The photo-oxidations of propyl acetates in synthetic air-HONO-NO x mixtures: Product formation studies and proposed kinetic mechanisms     

J. Alistair Kerr  David W. Stocker 《Journal of Atmospheric Chemistry》1986,4(2):263-276

The formation of products following the hydroxyl radical initiated photo-oxidations of n-and isopropyl acetates has been studied. Mixtures of synthetic air containing a few ppm of nitrous acid, nitric oxide, nitrogen dioxide and one of the propyl acetates were irradiated with sunlamps in a Teflon bag smog chamber. The decay of reactants and the formation of products was monitored by chemiluminescent analysis or by gas chromatography. The major primary products from the photo-oxidation of n-propyl acetate are acetaldehyde and propionaldehyde while from isopropyl acetate they are acetone and methyl nitrate. It was not possible to analyse for formaldehyde, an expected primary product in these systems. The nature and distribution of products indicate that a significant fraction of primary products arise from decomposition reactions of the alkoxy-type radicals generated following the initial attack of hydroxyl radicals on the esters. The derived reaction stoichiometries (molecules of NO oxidised per molecule of ester reacted) are also consistent with the proposed mechanisms.  相似文献   

Metasomatism of a depleted granulite facies terrain in the Arunta Block,central Australia     

Alistair R. Allen 《Contributions to Mineralogy and Petrology》1979,71(1):85-98

Geochemical investigations in the Utralanama Block, an intermediate pressure granulite facies terrain in the Arunta Block, central Australia, has revealed several anomalous features, not consistent with the depletion of granitophile components generally considered to accompany granulite facies metamorphism. However, other geochemical features are indicative of depletion. The mean K₂O for the Utralanama Block is exceptionally low relative to most other granulite facies terrains, but Rb contents are comparatively high. Consequently, the mean K/Rb ratio is relatively low for granulite facies terrains as is the mean Ba/Rb ratio, whilst mean K/Sr and Rb/Sr ratios are much higher than usual for such terrains. Only the K/Ba ratio shows equivalent values to depleted terrains elsewhere.Comparison of these ratios for the three main compositional groups of rocks in the Utralanama Block reveals that for mafic rocks all the above ratios are characteristic of extreme depletion, whereas, for all but the K/Ba ratio, mean ratios for the pelitic rocks, and to a lesser extent for the quartzofeldspathic rocks approach normal crustal values or values for metasomatic rocks. The abnormally high Rb/Sr ratios of these rocks compared to average crustal rocks suggest, however, that metasomatism is the cause of the anomalous geochemical features of the Utralanama Block, and this is supported by field and microstructural evidence. Thus, Rb/Sr ratios appear to be useful indicators of metasomatism where no gross mineralogical or microstructural evidence for metasomatism is obvious, and under such conditions the K/Ba ratio may be more reliable than the K/Rb ratio for indicating prior depletion of the terrain.  相似文献   

High-Pressure (~2000 MPa) Kyanite- and Glaucophane-bearing Pelitic Schist and Eclogite from Cordillera de la Costa Belt, Venezuela   总被引：4，自引：0，他引：4       下载免费PDF全文

Sisson  Virginia B.; Ertan  Inci Evren; Lallemant  Hans G. Ave 《Journal of Petrology》1997,38(1):65-83

Cretaceous melange of the Cordillera de la Costa belt, north–centralVenezuela, there are knockers of eclogite, barroisite-bearingeclogite, and pelitic glaucophane schist. These occur in a metamorphicmelange matrix that locally consists of marble, serpentinite,amphibolite, actinolite schist, feldspathic schist and gneiss,graphitic schist, chloritoid schist, and garnet-bearing micaschist. The protoliths for these various rock types exhibita wide age range (Cambrian to Early Cretaceous?). Recently discoveredknockers of pelitic glaucophane schist contain Mg-glaucophane+ paragonite + kyanite + garnet + talc + graphite + rutile +quartz. The coexistence of kyanite and Mg-glaucophane suggestsminimum P 2000 MPa at T > 600°C. Eclogite knockers fromthe same outcrop contain garnet and clinopyroxene which yield500°C for cores, 700°C for rims, and P 1200 MPa. Theassemblage garnet–biotite–phengite–albitewithin schists of the melange matrix of this locality indicatesmetamorphic conditions of T = 450–520°C at P = 1800MPa. Because all lithologies in this outcrop record high-P conditions,this metamorphic melange formed before or during peak metamorphismin a mid-Cretaceous subduction zone. KEY WORDS: geothermobarometry; high-P pelitic schist; eclogite; Puerto Cabello; Venezuela  相似文献   

