tarata Thrust Zone, and onlap of the basement block between the Taranaki Fault and the Patea-Tongaporutu-Herangi High (PTH). The Whangamomona megasequence accumulated during extensive reflooding of King Country Basin, onlap of the PTH High and of basement in the Wanganui Basin. This is an assymetrical sequence with a thin transgressive part (Otunui Formation) and a thick regressive part (Mount Messenger to Matemateaonga Formations). It represents the northward progradation of a continental margin wedge with bottom-set, slope-set and top-set components through Wanganui and King Country basins, with minor progradation over the PTH High and into Taranaki Basin. The Rangitikei megasequence is marked by extensive flooding at its base (Tangahoe Mudstone) and reflects the pull-down of the main Wanganui Basin depocentre. This megasequence comprises a second progradational margin wedge, which migrated on two fronts, one northward through Wanganui Basin and into King Country Basin, and a second west of the PTH High, through the Toru Trough and into the Central and Northern Grabens of Taranaki Basin and on to the Western Platform as the Giant Foresets Formation, thereby building up the modern shelf and slope. Fifth and 6th order sequences are well expressed in the shelf deposits (top-sets) of the upper parts of the Whangamomona and Rangitikei megasequences. They typically have a distinctive sequence architecture comprising shellbed (TST), siltstone (HST) and sandstone (RST) beds. Manutahi-1, which was continuously cored, provides calibration of this sequence architecture to wireline log character, thereby enabling shelf deposits to be mapped widely in the subsurface via the wireline data for hydrocarbon exploration holes. Similar characterization of slope-sets and bottom-sets is work ongoing. The higher order (eustatic) sequences profoundly influenced the local reservoir architecture and seal properties of formations, whereas the megasequence progradation has been responsible for the regional hydrocarbon maturation and migration. Major late tilting, uplift and erosion affected all three basins and created a regional high along the eastern Margin of Taranaki Basin, thereby influencing the migration paths of hydrocarbons sourced deeper in the basin and allowing late charge of structural and possibly stratigraphic traps

An integrated sequence stratigraphic, palaeoenvironmental, and chronostratigraphic analysis of the Tangahoe Formation, southern Taranaki coast, with implications for mid-Pliocene (c. 3.4–3.0 Ma) glacio-eustatic sea-level changes

Sediments of the mid-Pliocene (c. 3.4–3.0 Ma) Tangahoe Formation exposed in cliffs along the South Taranaki coastline of New Zealand comprise a 270 m thick, cyclothemic shallow-marine succession that has been gently warped into a north to south trending, low angle anticline. This study examines the sedimentologic, faunal, and petrographic characteristics of 10 Milankovitch-scale (6th order), shallow-marine depositional sequences exposed on the western limb of the anticline. The sequences are recognised on the basis of the cyclic vertical stacking of their constituent lithofacies, which are bound by sharp wave cut surfaces produced during transgressive shoreface erosion. Each sequence comprises three parts: (1) a 0.2–2 m thick, deepening upwards, basal suite of reworked bioclastic lag deposits (onlap shellbed) and/or an overlying matrix supported, molluscan shellbed of offshore shelf affinity (backlap shellbed); (2) a 5–20 m thick, gradually shoaling, aggradational siltstone succession; and (3) a 5–10 m thick, strongly progradational, well sorted “forced regressive” shoreline sandstone. The three-fold subdivision corresponds to transgressive, highstand, and regressive systems tracts (TSTs, HSTs, and RSTs) respectively, and represents deposition during a glacio-eustatic sea-level cycle. Lowstand systems tract sediments are not recorded because the outcrop is situated c. 100 km east of the contemporary shelf edge and was subaerially exposed at that time. Well developed, sharp- and gradational-based forced regressive sandstones contain a variety of storm-emplaced sedimentary structures, and represent the rapid and abrupt basinward translation of the shoreline on to a storm dominated, shallow shelf during eustatic sea-level fall. Increased supply of sediment from north-west South Island during “forced regression” is indicated from petrographic analyses of the heavy mineralogy of the sandstones. A chronology based on biostratigraphy and the correlation of a new magnetostratigraphy to the magnetic polarity timescale allows: (1) identification of the Mammoth (C2An.2r) and Kaena (C2An.1r) subchrons; (2) correlation of the coastal section to the Waipipian Stage; and (3) estimation of the age of the coastal section as 3.36–3.06 Ma. Qualitative assessment of foraminiferal census data and molluscan palaeoecology reveals cyclic changes in water depth from shelf to shoreline environments during the deposition of each sequence. Seven major cycles in water depth of between 20 and 50m have been correlated to individual 40 ka glacio-eustatic sea-level cycles on the marine oxygen isotope timescale. The coastal Tangahoe Formation provides a shallow-marine record of global glacio-eustasy prior to the development of significant ice sheets on Northern Hemisphere continents, and supports evidence from marine δ18O archives that changes in Antarctic ice volume were occurring during the Pliocene

