Kinetics of peptide hydrolysis and amino acid decomposition at high temperature

Dipeptide hydrolysis and amino acid decomposition appear to follow a first-order rate law. The hydrolysis rate increases exponentially with increasing temperature in aqueous solution at both 265 atm and water steam pressures over the temperature range of 100 to 220 degrees C. Dipeptide hydrolysis has a lower apparent activation energy at 265 atm (44.1 KJ/mol) than at water steam pressure (98.9 KJ/mol). At lower temperatures (<200-220 degrees C), the rate of peptide bond hydrolysis is faster at 265 atm than at water steam pressure. At higher temperatures (>200-220 degrees C), however, peptide bond hydrolysis is slower at 265 atm than at water steam pressure. In aqueous solution, amino acid decomposition rates also increase exponentially with increasing temperature. Amino acid decomposition rates are much higher at 265 atm than at water steam pressure over the entire temperature range investigated.     

Molecular and bulk isotopic analyses of organic matter in marls of the Mulhouse Basin (Tertiary, Alsace, France)

Contents of 13C in kerogens and carbonates in 21 samples from a core of the MAX borehole, Mulhouse Evaporite Basin, range from -27.3 to -23.5 and -3.7 to -1.8% vs PDB, respectively. Organic nitrogen in the same samples is enriched in 15N relative to atmospheric N2 by 12.2-15.7%. Hydrogen indices and delta values for kerogens vary systematically with facies, averaging 493 mg HC/g Corg and -25.7% in the most saline facies (dominated by inputs from aquatic sources) and 267 mg HC/g Corg and -23.7% in the least saline facies (50/50 aquatic/terrigenous). Values of delta were measured for individual aliphatic hydrocarbons from three samples representing three different organic facies. For all samples, terrigenous inputs were unusually rich in 13C, the estimated delta value for bulk terrigenous debris, apparently derived partly from CAM plants, being -22.5%. In the most saline facies, isotopic evidence indicates the mixing of 13C-depleted products of photosynthetic bacteria with 13C-enriched products of halotolerant eukaryotic algae. At lower salinities, a change in the producer community is marked by a decrease in the 13C content of algal lipids. The content of 13C in algal lipids increases in the least saline facies, due either to succession of different organisms or to decreased concentrations of dissolved CO2.     

Stratiform and vein U,Mo and Cu mineralization in the Novoveská Huta area,CSFR

U-Mo and Cu mineralization occurs in horizons as well as in veins in the Permian formations near Novoveská Huta. Ore mineralization is represented by uraninite, U-Ti oxides, coffinite, molybdenite, chalcopyrite, tennantite and pyrite. The isotopic composition of S and C displays a larger variability in the stratiform ores (³⁴S from –32.7 to +2.7 and ¹³C from –27.1 to — 0.5) These data suggest mixing of meteoric solutions with fluids of volcanic origin and a complex history. There is a narrower range of ³⁴S from –18.8 to –4.6 and ¹³C from –6.3 to –2.5% in quartz-carbonate veins with Cu mineralization suggesting a deep source of ore-bearing solutions. The Permian volcanics were a significant source of ore elements.Their contents of U, Mo, Cu and Y are from two to eight times higher than in sedimentary rocks. Accumulations of ore elements in the horizons were formed by the reduction and adsorption processes 240 ± 30 Ma ago according to U-Pb isotopic dating. Due to Alpine tectonism, these low-grade ores (U<0.1 wt%) were remobilized and higher-grade U-Mo ores (U>0.1 wt%) were formed 130 ± 20 Ma ago at temperatures ranging from 110 to 120° C, according to fluid inclusions. Younger veins with Cu mineralization were formed 115 ± 10 Ma according to the model age of Pb at temperatures ranging from 95 to 190°C.     

