Product study of the reaction of OH radicals with isoprene in the atmosphere simulation chamber SAPHIR

Atmospheric oxidation of isoprene and its oxidation products methacrolein (MACR) and methyl vinyl ketone (MVK) have an important impact on the photochemical activity in the boundary layer, in particular in forested areas. The oxidation of isoprene by OH radicals was investigated in chamber experiments conducted under tropospheric conditions in the atmosphere simulation chamber SAPHIR at the Research Center Jülich. The aim was to determine the product yield of MVK and MACR in the OH-induced isoprene oxidation and the rate constant of their reaction with OH under real atmospheric conditions. The recently published updated degradation scheme for isoprene from Geiger et al. (2003) was used to determine rate constants and product yields. The fractional yields in the isoprene peroxy radical reaction with NO were found to be 0.41±0.03 for MVK and 0.27±0.03 for MACR. The rate coefficient for MACR with OH was found to be in very good agreement with the recommended value of IUPAC Atkinson (Atkinson et al., 2005). while the rate coefficient for MVK with OH was 27% lower.     

Subaqueous pyroclastic flows and ignimbrites: an assessment

An assessment of the literature on subaqueous pyroclastic flows and their deposits shows that the term pyroclastic flow is frequently used loosely to describe primary, hot gas-rich pyroclastic flows, mass-flows which resulted from the transformation of gassupported flows into water-supported ones, and secondary mass-flows carrying redeposited pyroclastic debris. Based on subaerial pyroclastic flows, the term pyroclastic flow should be restricted to demonstrably hot, gas-rich mass-flows of pyroclastic debris. Using this definition, very few examples of subaqueous pyroclastic deposits with evidence for hot emplacement and of having been wholly submerged have been described. In the majority of these cases, the evidence for a hot state of emplacement and for the subaqueous nature of the host depositional environment is inadequate. The only unequivocal cases of hot pyroclastic flow deposits with adequate supporting evidence are the Ordovician nearshore, shallow marine ignimbrites of Ireland and Wales, and Miocene ignimbrites of southwest Japan, resulting from the passage of subaerially erupted pyroclastic flows into shallow water. Other possible examples are near-vent dense clast deposits in the Donzurobo Formation of Japan, possible submarine intra-caldera ponded ignimbrite successions in California and Wales, and near-vent pumiceous deposits of Ramsay Island, Wales. All other purported cases are either clearly the result of water-supported mass-flow transportation and deposition (debris avalanches, debris flows, turbidity currents), or lack adequate supporting evidence regarding the heat state or the palaeoenvironment. Only the shallow marine ignimbrites of Ireland and Wales show adequate evidence of welding, but even these could have been nearly wholly exposed above sea-level when welding occurred. We conclude that when pyroclastic flows enter water they are generally disrupted explosively and/or ingest water and transform into water-supported mass-flows, and we suggest the various scenarios in which this occurs. There is no evidence to suggest that welding in wholly subaqueous environments is common.     

Phase relations of osumilite and dehydration melting in pelitic rocks: a simple thermodynamic model for the KFMASH system

 Thermodynamic modelling of (1) osumilite solid solutions and (2) dehydration melting in pelitic compositions within the KFMASH system is quite successful in reproducing the invariant and univariant reactions determined in experimental studies. Even though rather preliminary, such melt thermodynamic models may be very useful in interpolating and extrapolating the limited information available from a small number of experimental runs. These methods allow the compositions of all phases to be monitored as a function of pressure, temperature and equilibrium phase assemblage for any desired bulk composition. Locating the higher variance phase fields (e.g. quadrivariant, quinivariant) is often difficult or impossible by inspection, but is made relatively easy using thermodynamic software such as thermocalc. In the KFMASH system the calculated partition of Fe and Mg between osumilite, garnet, cordierite, orthopyroxene and biotite are shown to be in good agreement with experimental and natural data and allow reliable calculation of mineral compositions coexisting with quartz-saturated and H₂O-undersaturated melts for a variety of bulk compositions. These phase diagram calculations allow quite tight limits to be placed on the pressure, temperature and water activity conditions which accompanied metamorphism of natural osumilite occurrences in Nain, Namaqualand, and Rogaland. At fixed bulk composition, the initial melting of pelites by dehydration of biotite can occur via univariant, divariant or trivariant equilibria depending upon pressure of metamorphism. Of particular interest is that, for low pressures or more magnesian bulk compositions, fluid-absent melting begins by generating liquid from the high-variance assemblage biotite+cordierite+K-feldspar+ quartz. This type of modelling allows investigation, at least qualitatively, of the fine scale details of melt production as a function of changes in pressure, temperature and bulk composition. Received: 29 November 1995 / Accepted: 22 April 1996     

Geoacoustic Characterisation of Fine-grained Sediments using Single and Multiple Reflection Data

Fine-grained sediments commonly occur in areas of the continental shelf where wave and current energy are weak. Bulk density, compressional wave speed and attenuation are fundamental physical properties of these sediments required for predicting the response of the seabed for diverse branches of marine science. The traditional coring approach is time and labor-intensive, with large uncertainties associated with sediment disturbance in the sampling phase. Acoustic methods offer the advantages of remote sensing, i.e., sampling the sediment structure without mechanical disturbance and a significantly larger seabed coverage rate per unit time. Two different acoustic methods are described: one using short-range single-bounce interactions with the seabed, and the second using long-range modal propagation to infer the sediment properties. The relative strengths and sensitivities of each approach are explored through simulations guided by experience with measured data.     