Pliocene-Pleistocene marine cyclothems, Wanganui Basin, New Zealand: a lithostratigraphic framework

The Rangitikei River valley between Mangaweka and Vinegar Hill and the surrounding Ohingaiti region in eastern Wanganui Basin contains a late Pliocene to early Pleistocene (c. 2.6-1.7 Ma), c. 1100 m thick, southward-dipping (4-9deg.), marine cyclothemic succession. Twenty sedimentary cycles occur within the succession, each of which contains coarse-grained (siliciclastic sandstone and coquina) and fine-grained (siliciclastic siltstone) units. Nineteen of the cycles are assigned to the Rangitikei Group (new). Six new formations are defined within the Rangitikei Group, and their distribution in the Ohingaiti region is represented in a new geologic map. The new formations are named: Mangarere, Tikapu, Makohine, Orangipongo, Mangaonoho, and Vinegar Hill. Each formation comprises one or more cyclothems and includes a previously described and named distinctive basal horizon. Discrete sandstones, siltstones, and coquinas within formations are assigned member status and correspond to systems tracts in sequence stratigraphic nomenclature. The members provide the link between the new formational lithostratigraphy and the sequence stratigraphy of the Rangitikei Group. Base of cycle coquina members accumulated during episodes of sediment starvation associated with stratigraphic condensation on an open marine shelf during sea-level transgressions. Siltstone members accumulated in mid-shelf environments (50-100 m water depth) during sea-level highstands, whereas the overlying sandstone members are ascribed to inner shelf and shoreface environments (0-50 m water depth) and accumulated during falling eustatic sea-level conditions. Repetitive changes in water depth of 50-100 m magnitude are consistent with a glacio-eustatic origin for the cyclothems, which correspond to an interval of Earth history when successive glaciations in the Northern Hemisphere are known to have occurred. Moreover, the chronology of the Rangitikei River section indicates that Rangitikei Group cyclothems accumulated during short duration, 41 ka cycles in continental ice volume attributed to the dominance of the Milankovitch obliquity orbital parameter. The Ohingaiti region has simple postdepositional structure. The late Pliocene formations dip generally to the SSW between 4deg. and 9deg.. Discernible discordances of c. 1deg. between successively younger formations are attributed to synsedimentary tilting of the shelf concomitant with migration of the tectonic hingeline southward into the basin. The outcrop distribution of the Rangitikei Group is strongly influenced by this regional tilt and also by three major northeast-southwest oriented, high-angle reverse faults (Rauoterangi, Pakihikura, and Rangitikei Faults)

Petrogenesis of diachronous mixed siliciclastic-carbonate megafacies in the cool-water Oligocene Tikorangi Formation, Taranaki Basin, New Zealand

The Oligocene (Whaingaroan-Waitakian) Tikorangi Formation is a totally subsurface, lithostratigraphically complex, mixed siliciclastic-limestone-rich sequence forming an important fracture reservoir within Taranaki Basin, New Zealand. Petrographically the formation comprises a spectrum of interbedded rock types ranging from calcareous mudstone to wackestone to packstone to clean sparry grainstone. Skeletal and textural varieties within these rock types have aided in the identification of three environmentally distinctive megafacies for the Tikorangi Formation rocks-shelfal, foredeep, and basinal. Data from these megafacies have been used to detail previous conclusions on the petrogenesis and to further refine depositional paleoenvironmental models for the Tikorangi Formation in the central eastern Taranaki Basin margin.Shelfal Megafacies 1 rocks (reference well Hu Road-1A) are latest Oligocene (early Waitakian) in age and formed on or proximal to the Patea-Tongaporutu-Herangi basement high. They are characterised by coarse, skeletal-rich, pure sparry grainstone comprising shallow water, high energy taxa (bryozoans, barnacles, red algae) and admixtures of coarse well-rounded lithic sand derived from Mesozoic basement greywacke. This facies type has previously gone unrecorded in the Tikorangi Formation. Megafacies 2 is a latest Oligocene (early Waitakian) foredeep megafacies (formerly named shelfal facies) formed immediately basinward and west of the shelfal basement platform. It accumulated relatively rapidly (>20 cm/ka) from redeposition of shelfal megafacies biota that became intermixed with bathyal taxa to produce a spectrum of typically mudstone through to sparry grainstone. The resulting skeletal mix (bivalve, echinoderm, planktic and benthic foraminiferal, red algal, bryozoan, nannofossil) is unlike that in any of the age-equivalent limestone units in neighbouring onland King Country Basin. Megafacies 3 is an Oligocene (Whaingaroan-Waitakian) offshore basinal megafacies (formerly termed bathyal facies) of planktic foraminiferal-nannofossil-siliciclastic wackestone and mudstone formed away from redepositional influences. The siliciclastic input in this distal basinal setting (sedimentation rates <7 mm/ka) was probably sourced mainly from oceanic currents carrying suspended sediment from South Island provenances exposed at this time.Tikorangi Formation rocks record the Taranaki Basin’s only period of carbonate-dominated sedimentation across a full range of shelfal, foredeep, and basinal settings. Depositional controls on the three contrasting megafacies were fundamentally the interplay of an evolving and complex plate tectonic setting, including development of a carbonate foredeep, changes in relative sea level within an overall transgressive regime, and changing availability, sources, and modes of deposition of both bioclastic and siliciclastic sediments. The mixed siliciclastic-carbonate nature of the formation, and its skeletal assemblages, low-Mg calcite mineralogy, and delayed deep burial diagenetic history, are features consistent with formation in temperate-latitude cool waters