Cu 2p absorption spectroscopy as a probe for the site occupancy of (ZnxCu1−x)WO4 solid solution

The solid solution sanmartinite (ZnWO₄)—cuproscheelite (CuWO₄) has been studied using Cu 2p X-ray absorption spectroscopy. While a single L₃ absorption peak is observed for CuWO₄, two distinct L₃ absorption peaks with a separation of ～0.8 eV are observed for the intermediate samples in the solid solution. The two peaks represent distinct Cu sites: one with all CuO₆ next nearest neighbours in the (Cu,Zn)O₆ chains, another having at least one ZnO₆ next nearest neighbour. Both sites show a linear increase in covalency as a function of increasing Cu-content. The relative intensities of the two absorption peaks is dependent upon the Cu-content and has been used to model the site occupancies. The results reveal that the local structural effects can be associated with a composition-dependent structural phase transition from P2/c (ZnWO₄) to P $\bar 1$ (CuWO₄). Deviations from a single-site model are explained in terms of the local environments, and evidence for site preferences and local clustering are explored.     

Effects of onshore and offshore topography on sea breeze circulation: An observational study at eastern Attica,Greece

Field measurements of wind, air temperature and humidity were taken at the eastern part of the Attika district in June 1991, to examine the topographic influences exerted on the local sea breezes. These influences are due either to the elongated Evia island, faced by the northern half of Attica coastline some tens of kilometers offshore, or to the coast-parallel range of Hymettos mountain, rising steeply 12 km onshore. The instrumentation consisted mainly of three tethered meteorological balloons released at characteristic sires (i.e., the coast, a location between shoreline and mountain foot and the mountain top) and three autographic ground-based anemometers operating at selected locations. Data from the ground-based and upper air stations of the Hellenic National Meteorological Service, as well as the diurnal weather maps were also obtained and analyzed. Observations were made under different synoptic wind and the latter was found to determine remarkably the significance of the topographic effects. A preliminary two-dimensional numerical approach was also made concerning the sea breeze capability to reach the Hymettos mountain top in the case of a weak opposing geostrophic flow.     

The emplacement of intermediate volume ignimbrites: A case study from Roccamonfina Volcano,Southern Italy

A model is presented for the emplacement of intermediate volume ignimbrites based on a study of two 6 km³ volume ignimbrites on Roccamonfina Volcano, Italy. The model considers that the flows were slow moving, and quickly deflated from turbulent to non-turbulent conditions. Yield strength and density increased whereas fluidisation decreased with time and runout of the pyroclastic flows. In proximal locations, on the caldera rim, heterogeneous exposures including discontinuous lithic breccias, stratified and cross-stratified units interbedded with massive ignimbrite suggest deposition from turbulent flows. In medial locations thick, massive ignimbrite occurs associated with three types of co-ignimbrite lithic breccia which we interpret as being emplaced by non-turbulent flows. Multiple grading of different breccia/lithic concentration types within single flow units indicates that internal shear occurred producing overriding or overlapping of the rear of the flow onto the slower-moving front part. This overriding of different parts of non-turbulent pyroclastic flows could be caused by at least two different mechanisms: (1) changes in flow regime, such as hydraulic jumps that may occur at breaks in slope; and (2) periods of increased discharge rate, possibly associated with caldera collapse, producing fresh pulses of lithic-rich material that sheared onto the slower-moving part of the flow in front.We propose that ground surge deposits enriched in pumice compared with their associated ignimbrite probably formed by a flow separation mechanism from the top and front of the pyroclastic flow. These turbulent clouds moved ahead of the non-turbulent lower part of the flow to form stratified pumice-rich deposits. In distal regions well-developed coarse, often clast-supported, pumice concentrations zones and coarse intra-flow-unit lithic concentrations occur within the massive ignimbrite. We suggest that the flows were non-turbulent, possessed a relatively high yield strength and may have moved by plug flow prior to emplacement.     

Automatic equipment to monitor groundwater radon

Prototype instrumentation, able to automatically measure groundwater radon content variations, is presented. The equipment is made of stainless steel and has spherical valves with automatic and pneumatic control. The deemanation of the gases from the water is obtained by evacuating a suitable expansion chamber. The instrumentation can make discrete sampling ranging from 1 per hour to 1 per 99 hours. The equipment was tested in the laboratory: the efficiency was measured by means of a²⁶⁶Ra solution. A mean value of (0.65±0.07) count/s/Bq was obtained. A calibration test was carried out by comparing countings from the automatic equipment with those obtained by the standard laboratory cell. Results of an operational check over a period of approximately one year indicate that variations in radon at the calibration site are attributable more to meteorological than to tectonic causes.     

