Geochemistry of waters in the Valley of Ten Thousand Smokes region, Alaska

Meteoric waters from cold springs and streams outside of the 1912 eruptive deposits filling the Valley of Ten Thousand Smokes (VTTS) and in the upper parts of the two major rivers draining the 1912 deposits have similar chemical trends. Thermal springs issue in the mid-valley area along a 300-m lateral section of ash-flow tuff, and range in temperature from 21 to 29.8°C in early summer and from 15 to 17°C in mid-summer. Concentrations of major and minor chemical constituents in the thermal waters are nearly identical regardless of temperature. Waters in the downvalley parts of the rivers draining the 1912 deposits are mainly mixtures of cold meteoric waters and thermal waters of which the mid-valley thermal spring waters are representative. The weathering reactions of cold waters with the 1912 deposits appear to have stabilized and add only subordinate amounts of chemical constituents to the rivers relative to those contributed by the thermal waters. Isotopic data indicate that the mid-valley thermal spring waters are meteoric, but data is inconclusive regarding the heat source. The thermal waters could be either from a shallow part of a hydrothermal system beneath the 1912 vent region or from an incompletely cooled, welded tuff lens deep in the 1912 ash-flow sheet of the upper River Lethe area.Bicarbonate-sulfate waters resulting from interaction of near-surface waters and the cooling 1953–1968 southwest Trident plug issue from thermal springs south of Katmai Pass and near Mageik Creek, although the Mageik Creek spring waters are from a well-established, more deeply circulating hydrothermal system. Katmai caldera lake waters are a result of acid gases from vigorous drowned fumaroles dissolving in lake waters composed of snowmelt and precipitation.     

Lower palaeozoic and precambrian petroleum source rocks and the coalification path of alginite

Organic-rich samples derived from a Middle Cambrian Formation in the Georgina Basin, and from the Middle Proterozoic of the McArthur Basin in northern and central Australia, yielded alginite ranging from immature oil shale material to overmature residue. A maturation scale has been developed based on the thermal evolution of alginite as determined from reflectance and fluorescence. The coalification path of alginite is marked by jumps in contrast to the linear path of wood-derived vitrinite. Six zones have been recognised, ranging from undermature (zone I), through the mature (zones II/III), followed by a stable stage of no change (zone IV) to the overmature (zones V and VI). The onset of oil generation in alginite as evident from the present study is at 0.3% R_{o Alg.} and is expressed in a change of fluorescence from yellow to brown, and a coalification jump from 0.3 to 0.6% R_o of Alg. In many boreholes zone III can be distinguished between 0.6 and 0.8% R_o of Alg. where subsequent oil generation occurs. Zones II and III represent the oil window.A zone of little or no change designated zone IV, at of alginite follows zones II/III. A marked coalification jump characterises zone V, where a pronounced change in reflectance occurs to >1.0% R_{o Alg.}, signifying peak gas generation. The border of oil preservation lies at the transition of zone V and VI, at 1.6% R_{o Alg.} In zone VI gas generation only occurs.Comparison of reflectance results with experimental and geochemical pyrolysis data supports high activation energies for hydrocarbon generation from alginite, and therefore a later onset of oil generation than other liptinite macerals (i.e. cutinite, exinite, resinite) as well as a narrow oil window.Transmission electron microscopy (TEM) confirms that alginite does not go through a distinct intermediate stage but that the percentage of unreacted organic matter decreases as maturation proceeds. A clear distinction can be made in TEM between immature alginite, alginite after oil generation, and alginite residue following gas generation. Alginite beyond 1.6% R_o acquires very high densities and the appearance of inertinite in TEM.Bitumens/pyrobitumens make a pronounced contribution to the organic matter throughout the basins and have been shown to effect pyrolysis results by suppressing T_max. The bitumens/pyrobitumens have been divided into four groups, based on their reflectance and morphology, which in turn appears to be an expression of their genetic history. Their significance is in aiding the understanding of the basins' thermal history, and the timing of oil and gas generation.     

Barium- and LREE-rich, olivine-mica-lamprophyres with affinities to lamproites, Mt. Bundey, Northern Territory, Australia