Aqueous fluids and hydrous melts in high-pressure and ultra-high pressure rocks: Implications for element transfer in subduction zones   总被引：10，自引：0，他引：10  

Jrg Hermann  Carl Spandler  Alistair Hack  Andrey V. Korsakov 《Lithos》2006,92(3-4):399-417

High-pressure (HP) and ultra-high pressure (UHP) terranes are excellent natural laboratories to study subduction-zone processes. In this paper we give a brief theoretical background and we review experimental data and observations in natural rocks that constrain the nature and composition of the fluid phase present in HP and UHP rocks. We argue that a fluid buffered by a solid residue is compositionally well defined and is either an aqueous fluid (total amount of dissolved solids < 30 wt.%) or a hydrous melt (H₂O < 35 wt.%). There is only a small temperature range of approximately 50–100 °C, where transitional solute-rich fluids exist. A review of available experimental data suggest that in felsic rocks the second critical endpoint is situated at 25–35 kbar and  700 °C and hence must be considered in the study of UHP rocks. Despite this, the nature of the fluid phase can be constrained by relating the peak metamorphic conditions of rocks to the position of the wet solidus even if the peak pressure exceeds the pressure where the wet solidus terminates at the second critical endpoint. Transitional solute-rich fluids are expected in UHP terrains (P > 30 kbar) with peak temperatures of about 700 ± 50 °C. At higher temperatures, hydrous granitic melts occur whereas at lower temperatures aqueous fluids coexists with eclogite-facies minerals. This argument is complemented by evidence on the nature of the fluid phase from high-pressure terrains. We show that in the diamond-bearing, high-temperature UHP rocks from the Kokchetav Massif there are not only hydrous felsic melts, but probably also carbonate and sulfide melts present.

Hydrous quartzo-feldspathic melts are mainly produced in high temperature UHP rocks and their composition is relatively well constrained from experiments and natural rocks. In contrast, constraining the composition of aqueous fluids is more problematic. The combined evidence from experiments and natural rocks indicates that aqueous fluids liberated at the blueschist to eclogite facies transition are dilute. They contain only moderate amounts of LILE, Sr and Pb and do not transport significant amounts of key trace elements such as LREE, U and Th. This indicates that there is a decoupling of water and trace element release in subducted oceanic crust and that aqueous fluids are unable to enrich the mantle wedge significantly. Instead we propose that fluid-present melting in the sediments on top of the slab is required to transfer significant amounts of trace elements from the slab to the mantle wedge. For such a process to be efficient, top slab temperature must be at least 700–750 °C at sub-arc depth. Slab melting is likely to be triggered by fluids that derive from dehydration of mafic and ultramafic rocks in colder (deeper) portions of the slab.  相似文献   

Visualization of the turbulent flow structure in a gravel-bed river     

Alistair D. Kirkbride  Stuart J. McLelland 《地球表面变化过程与地形》1994,19(9):819-825

A novel technique for visualizing turbulent flow data from a gravel-bed river is presented. The time development of flow velocity and shear stress at three heights is displayed using a computer program. This can be used to observe how the fluctuations of velocity and shear stress interact both spatially and temporally. We highlight examples of flow events which are important for the understanding of flow dynamics. The visualization suggests that the turbulent flow-field is characterized not only by coherence over time at a point, but also by spatial interdependence between points. We suggest that this new visualization approach will assist further interpretation of statistical analyses of turbulent signals, as well as focusing future measurement strategies by providing a clearer spatio-temporal picture of the flow structure.  相似文献   

Experimental investigations of the role of H2O in calc-alkaline differentiation and subduction zone magmatism   总被引：6，自引：3，他引：6  

