Organic Acid Derivatization Techniques Applied to Petroleum Hydrocarbon Transformations in Subsurface Environments

Evidence for the natural microbial remediation of subsurface fuel contamination situations should include identification and analysis of transformation or degradation products. In this way. u mass balance between fuel constituents and end products may be approached to monitor cleanup progress. Application of advanced organic acid metabolite derivatization techniques to several known sites of organic compounds and fuel mixture contamination provide valuable information on the pathways and progress of microbial transformation. Good correlation between observed metabolites and transformation pathways of aromatic fuel constituents were observed at the sites.     

The Pan-African continental margin in northeastern Africa: evidence from a geochronological study of granulites at Sabaloka, Sudan

Ion microprobe zircon ages, a Nd model age and RbSr whole-rock dates are reported from the high-grade gneiss terrain at Sabaloka on the River Nile north of Khartoum, formally considered to be part of the Archaean/early Proterozoic Nile craton. The granulites, which are of both sedimentary and igneous derivation, occur as remnants in migmatites. Detrital zircon ages range from ≈ 1000 to ≈ 2650 Ma and prove the existence of Archaean to late Proterozoic continental crust in the sedimentary source region. The Nd model age for one sedimentary granulite is between 1.26 (T_CHUR) and 1.70 (T_DM) Ga and provides a mean crustal residence age for the sedimentary precursor. Igneous zircons in enderbitic gneiss crystallized at 719 ± 81 Ma ago, an age that also corresponds to severe Pb loss in the detrital zircons and which probably reflects the granulite event at Sabaloka. The RbSr data indicate isotopic homogenization at about 700 Ma ago in the granulites and severe post-granulite disturbance at ≈ 570 Ma in the migmatites. We associate this disturbance with hydration, retrograde metamorphism and anatexis that produced undeformed granites ≈ 540 Ma ago. The ≈ 700 Ma granulite event at Sabaloka suggests that this part of the Sudan belongs to the Pan-African Mozambique belt while the ancient Nile craton lay farther west. The gneisses studied here may represent the infrastructure of the ancient African continental margin onto which the juvenile arc assemblage of the Arabian-Nubian shield was accreted during intense horizontal shortening and crustal interstacking of a major collision event.     

Rhyolites contaminated with metapelite and gabbro,Lipari, Aeolian Islands,Italy: products of lower crustal fusion or of assimilation plus fractional crystallization?

Pleistocene lavas from Monte S. Angelo and Chiesa Vecchia volcanoes on Lipari contain two suites of inclusions. A metapelitic suite consists of gneisses and granulites with combinations of cordierite, garnet, corundum, hercynite, andalusite, sillimanite, orthopyroxene, ilmenite, magnetite, biotite, plagioclase, and quartz. A gabbroic suite has cumulus texture and contains plagioclase, orthopyroxene, clinopyroxene, and magnetite. All megacryst phases in the lavas appear to be derived from rock fragments, with the exception of euhedral strongly zoned calcic plagioclase, and none has grown by homogeneous nucleation from liquid represented by the groundmass, which is peraluminous rhyolite (>70 wt% SiO₂, >6 wt% K₂O). Ground-mass microcrysts were nearly all derived from disaggregated metapelites; overgrowths of alkali feldspar on plagioclase and of orthopyroxene on clinopyroxene, and quartz intergrown with alkali feldspar, are the only phases that grew from the rhyolitic liquid. Euhedral cordierite, hercynite, and plagioclase at the margins of some rock fragments grew by reaction of metapelite with liquid.For grains in contact within metapelite inclusions, geothermometers and geobarometers yield estimates of equilibration conditions in the range of 800±100° C and 5±1 kbar. Compositions of phases in the same thin section, but not in the same inclusion, yield broadly erratic P and T estimates indicating disequilibrium among metapelite inclusions. Pyroxene thermometry in the gabbro suite indicates a crystallization temperature of 1020±50° C and a lack of subsequent thermal equilibration with the rhyolitic liquid.The metapelite suite may partly be restite, but much is xenolithic, derived from a vertical interval of perhaps several kilometers, and may have undergone a much earlier episode of melting. The gabbro fragments are accidental xenoliths incorporated as the magma rose. Contaminants (metapelite and gabbro) account for 50 vol.% of the lavas, and cause them to be classified as high-K andesite according to whole-rock major element analysis.The rhyolitic liquid may have originated by partial fusion of metapelites in the lower crust, or by fractional crystallization of mafic mantle-derived magma combined with assimilation of metapelite; the bulk of the evidence favors assimilation-fractional crystallization. Miocene and younger metapelite-contaminated rhyolites also occur in Tuscany, SE Spain, E Morocco, and NW Tunisia, and are associated in each region with mafic silica-undersaturated lavas, implying crustal underplating around the western Mediterranean before, during, and after formation of the Tyrrhenian basin.     