Isotope and trace element evidence for three component mixing in the genesis of the North Luzon arc lavas (Philippines)

Post-3Ma volcanics from the N Luzon arc exhibit systematic variations in ⁸⁷Sr/⁸⁶Sr (0.70327–0.70610), ¹⁴³Nd/¹⁴⁴Nd (0.51302–0.51229) and ²⁰⁸Pb^*/²⁰⁶Pb^* (0.981–1.035) along the arc over a distance of about 500 km. Sediments from the South China Sea west of the Manila Trench also exhibit striking latitudinal variations in radiogenic isotope ratios, and much of the isotopic range in the volcanics is attributed to variations in the sediment added to the mantle wedge during subduction. However, Pb-Pb isotope plots reveal that prior to subduction, the mantle end-member had high 8/4, and to a lesser extent high 7/4, similar to that in MORB from the Indian Ocean and the Philippine Sea Plate. Th isotope data on selected Holocene lavas indicate a source with unusually high Th/U ratios (4.5–5.5). Combined trace element and isotope data require that three end-members were implicated in the genesis of the N Luzon lavas: (1) a mantle wedge end-member with a Dupal-type Pb isotope signature, (2) a high LIL/HFS subduction component interpreted to be a slab-derived hydrous fluid, and (3) an isotopically enriched end-member which reflects bulk addition (<5%) of subducted S China Sea terrigenous sediment. The ⁸⁷Sr/⁸⁶Sr ratios in the volcanics show a restricted range compared with that in the sediments, and this contrasts with ¹⁴³Nd/¹⁴⁴Nd and ²⁰⁸Pb^*/²⁰⁶Pb^*, both of which have similar ranges in the volcanics and sediments. Such differences imply that whereas the isotope ratios of Nd, Pb and Th are dominated by the component from subducted sediment, those of Sr reflect a larger relative contribution from the slab-derived fluid.     

Crystal-chemistry of clinopyroxene from Sunda volcanic arc

Summary The crystal-chemistry of clinopyroxene from a suite of Sunda arc volcanic rocks was investigated by X-ray structure refinement and microprobe analysis. Relationships with clinopyroxene from volcanic rocks of the intraplate environment were highlighted.Sunda clinopyroxenes were distinguished into two groups. The first consists of clinopyroxene from SiO₂-saturated rock types and crystal rim from SiO₂-undersaturated rock types, the second of crystal core from SiO₂-undersaturated rock types. The crystal chemical behaviour of the two groups differs significantly, mainly in the geometrical relationships between M2 and T sites. While in the first group M2-O3 and T-O3 bond lengths shorten and lengthen respectively due to Ca and Al^IV increase, in the second group in which M2 site is almost fully coordinated by Ca, -O3 bond lengths are forced to lengthen in spite of low Al^IV content, in order to mantain the local charge balance around the O3 oxygens.It is noteworthy that Sunda clinopyroxene shows strong analogies with that from basaltic rocks from the Ethiopian plateau and K-rich lavas from the Roman Province respectively, reflecting similarities between the composition and mineralogical assemblages of the host rocks, although they all came from different tectonic environments. A relationship between intracrystalline Mg-Fe 2+ disorder and the explosive character of the volcanism is demonstrated.

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Kristallchemie von Klinopyroxenen aus Gesteinen des Vulkanbogens der Sunda-Inseln

Zusammenfassung Die Kristallchemie von Klinopyroxenen aus einer Serie von vulkanischen Gesteinen des Sunda-Bogens wurde mit Röntgen-Strukturverfeinerungen und Mikrosonden-analysen untersucht. Beziehungen zu Klinopyroxenen vulkanischer Gesteine aus intra-Plattenpositionen werden beleuchtet. Die Sunda-Klinopyroxene wurden in zwei Gruppen eingeteilt. Die erste umfaßt Klinopyroxene SiO₂-gesättigter Gesteinstypen und Kristallsäume SiO₂-untersättigter Gesteinstypen, die zweite Kristallkerne SiO₂-untersättigter Gesteinstypen. Das kristallchemische Verhalten der beiden Gruppen unterscheidet sich beträchtlich, hauptsächlich in den geometrischen Beziehungen zwischen den M2 und T Positionen. Während in der ersten Gruppe die M2-O3 und T-O3 Bindungsldngen durch Zunahme von Ca und Al^IV kleiner bzw. größer werden, sind in der zweiten Gruppe die T-O3 Bindungslängen trotz niedrigen Al^IV Gehaltes zu einer Vergrößerung gezwungen, damit um die O3 Atome der lokale Ladungsausgleich erhalten bleibt.Es ist bemerkenswert, daß die Sunda-Klinopyroxene große Analogien zu denen aus basaltischen Gesteinen des Abessinischen Plateaus und aus K-reichen Laven sowohl der Römischen Provinz als auch des Westafrikanischen Grabens zeigen. Dies spiegelt Ähnlichkeiten zwischen Zusammensetzung und Mineralbestand der Muttergesteine wider, obwohl sie all aus tektonisch unterschiedlichen Positionen kommen.Eine Beziehung zwischen intrakristalliner Mg-Fe²⁺ Unordnung und dem explosiven Charakter des Vulkanismus wird aufgezeigt.