Primitive olivine-mica-K-feldspar lamprophyre dykes, dated at 1831 ± 6 Ma, intrude lower greenschist facies rocks of the Early Proterozoic Pine Creek Inlier, of northern Australia. They are spatially, temporally and probably genetically associated with a post-tectonic composite granite-syenite pluton (Mt. Bundey pluton). The dykes have unusually high contents of large-ion-lithophile (LILE) and LREE elements (e.g. Ba up to 10,000 ppm, Ce up to 550 ppm, K₂O up to 7.5 wt. %) that resemble the concentrations found in the West Kimberley olivine and leucite lamproites. However, mineralogically the Mt. Bundey lamprophyres resemble shoshonitic lamprophyres and lack any minerals diagnostic of lamproites; leucite or leucite-pseudomorphs are absent. Mineral compositions are also unlike those in lamproites: micas contain higher Al₂O₃ than lamproitic mica; amphiboles are secondary actinolites after diopside; and oxides consist of zincian-chromian magnetite and groundmass magnetite. Heavy mineral concentrates contain mantle-derived xenocrysts of magnesiochromite, pyrope, Cr-diopside and rutile indicating a depth of sampling > 70 km. The Mt. Bundey lamprophyres are non-peralkaline to borderline peralkaline (molar (K + Na)/Al = 0.8 − 1.0) and potassic rather than ultrapotassic (molar K/Na < 2.5). They have distinctive major element compositions (≈46−49 wt. % SiO₂, ≈1.5−2 wt. % MgO, ≈7 wt. % CaO), and element ratios (e.g. molar Al/Ti ≈10, K/Na ≈2) that indicate they are best classified amongst transitional lamproites, i.e. potassic rocks such as cocites, jumillites and Navajominettes, that have geochemical characteristics transitional between Groups I and III. (Foley et al., 1987). The Mt. Bundey lamprophyres have LILE enrichment patterns that resemble the W. Kimberley pamproites but have moderate negative Ta---Nb---Ti anomalies and HREE abundances that are closely similar to the jumillites of southeastern Spain and Mediterranean-type lamproites. Single-stage modelling of Rb---Sr data is consistent with enrichment of the source-region of the Mt. Bundey lamprophyres ≈ 120–170 Ma before partial melting; i.e. at 1.95–2.10 Ga. Source enrichment does not appear to be associated with subduction processes, but may instead relate to incipient rifting of the Archaean basement. Negative Ta---Nb---Ti anomalies in the Mt. Bundey dykes may, therefore, relate to stability of residual titanate minerals in an oxidized subcontinental mantle source. This view is supported by high Fe³⁺/ΣFe ratios of mantle-derived magnesiochromite xenocrysts which indicate oxidized mantle conditions (ƒ_o2 ≈ FMQ + 1 long units), and by the presence of xenocrystic Cr-bearing rutile. Although the Mt. Bundey dykes have sampled upper mantle material, the oxidized nature of the magma source-region, and of the magma itself, suggests that conditions may not be favourable for diamond survival at depth nor for diamond transport in transitional lamproite magmas of this kind.     

Wind profile development above a locally adjusted sea surface

Results are presented from a numerical experiment of wind and shear stress profile development away from a shore line; the water surface is assumed to obey the Charnock-Ellison relation between surface roughness and friction velocity. In typical cases the upwind, land surface is rough relative to the sea and the velocity and shear stress results are qualitatively similar to those for flows from relatively rough to relatively smooth solid surfaces. In the present case, however, the downwind surface roughness and friction velocity vary with position and we find that wind profile development may play a significant role in the relationship between sea surface roughness and fetch.     

Temperatures of serpentinization of ultramafic rocks based on O18/O16 fractionation between coexisting serpentine and magnetite

Five lizardite-chrysotile type serpentinites from California, Guatemala and the Dominican Republic show oxygen isotope fractionations of 15.1 to 12.9 per mil between coexisting serpentine and magnetite (O¹⁸ magnetite=–7.6 to –4.6 per mil relative to SMOW). Nine antigorites (mainly from Vermont and S. E. Pennsylvania) show distinctly smaller fractionations of 8.7 to 4.8 per mil (O¹⁸ magnetite=–2.6 to +1.7 per mil). Two lizardite and chrysotile serpentinites dredged from the Mid-Atlantic Ridge exhibit fractionations of 10.0 and 12.4 per mil (O¹⁸ magnetite=–6.8 and –7.9 per mil, respectively), whereas an oceanic antigorite shows a value of 8.2 per mil (O¹⁸ magnetite=–6.2). These data all clearly indicate that the antigorites formed at higher temperatures than the chrysotilelizardites. Electron microprobe analyses of magnetites from the above samples show that they are chemically homogeneous and essentially pure Fe₃O₂. However, some magnetites from certain other samples that show a wide variation of Cr content also give very erratic oxygen isotopic results, suggesting non-equilibrium. An approximate serpentine-magnetite geothermometer curve was constructed by (1) extrapolation of observed O¹⁸ fractionations between coexisting chlorites and Fe-Ti oxides in low-grade pelitic schists whose isotopic temperatures are known from the quartz-muscovite O¹⁸ geothermometer, and (2) estimates of the O¹⁸ fractionation factor between chlorite and serpentine (assumed to be equal to unity). This serpentine-magnetite geothermometer suggests approximate equilibrium temperatures as follows: continental lizardite-chrysotile, 85° to 115° C; oceanic lizardite and chrysotile, 130° C and 185° C, respectively; oceanic antigorite, 235° C; and continental antigorites, 220° to 460° C.Contribution No. 2029 of the Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, California 91109.     