T. W. Sisson  T. L. Grove 《Contributions to Mineralogy and Petrology》1993,113(2):143-166

Phase relations of natural aphyric high-alumina basalts and their intrusive equivalents were determined through rock-melting experiments at 2 kb, H₂O-saturated with fO₂ buffered at NNO. Experimental liquids are low-MgO high-alumina basalt or basaltic andesite, and most are saturated with olivine, calcic plagioclase, and either high-calcium pyroxene or hornblende (±magnetite). Cr-spinel or magnetite appear near the liquidus of wet high-alumina basalts because H₂O lowers the appearance temperature of crystalline silicates but has a lesser effect on spinel. As a consequence, experimental liquids follow calcalkaline differentiation trends. Hornblende stability is sensitive to the Na₂O content of the bulk composition as well as to H₂O content, with the result that hornblende can form as a near liquidus mineral in wet sodic basalts, but does not appear until liquids reach andesitic compositions in moderate Na₂O basalts. Therefore, the absence of hornblende in basalts with low-to-moderate Na₂O contents is not evidence that those basalts are nearly dry. Very calcic plagioclase (>An₉₀) forms from basaltic melts with high H₂O contents but cannot form from dry melts with normal are Na₂O and CaO abundances. The presence of anorthite-rich plagioclase in high-alumina basalts indicates high magmatic H₂O contents. In sum, moderate pressure H₂O-saturated phase relations show that magmatic H₂O leads to the early crystallization of spinel, produces calcic plagioclase, and reduces the total proportion of plagioclase in the crystallizing assemblage, thereby promoting the development of the calc-alkaline differentiation trend.  相似文献   

Temperatures and H2O contents of low-MgO high-alumina basalts   总被引：1，自引：1，他引：1  

T. W. Sisson  T. L. Grove 《Contributions to Mineralogy and Petrology》1993,113(2):167-184

Experimental evidence is used to estimate H₂O contents in low-MgO high-alumina basalts (HABs) (<6 wt.% MgO) and basaltic andesites (BAs) (<5 wt.% MgO) that occur worldwide in magmatic arcs. Wholerock compositions of low-MgO HABs and BAs, phenocryst assemblages, and mineral chemistry match the compositions of liquids, phase assemblages, and mineral-compositions produced in H₂O-saturated melting experiments on HABs at moderate pressure (1–2 kb). Low-MgO HABs and BAs therefore could have existed as H₂O-rich multiply-saturated liquids within the crust. Results are presented for melting experiments on two HABs and an andesite at 1 kb pressure, H₂O-saturated, with fO₂ at the NNO buffer. These data and other experimental results on HABs are used to develop a method to estimate the temperature and H₂O content of HAB or BA liquids saturated with olivine, plagioclase, and either high-Ca pyroxene or hornblende. Estimated H₂O contents of HAB liquids are variable and range from 1 to 8 wt.%. High-MgO HABs (>8wt.% MgO) could have H₂O contents reaching no more than 1–2wt.%. The more common low-MgO HABs could have existed as liquids within the crust with H₂O contents of 4 wt.% or higher at temperatures<1100°C. Magmas with these high H₂O contents will saturate with and exsolve aqueous fluid upon approaching the surface. They cannot erupt as liquids and must grow crystals at shallow depths, thus accounting for the abundant phenocrysts in low-MgO HABs and BAs.  相似文献   

Seagrass tolerance to herbivory under increased ocean temperatures     

Ruby G. Garthwin  Alistair G.B. Poore  Adriana Vergés 《Marine pollution bulletin》2014

Climate change is acknowledged as a major threat to marine ecosystems, but the effect of temperature on species interactions remains poorly understood. We quantified the effects of long-term warming on plant-herbivore interactions of a dominant seagrass, Zostera muelleri. Growth, herbivory and tolerance to damage were compared between a meadow warmed by the thermal plume from a power station for 30 years (2–3 °C above background temperatures) and three control locations. Leaf growth rates and tissue loss were spatially variable but unrelated to temperature regimes. Natural herbivory was generally low. Simulated herbivory experiments showed that the tolerance of Z. muelleri to defoliation did not differ between warm and unimpacted meadows, with damaged and undamaged plants maintaining similar growth rates irrespective of temperature. These results suggest that the ability of temperate Z. muelleri to tolerate herbivory is not strongly influenced by warming, and this species may be relatively resilient to future environmental change.  相似文献   

Voluminous arc dacites as amphibole reaction-boundary liquids     

Dawnika?L.?BlatterEmail author  Thomas?W.?Sisson  W.?Ben?Hankins 《Contributions to Mineralogy and Petrology》2017,172(5):27

