2,024 research outputs found

    Picosecond fluorescence of intact and dissolved PSI-LHCI crystals

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    Over the last years many crystal structures of photosynthetic pigment-protein complexes have been determined, and used extensively to model spectroscopic results obtained on the same proteins in solution. However, the crystal structure is not necessarily identical to the structure of the protein in solution. Here we studied picosecond fluorescence of Photosystem I-Light Harvesting Complex I (PSI-LHCI), a multisubunit pigment protein complex that catalyzes the first steps of photosynthesis. The ultrafast fluorescence of PSI-LHCI crystals is identical to that of dissolved crystals, but differs considerably from most kinetics presented in literature. In contrast to most studies, the present data can be modeled quantitatively with only 2 compartments: PSI core and LHCI. This yields the rate of charge separation from an equilibrated core (22.5+/-2.5 ps) and rates of excitation energy transfer from LHCI to core (kLC) and vice versa (kCL). The ratio R=kCL/kLC between these rates appears to be wavelength-dependent and scales with the ratio of the absorption spectra of LHCI and core, indicating the validity of a detailed balance relation between both compartments. kLC depends slightly but non systematically on detection wavelength, averaging (9.4+/-4.9 ps)(-1). R ranges from 0.5 (below 690 nm) to around 1.3 above 720 nm

    Constraints on the evolution of Taranaki Fault from thermochronology and basin analysis: Implications for the Taranaki Fault play

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    Taranaki Fault is the major structure defining the eastern margin of Taranaki Basin and marks the juxtaposition of basement with the Late Cretaceous-Paleogene succession in the basin. Although the timing of the basement over-thrusting on Taranaki Fault and subsequent marine onlap on to the basement block are well constrained as having occurred during the Early Miocene, the age of formation of this major structure, its character, displacement history and associated regional vertical movement during the Late Cretaceous- Recent are otherwise poorly known. Here we have applied (i) apatite fission track thermochronology to Mesozoic basement encountered in exploration holes and in outcrop to constrain the amount and timing of Late Cretaceous-Eocene exhumation of the eastern side of the fault, (ii) basin analysis of the Oligocene and Miocene succession east of the fault to establish the late-Early Miocene - Early Pliocene subsidence history, and (iii), regional porosity-bulk density trends in Neogene mudstone to establish the late uplift and tilting of eastern Taranaki Basin margin, which may have been associated with the main period of charge of the underlying Taranaki Fault play. We make the following conclusions that may be useful in assessing the viability of the Taranaki Fault play. (1) Mid-Cretaceous Taniwha Formation, intersected in Te Ranga-1 was formerly extensive across the western half of the Kawhia Syncline between Port Waikato and Awakino. (2) Taranaki Fault first formed as a normalfault during the Late Cretaceous around 85±10 Ma, and formed the eastern boundary of the Taranaki Rift-Transform basin. (3) Manganui Fault, located onshore north of Awakino, formed as a steeply east dipping reverse fault and accommodated about four km of displacement during the mid-Cretaceous. (4) Uplift and erosion, involving inversion of Early Oligocene deposits, occurred along the Herangi High during the Late Oligocene. This may have been associated with initial reverse movement on Taranaki Fault. (5) During the Early Miocene (Otaian Stage) the Taranaki and Manganui Faults accommodated the westward transport of Murihiku basement into the eastern margin of Taranaki Basin, but the amount of topography generated over the Herangi High can only have been a few hundred metres in elevation. (6) The Altonian (19-16 Ma) marked the start of the collapse of the eastern margin of Taranaki Basin that lead during the Middle Miocene to the eastward retrogradation of the continental margin wedge into the King Country region. During the Late Miocene, from about 11 Ma, a thick shelf-slope continental margin wedge prograded northward into the King Country region and infilled it (Mt Messenger, Urenui, Kiore and Matemateaonga Formations). (7) During the Pliocene and Pleistocene the whole of central New Zealand, including the eastern margin of Taranaki Basin, became involved in long wavelength up-doming with 1-2 km erosion of much of the Neogene succession in the King Country region. This regionally elevated the Taranaki Fault play into which hydrocarbons may have migrated from the Northern Graben region

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

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    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.

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    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

    Neogene stratigraphic architecture and tectonic evolution of Wanganui, King Country, and eastern Taranaki Basins, New Zealand

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    Analysis of the stratigraphic architecture of the fills of Wanganui, King Country, and eastern Taranaki Basins reveals the occurrence of five 2nd order Late Paleocene and Neogene sequences of tectonic origin. The oldest is the late Eocene-Oligocene Te Kuiti Sequence, followed by the early-early Miocene (Otaian) Mahoenui Sequence, followed by the late-early Miocene (Altonian) Mokau Sequence, all three in King Country Basin. The fourth is the middle Miocene to early Pliocene Whangamomona Sequence, and the fifth is the middle Pliocene-Pleistocene Rangitikei Sequence, both represented in the three basins. Higher order sequences (4th, 5th, 6th) with a eustatic origin occur particularly within the Whangamomona and Rangitikei Sequences, particularly those of 6th order with 41 000 yr periodicity

    Mechanism of Fluoride Uptake by Hydroxyapatite from Acidic Fluoride Solutions: I. Theoretical Considerations

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    A mathematical model for the mechanism of calcium fluoride formation on hydroxyapatite in buffered fluoride solutions is proposed. It takes into account the physical and chemical processes that occur during the reaction. With the model it is possible to evaluate a priori the fluoride uptake potential of fluoride solutions.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/67263/2/10.1177_00220345700490066601.pd

    Observation of the Smectic C -- Smectic I Critical Point

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    We report the first observation of the smectic C--smectic I (C--I) critical point by Xray diffraction studies on a binary system. This is in confirmity with the theoretical idea of Nelson and Halperin that coupling to the molecular tilt should induce hexatic order even in the C phase and as such both C and I (a tilted hexatic phase) should have the same symmetry. The results provide evidence in support of the recent theory of Defontaines and Prost proposing a new universality class for critical points in layered systems.Comment: 9 pages Latex and 5 postscript figures available from [email protected] on request, Phys.Rev.Lett. (in press

    Urate production by human heart

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    Xanthine oxidoreductase has been demonstrated in the heart of various species. However, its presence in human heart is still debated. In the literature, high to undetectable levels have been reported. We studied the arterial-venous urate difference across the heart of patients undergoing both routine cardiac catheterization and percutaneous transluminal coronary angioplasty. Urate is the end product of the reaction catalysed by xanthine oxidoreductase. In 10 patients, studied before angioplasty, the plasma urate level in the great cardiac vein exceeded the arterial one by 26 +/- 10 nmol/ml (P = 0.028). In a further 13 patients, urate production was maximal immediately after the last of four consecutive occlusions (23 +/- 8 nmol/ml, P = 0.018) and concomitant with increased coronary sinus hypoxanthine levels. We conclude that xanthine oxidoreductase is probably present in the heart of patients, suffering from ischemic heart disease, and responsible for the increase in urate production during transient myocardial ischemia
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