Geochemistry,geochronology, and petrogenesis of a Late Precambrian (∼ 590 Ma) composite dike from the North Eastern Desert of Egypt

Late Precambrian (575–600 Ma) igneous activity in the North Eastern Desert of Egypt produced large volumes of compositionally bimodal magmas. A single composite dike was studied to further examine petrogenetic relationships between andesitic and rhyolitic melts. The dike consists of 1.5–2 m of andesite on either side of a 5–6 m wide rhyolite core. Contact relations indicate that the andesite and rhyolite simultaneously existed as porphyritic liquids. Wholerock Rb-Sr dating indicates an age of 591 Ma, but with considerable scatter. Andesite and rhyolite had similar initial⁸⁷Sr/⁸⁶Sr of 0.7032±2, indicating derivation from a low Rb/Sr source, either the upper mantle, very young upper crust, or depleted lower crust. The composition of the andesites on either margin cannot be distinguished; these are very similar to andesites of the Dokhan Volcanics of similar age. Correspondingly, the rhyolite is compositionally similar to the epizonal Pink Granites. This dike and others like it represent hypabyssal feeders for the extrusive and shallow intrusive members of the North Eastern Desert bimodal suite.Major and trace element studies of the dike rocks show no evidence of mixing. With the exception of the alkaline earths, there is no evidence of diffusional transport across the rhyolite-andesite contacts. REE patterns indicate that petrogenesis of the andesite must have left a garnetiferous residue: either 10% melting of LREE-enriched garnet lherzolite or 25% melting of eclogite, followed by a small amount of shallow fractionation. Petrogenesis of the rhyolites remains enigmatic. Partitioning of trace elements and different plagioclase compositions in andesite and rhyolite argue against an origin by liquid immiscibility. Major and trace element models indicate that the rhyolite formed by fractional crystallization of the andesite or by anatexis of young amphibolite-facies crust.