A review of the physics and ecological implications of the thermal bar circulation

Following recent applications of numerical modelling and remote sensing to the thermal bar phenomenon, this paper seeks to review the current state of knowledge on the effect of its circulation on lacustrine plankton ecosystems. After summarising the literature on thermal bar hydrodynamics, a thorough review is made of all plankton observations taken in the presence of a thermal bar. Two distinct plankton growth regimes are found, one with production favoured throughout the inshore region and another with a maximum in plankton biomass near the position of the thermal bar. Possible explanations for the observed distributions are then discussed, with reference to numerical modelling studies, and the scope for future study of this interdisciplinary topic is outlined.     

Stratigraphic Model Predictions of Geoacoustic Properties

Geoacoustic properties of the seabed have a controlling role in the propagation and reverberation of sound in shallow-water environments. Several techniques are available to quantify the important properties but are usually unable to adequately sample the region of interest. In this paper, we explore the potential for obtaining geotechnical properties from a process-based stratigraphic model. Grain-size predictions from the stratigraphic model are combined with two acoustic models to estimate sound speed with distance across the New Jersey continental shelf and with depth below the seabed. Model predictions are compared to two independent sets of data: 1) Surficial sound speeds obtained through direct measurement using in situ compressional wave probes, and 2) sound speed as a function of depth obtained through inversion of seabed reflection measurements. In water depths less than 100 m, the model predictions produce a trend of decreasing grain-size and sound speed with increasing water depth as similarly observed in the measured surficial data. In water depths between 100 and 130 m, the model predictions exhibit an increase in sound speed that was not observed in the measured surficial data. A closer comparison indicates that the grain-sizes predicted for the surficial sediments are generally too small producing sound speeds that are too slow. The predicted sound speeds also tend to be too slow for sediments 0.5-20 m below the seabed in water depths greater than 100 m. However, in water depths less than 100 m, the sound speeds between 0.5-20-m subbottom depth are generally too fast. There are several reasons for the discrepancies including the stratigraphic model was limited to two dimensions, the model was unable to simulate biologic processes responsible for the high sound-speed shell material common in the model area, and incomplete geological records necessary to accurately predict grain-size     

Calculation of partial melting equilibria in the system Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O (NCKFMASH)

A thermodynamic model for haplogranitic melts in the system Na₂O–CaO–K₂O–Al₂O₃–SiO₂–H₂O (NCKASH) is extended by the addition of FeO and MgO, with the data for the additional end‐members of the liquid incorporated in the Holland & Powell (1998) internally consistent thermodynamic dataset. The resulting dataset, with the software thermocalc , is then used to calculate melting relationships for metapelitic rock compositions. The main forms for this are P–T and T–X pseudosections calculated for particular rock compositions and composition ranges. The relationships in these full‐system pseudosections are controlled by the low‐variance equilibria in subsystems of NCKFMASH. In particular, the solidus relationships are controlled by the solidus relationships in NKASH, and the ferromagnesian mineral relationships are controlled by those in KFMASH. However, calculations in NCKFMASH allow the relationships between the common metapelitic minerals and silicate melt to be determined. In particular, the production of silicate melt and melt loss from such rocks allow observations to be made about the processes involved in producing granulite facies rocks, particularly relating to open‐system behaviour of rocks under high‐grade conditions.     

Iodine-xenon analysis of Chainpur (LL3.4) chondrules

We present I-Xe analyses of ten chondrules from Chainpur LL3.4 by IR laser-stepped heating. Five chondrules provided isochrons of varying quality, giving a range of ages from 0.5 Ma before Shallowater to 17.8 after Shallowater. This confirms the extended range of Chainpur chondrule ages determined by previous data. We discuss evidence for fluid alteration, shock, and thermal events in explaining the chondrule ages and suggest that chondrule remelting events, presumably from bombardment of the parent body surface, are responsible for resetting the I-Xe chronometer. Previous data show a negative correlation between ¹³²Xe/¹²⁹Xe of the trapped Xe component and ¹²⁷I/¹²⁹I of an initial iodine component. This behaviour that requires the presence of a component with trapped ¹²⁹Xe/¹³²Xe lower than the planetary value has been cited as evidence for closed system evolution of the I-Xe system. We find no evidence of an unambiguous trapped component lower than planetary and no evidence of a negative correlation in our data. Therefore we suggest that open system behaviour more suitably explains the I-Xe systematics of Chainpur chondrules.     

Agents of landscape change in southern New Zealand, 1896–1920

The records of two large stock and station agents, Loan & Mercantile Agency in Dunedin and Wright Stephenson in Invercargill, allowed us to track the timing, nature, magnitude and rate of landscape change in southern New Zealand between 1896 and 1920. This period extends from the final years of subdivision of large estates, and includes closer settlement, the shift from pastoral farming to intensive agriculture, growth of dairying, and increasing mechanisation of agriculture. These changes are reflected in clients’ annual expenditures on capital items such as fencing and building materials, tools and implements, materials for drains.