A pilot study of the manual force levels required to produce manipulation induced hypoalgesia

Objective. A pilot investigation of the influence of different force levels on a treatment technique's hypoalgesic effect. Design. Randomised single blind repeated measures. Background. Optimisation of such biomechanical treatment variables as the point of force application, direction of force application and the level of applied manual force is classically regarded as the basis of best practice manipulative therapy. Manipulative therapy is frequently used to alleviate pain, a treatment effect that is often studied directly in the neurophysiological, paradigm and seldom in biomechanical research. The relationship between the level of force applied by a technique (e.g. biomechanics) and its hypoalgesic effect was the focus of this study. Method. The experiment involved the application of a lateral glide mobilisation with movement treatment technique to the symptomatic elbow of six subjects with lateral epicondylalgia. Four different levels of force, which were measured with a flexible pressure-sensing mat, were randomly applied while the subject performed a pain free grip strength test. Results. Standardised manual force data varied from 0.76 to 4.54 N/cm, lower-upper limits 95 Cl, respectively. Pain free grip strength expressed as a percentage change from pre-treatment values was significantly greater with manual forces beyond 1.9 N/cm (P = 0.014). Conclusions. This study, albeit a pilot, provides preliminary evidence that in terms of the hypoalgesic effect of a mobilisation with movement treatment technique, there may be an optimal level of applied manual force

Late Holocene palynology and palaeovegetation of tephra-bearing mires at Papamoa and Waihi Beach, western Bay of Plenty, North Island, New Zealand.

The vegetation history of two mires associated with Holocene dunes near the western Bay of Plenty coast, North Island, New Zealand, is deduced from pollen analysis of two cores. Correlation of airfall tephra layers in the peats, and radiocarbon dates, indicate that the mires at Papamoa and Waihi Beach are c. 4600 and c. 2900 conventional radiocarbon years old, respectively. Tephras used to constrain the chronology of the pollen record include Rotomahana (1886 AD), Kaharoa (700 yr B.P.), Taupo (Unit Y; 1850 yr B.P.), Whakaipo (Unit V; 2700 yr B.P.), Stent (Unit Q; 4000 yr B.P.), Hinemaiaia (Unit K; 4600 yr B.P.), and reworked Whakatane (c. 4800 yr B.P.) at Papamoa, and Kaharoa and Taupo at Waihi Beach. Peat accumulation rates at Papamoa from 4600 - 1850 yr B.P. range from 0.94 to 2.64 mm/yr (mean 1.37 mm/yr). At Waihi Beach, from 2900 yr B.P. - present day, they range from 0.11 to 0.21 mm/yr (mean 0.20 mm/yr). Peat accumulation at both sites was slowest from 1850 to 700 yr B.P., suggesting a drier overall climate during this interval. At both sites, the earliest organic sediments, which are underlain by marine or estuarine sands, yield pollen spectra indicating salt marsh or estuarine environments. Coastal vegetation communities declined at both sites, as sea level gradually fell or the coast prograded, and were eventually superseded by a low moor bog at Papamoa, and a mesotrophic swamp forest at Waihi Beach. These differences, and the marked variation in peat accumulation rates, probably reflect local hydrology and are unlikely to have been climatically controlled. The main regional vegetation during this period was mixed northern conifer-angiosperm forest. Kauri (Agathis australis) formed a minor component of these forests, but populations of this tree have apparently not expanded during the late Holocene at these sites, which are near its present southern limit. Occasional shortlived forest disturbances are detectable in these records, in particular immediately following the deposition of Taupo Tephra. However, evidence for forest clearance during the human era is blurred by the downward dislocation of modern adventi ve pollen at these sites, preventing the clear differentiation of the Polynesian and European eras