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Zusammenfassung SpÄtprÄkambrische (575–600 Ma) magmatische AktivitÄt in der »North Eastern Desert« Ägyptens förderte gro\e Mengen bimodaler Magmen. Um die petrogenetischen Beziehungen zwischen andesitischen und rhyolitischen Schmelzen zu studieren, wurde ein einzelner, »bimodaler« Gang (composite dyke) untersucht.Der Gang besteht aus einem Rand von 1,5–2 m mÄchtigem Andesit auf beiden Seiten eines 5–6 m mÄchtigen Kernbereiches von Rhyolit. Die Kontaktbeziehungen zeigen, da\ Andesite und Rhyolite gleichzeitig als porphyritische Schmelzen existierten. »Whole-Rock« Rb-Sr Datierung ergab ein Alter von 591 Ma, jedoch mit einem erheblichen Fehler. Andesit und Rhyolith hatten Ähnliche initiale⁸⁷Sr/⁸⁶Sr VerhÄltnisse von 0.7032±2, die eine Herkunft aus Bereichen mit niedrigen Rb/Sr VerhÄltnissen erkennen lassen: Oberer Mantel, sehr junge obere Kruste, oder verarmte untere Kruste. Die Zusammensetzung der Andesite von den verschiedenen Seiten des Ganges ist nicht zu unterscheiden. Sie sind den Andesiten der Dokhan Vulkanite Ähnlich und etwa gleich alt. Entsprechend sind die Rhyolite den epizonalen rosa Graniten (»pink granite«) in der Zusammensetzung Ähnlich. Dieser Gang und andere gleich ihm stellen die Zufuhrspalten für die extrusiven und seichtintrusiven Magmatite der »North Eastern Desert« bimodalen Folge dar.Haupt- und Spurenelemente der Ganggesteine zeigen keine Anzeichen einer Mischung. Mit Ausnahme der Erdalkalien gibt es keinen Hinweis auf eine Diffusion der Elemente über den Rhyolit-Andesit Kontakt. Die Verteilung der Seltenen Erden deutet auf ein granatführendes Residuum bei der Petrogenese der Andesite: entweder10% Aufschmelzen von Granat-Lherzolit, angereichert an leichten Seltenen Erden, oder 25% Aufschmelzen von Eklogit, gefolgt von geringer Fraktionierung unter niedrigem Druck.Die Petrogenese der Rhyolite bleibt unklar. Die Verteilung der Spurenelemente und die unterschiedliche Plagioklas-Zusammensetzung in Andesit und Rhyolith sprechen gegen eine Entstehung aus unvermischbaren Schmelzen. Modelle basierend auf Haupt- und Spurenelementen deuten darauf hin, da\ der Rhyolit entweder durch fraktionierte Kristallisation des Andesits entstand oder durch Anatexis junger Kruste im Bereich der Amphibolit-Fazies.

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Résumé L'activité magmatique au Précambrien supérieur (575–600 Ma) dans le »North Eastern Desert« d'Egypte a engendré de grandes quantités de magmas bimodaux. De manière à préciser les relations entre fusions andésitiques et rhyolitiques, un dyke composite a été étudié.Ce dyke est constitué d'un coeur rhyolitique de 5 à 6 m, encadré de deux bordures andésitiques de 1,5 à 2 m. Les contacts indiquent que ces deux roches ont coexisté sous la forme de liquides porphyriques. Une datation Rb-Sr sur roche totale donne un âge de 591 Ma, mais avec une approximation importante. L'andésite et la rhyolite ont un mÊme rapport initial de 0,7032±2, indiquant une source à faible rapport Rb/Sr: manteau supérieur, croûte supérieure jeune ou croûte inférieure appauvrie. Les compositions des deux bordures andésitiques sont identiques et très semblables à celle des andésites de mÊme âge du complexe volcanique du Dokhan. De mÊme, la rhyolite a une composition semblable à celle des granites roses épizonaux. Ce dyke et d'autres du mÊme type représentent les voies d'alimentation des termes extrusifs et intrusifs superficiels de la série bimodale du »North Eastern Desert«.L'étude des éléments majeurs et en traces ne montre aucun mélange entre les roches du dyke. A l'exception des alcalino-terreux, il n'existe aucune indication de diffusion des éléments à travers le contact rhyolite — andésite. La distribution des terres rares montre que la genèse de l'andésite doit avoir laissé un résidu grenatifère: soit une lherzolite à grenat enrichie en terres rares légères et représentant moins de 10% de taux de fusion, soit une éclogite (jusqu'à 25% de taux de fusion) suivie d'un léger fractionnement à basse pression.La pétrogenèse de la rhyolite reste obscure. La répartition des éléments en traces et la différence de composition du plagioclase entre l'andésite et la rhyolite plaident contre une origine par immiscibilité. Les modèles tirés des éléments majeurs et en traces indiquent comme origine pour la rhyolite soit la cristallisation fractionnée de l'andésite, soit l'anatexie de matériaux crustaux jeunes dans les conditions du facies des amphibolites.