     

Corona textures in Proterozoic olivine melanorites of the Equeefa Suite,Natal Metamorphic Province,South Africa

Summary Olivine-plagioclase and phlogopite-plagioclase coronas have been identified from olivine melanorites of the Mid- to Late Proterozoic Equeefa Suite in southern Natal, South Africa. Olivine, in contact with plagioclase, is mantled by a shell of clear orthopyroxene, in turn rimmed by pale green (pargasitic) clinoamphibole. Locally a third rim, composed of a fine pargasite-spinel symplectite is developed adjacent to the plagioclase. The second corona reaction has produced greenish-brown pargasite at phlogopite-plagioclase interfaces. A third, less obvious reaction, between olivine and phlogopite is also noted. Analytical data of all the mineral phases present, along with the coronas, are given. Two-pyroxene thermometry yields magmatic core temperatures ( 1120°C), with rim compositions indicating equilibration at 850°C. Consistent with this, the modelled olivine-plagioclase reaction occurs between 830–1050°C with a_waterbetween 0.1 and 1.0 at 7 kbar. The three reactions took place during a prolonged history of cooling and partial hydration of the magmatic olivine melanorites from over 1000°C down to 600°C. The P-T conditions indicated by the reactions suggest this cooling process was essentially isobaric, indicating that the area was not subjected to rapid uplift or burial throughout this entire period.

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Korona-Texturen in proterozoischen Olivin-Melanoriten der Equeefa Suite, Natal Metamorphic Province, Südafrika

Zusammenfassung Aus Olivin-Melanoriten der mittel- bis spätproterozoischen Equeefa Suite im südlichen Natal, Südafrika, wurden Olivin-Plagioklas und Phlogopit-Plagioklas-Koronartexturen beobachtet. Olivin, der mit Plagioklas im Kontakt steht, wird von einem klaren Saum vom Orthopyroxen ummantelt, der seinerseits von blaßgrünem (pargasitischem) Klinoamphibol umsäumt wird. Stellenweise ist ein dritter Saum, bestehend aus feinkörnigem symplektitischem Pargasit-Spinell im Kontakt mit Plagioklas ausgebildet. Die zweite koronabildende Reaktion resultiert in Bildung eines grünbraunen Pargasites an Phlogopit-Plagioklas Kornkontakten. Eine dritte, weniger auffällige Reaktion zwischen Olivin und Phlogopit wurde ebenfalls beobachtet. Zwei-Pyroxen-Thermometrie ergab magmatische Temperaturen der Kernbereiche ( 1120°C) und belegt eine Gleichgewichtseinstellung in den Randzonen bei ca. 850°C. Olivin-Plagioklas-Modellreaktionen liegen ebenfalls in einem Temperaturbereich von 830–1050°C bei Wasseraktivitäten von 0.1 bis 1.0 und einem Druck von 7 kbar. Die drei Reaktionen liefen im Zuge einer länger andauernden Abkühlung unter teilweiser Hydratisierung der magmatischen Melanorite in einem Temperaturbereich von 1000°C bis ca. 600°C ab. Die aus den Reaktionen ableitbaren P-T-Bedingungen sprechen für eine im wesentlichen isobare Abkhlungsgeschichte und zeigen, daß dieses Gebiet wáhrend dieser gesamten Periode keiner raschen Hebung bzw. keiner Versenkung unterworfen worden ist.