Dacites dominate the large-volume, explosive eruptions in magmatic arcs, and compositionally similar granodiorites and tonalites constitute the bulk of convergent margin batholiths. Shallow, pre-eruptive storage conditions are well known for many dacitic arc magmas through melt inclusions, Fe–Ti oxides, and experiments, but their potential origins deeper in the crust are not well determined. Accordingly, we report experimental results identifying the P–T–H₂O conditions under which hydrous dacitic liquid may segregate from hornblende (hbl)-gabbroic sources either during crystallization–differentiation or partial melting. Two compositions were investigated: (1) MSH–Yn?1 dacite (SiO₂: 65 wt%) from Mount St. Helens’ voluminous Yn tephra and (2) MSH–Yn?1?+?10% cpx to force saturation with cpx and map a portion of the cpx?+?melt?=?hbl peritectic reaction boundary. H₂O-undersaturated (3, 6, and 9 wt% H₂O) piston cylinder experiments were conducted at pressures, temperatures, and fO₂ appropriate for the middle to lower arc crust (400, 700, and 900 MPa, 825–1100?°C, and the Re–ReO₂ buffer?≈?Ni–NiO?+?2). Results for MSH–Yn?1 indicate near-liquidus equilibrium with a cpx-free hbl-gabbro residue (hbl, plg, magnetite, ± opx, and ilmeno-hematite) with 6–7 wt% dissolved H₂O, 925?°C, and 700–900 MPa. Opx disappears down-temperature consistent with the reaction opx?+?melt?=?hbl. Cpx-added phase relations are similar in that once ~10% cpx crystallizes, multiple saturation is attained with cpx, hbl, and plg, +/? opx, at 6–7 wt% dissolved H₂O, 940?°C, and 700–900 MPa. Plg–hbl–cpx saturated liquids diverge from plg–hbl–opx saturated liquids, consistent with the MSH–Yn?1 dacite marking a liquid composition along a peritectic distributary reaction boundary where hbl appears down-temperature as opx?+?cpx are consumed. The abundance of saturating phases along this distributary peritectic (liquid?+?hbl?+?opx?+?cpx?+?plg?+?oxides) reduces the variance, so liquids are restricted to dacite–granodiorite–tonalite compositions. Higher-K dacites than the Yn would also saturate with biotite, further limiting their compositional diversity. Theoretical evaluation of the energetics of peritectic melting of pargasitic amphiboles indicates that melting and crystallization of amphibole occur abruptly, proximal to amphibole’s high-temperature stability limit, which causes the system to dwell thermally under the conditions that produce dacitic compositions. This process may account for the compositional homogeneity of dacites, granodiorites, and tonalites in arc settings, but their relative mobility compared to rhyolitic/granitic liquids likely accounts for their greater abundance.  相似文献   

Frequent eruptions of Mount Rainier over the last ∼2,600 years     

T. W. Sisson  J. W. Vallance 《Bulletin of Volcanology》2009,71(6):595-618

Field, geochronologic, and geochemical evidence from proximal fine-grained tephras, and from limited exposures of Holocene lava flows and a small pyroclastic flow document ten–12 eruptions of Mount Rainier over the last 2,600 years, contrasting with previously published evidence for only 11–12 eruptions of the volcano for all of the Holocene. Except for the pumiceous subplinian C event of 2,200 cal year BP, the late-Holocene eruptions were weakly explosive, involving lava effusions and at least two block-and-ash pyroclastic flows. Eruptions were clustered from ∼2,600 to ∼2,200 cal year BP, an interval referred to as the Summerland eruptive period that includes the youngest lava effusion from the volcano. Thin, fine-grained tephras are the only known primary volcanic products from eruptions near 1,500 and 1,000 cal year BP, but these and earlier eruptions were penecontemporaneous with far-traveled lahars, probably created from newly erupted materials melting snow and glacial ice. The most recent magmatic eruption of Mount Rainier, documented geochemically, was the 1,000 cal year BP event. Products from a proposed eruption of Mount Rainier between AD 1820 and 1854 (X tephra of Mullineaux (US Geol Surv Bull 1326:1–83, 1974)) are redeposited C tephra, probably transported onto young moraines by snow avalanches, and do not record a nineteenth century eruption. We found no conclusive evidence for an eruption associated with the clay-rich Electron Mudflow of ∼500 cal year BP, and though rare, non-eruptive collapse of unstable edifice flanks remains as a potential hazard from Mount Rainier. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users. T. W. Sisson and J. W. Vallance contributed equally to this study.  相似文献