Trace element geochemistry of the rhyolitic volcanic rocks,Central North Island,New Zealand. Phenocryst data

Data are presented for K, Ba, Sr, Rb, Li, Ga, Mg, Mn, and Fe for twelve rhyolitic plagioclases (An₂₈-An₄₆), one dacitic (An₅₃), and three andesitic plagioclases (An₆₈-An₈₁). Additional data are presented for Ga, Gr, V, Ni, Co, Sc, Y, La, Sr, and Ba for two augites, nine hypersthenes, and five hornblendes separated from the same rocks. Distribution factors have been calculated, using these data, and previously published results for coexisting groundmass compositions (=liquids).The plagioclases show a positive correlation between, and a progressive increase in K and Ba (range 0.09–0.58% and 61–610 p.p.m. respectively) with increasing Ab-content. Sr (range 465–880 p.p.m.) shows a well defined maximum between An₄₀-An₅₅. The plagioclases have extremely high K/Rb ratios (mostly > 1,000).This volcanic series is characterised by relatively Mg-rich pyroxenes and hornblendes. The augites contain higher Sc, Cr, Y, Sr, and Y relative to their coexisting hypersthenes, while the hornblendes exhibit higher Sc, V, Ba, Sr, Y, and La relative to coexisting hypersthenes. Very marked differences in concentrations of these elements exist between the rhyolitic and andesitic ferromagnesian phenocrysts. There is also evidence of a systematic distribution of Sc, V, Cr, Y, Co, and Ni between coexisting hypersthenes and hornblendes, and between these minerals and their coexisting whole rock and groundmass compositions.The data are discussed from a petrological viewpoint, as they are interpreted to indicate that the phenocrysts crystallised in the magmas in which they are found, and are not xenocrystic. No evidence of hybridisation or contamination, subsequent to the onset of crystallisation, is found.     

The oxygen isotope geochemistry of igneous rocks

Oxygen isotope analyses have been obtained for 443 igneous rock and mineral samples from various localities throughout the world. Detailed studies were made on the Medicine Lake, Newberry, Lassen, Clear Lake, S. E. Guatemala, Hawaii and Easter I. volcanic complexes and on the Bushveld, Muskox, Kiglapait, Guadalupe, Duluth, Nain, Egersund, Lac St. Jean, Laramie, Skaergaard, Mull, Skye, Ardnamurchan and Alta, Utah plutonic complexes, as well as upon several of the zoned ultramafic intrusions of S. E. Alaska. Basalts, gabbros, syenites and andesites are very uniform in O¹⁸/O¹⁶, commonly with δ-values of 5.5 to 7.0 per mil. Many rhyolite obsidians, particularly those from oceanic areas and the Pacific Coast of the United States, also lie in this range; this indicates that such obsidians are differentiates of basaltic or andesitic magma at high temperatures (about 1,000° C). They cannot represent melted sialic crust. The only plutonic granites with such low δ-values are some of the hypersolvus variety, suggesting that these also might form by fractional crystallization. Obsidians from the continental interior, east of the quartz-diorite line, have higher δ-values. This is compatible with their having assimilated O¹⁸-rich sialic crust. A correlation generally exists between the O¹⁸/O¹⁶ ratios of SiO₂-rich differentiates and the chemical trends in volcanic complexes. High O¹⁸/O¹⁶ ratios accompany those trends having the lower Fe/Mg ratios, while ferrogabbro trends are associated with depletion in O¹⁸. Variations in oxygen fugacity may be responsible for these effects, as abundant early precipitation of magnetite should lead to both O¹⁸-enrichment and Fe-depletion in later differentiates. Plutonic granites have higher O¹⁸/O¹⁶ ratios than their volcanic equivalents, because (a) their differentiation occurred at much lower temperatures, or (b) they are in large part derived from O¹⁸-rich sialic crust by partial melting or assimilation. Also, the oxygen isotope fractionations among coexisting minerals are distinctly larger in plutonic rocks than in volcanic rocks. This is in keeping with their lower crystallization temperatures and their longer cooling history, which promotes post-crystallization oxygen isotope exchange. Hydrated obsidians and perlites have δO¹⁸-values that are much different from their primary, magmatic values. A correlation exists between D/H and O¹⁸/O¹⁶ ratios in hydrated volcanic glass from the western U.S.A., proving that the isotopic compositions are a result of exchange with meteoric waters. The O¹⁸ contents of the glasses appear to be about 25 per mil higher than their associated waters; hence, these hydrated glasses have not simply absorbed H₂O, but they have exchanged with large quantities of it. The igneous rocks from Mull, Skye, Ardnamurchan and the Skaergaard intrusion are all abnormally depleted in O¹⁸ relative to “normal” igneous rocks. This is a result of their having exchanged at high temperatures with meteoric water that was apparently abundant in the highly jointed plateau lavas into which these igneous rocks were intruded. In part, this exchange occurred with liquid magma and in part with the crystalline rock; in the latter case the feldspar was more easily exchanged and has become much more depleted in O¹⁸ than has coexisting quartz or pyroxene. The later differentiates of the Muskox intrusion are markedly O¹⁸-rich, but this is not a result of fractional crystallization. It is in large part a result of deuteric exchange between feldspars and an oxygen-bearing fluid (H₂O ?) that was either O¹⁸-rich or had a relatively low temperature. This phenomenon was also observed in a number of granophyres from other localities, particularly those containing brick-red alkali feldspar. The exchanged feldspars in all these examples are turbid or cloudy, and may be filled with hematite dust. It is concluded that most such feldspar in nature is the result of deuteric exchange and is probably drastically out of oxygen isotopic equilibrium with its coexisting quartz.