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Compositional and thermal convection in magma chambers

Magma chambers cool and crystallize at a rate determined by the heat flux from the chamber. The heat is lost predominantly through the roof, whereas crystallization takes place mainly at the floor. Both processes provide destabilizing buoyancy fluxes which drive highly unsteady, chaotic convection in the magma. Even at the lowest cooling rates the thermal Rayleigh number Ra is found to be extremely large for both mafic and granitic magmas. Since the compositional and thermal buoyancy fluxes are directly related it can be shown that the compositional Rayleigh number Rs (and therefore a total Rayleigh number) is very much greater than Ra. In the case of basaltic melt crystallizing olivine Rs is up to 10⁶ times greater than Ra. However compositional and thermal buoyancy fluxes are roughly equal. Therefore thermal and compositional density gradients contribute equally to convection velocities in the interior of the magma. Effects of thermal buoyancy generated by latent heat release at the floor are included.The latent heat boundary layer at the floor of a basaltic chamber is shown to be of the order of 1 m thick with very low thermal gradients whereas the compositional boundary layer is about 1 cm thick with large compositional gradients. As a consequence, the variation in the degree of supercooling in front of the crystal-liquid interface is dominated by compositional effects. The habit and composition of the growing crystals is also controlled by the nature of the compositional boundary layer. Elongate crystals are predicted to form when the thickness of the compositional boundary layer is small compared with the crystal size (as in laboratory experiments with aqueous solutions). In contrast, equant crystals form when the boundary layer is thicker than the crystals (as in most magma chambers). Instability of the boundary layer in the latter case gives rise to zoning within crystals. Diffusion of compatible trace elements through the boundary layer can also explain an inverse correlation, observed in layered intrusions, between Ni concentration in olivine and the proportion of Ni-bearing phases in the crystallizing assemblage.     

Some critical remarks on the analysis of phengite and paragonite components in muscovite by X-ray diffractometry

In the past lattice parameters b and c of muscovite s.1. from pelitic schists have been used to determine its phengite and paragonite component. A critical review of the literature and of some new data shows, however,

that a convincing statistical correlation between these physical and chemical properties does not exist

that an eventual trend-like correlation cannot be used for a quantitative analysis of phengite and/or paragonite components in muscovite.

Obviously further factors influence the lattice parameters of muscovite s.1., besides octahedral and interlayer chemistry.     

Dynamics of lava flow fronts, Arenal Volcano, Costa Rica

Arenal Volcano has effused basaltic andesite lava flows nearly continuously since September, 1968. The two different kinds of material in flows, lava and lava debris, have different rheologic properties and dynamic behavior. Flow morphology depends on the relationship between the amount and distribution of the lava and the debris, and to a lesser extent the ground morphology.Two main units characterize the flows: the channel zone and the frontal zone. The channel zone consists of two different units, the levées and the channel proper. A velocity profile in the channel shows a maximum value at the plug where the rate of shear is zero, and a velocity gradient increasing outward until, at the levées, the velocity becomes zero. Cooling produces a marked temperature gradient in the flow, leading to the formation of debris by brittle fracture when a critical value of shear rate to viscosity is reached. When the lava supply ceases, much of this debris and part of the lava is left behind after the flow nucleus drains out, forming a collapsed channel.Processes at the frontal zone include levée formation, debris formation, the change in shape of the front, and the choice of the flow path. These processes are controlled primarily by the rheological properties of the lava.Frontal zone dynamics can be understood by fixing the flow front as the point of reference. The lava flows through the channel into the front where it flows out into the levées, thereby increasing the length of the channel and permitting the front to advance. The front shows a relationship of critical height to the yield strength (τ₀) surface tension, and slope; its continued movement is activated by the pressure of the advancing lava in the channel behind. For an ideal flow (isothermal, homogeneous, and isotropic) the ratio of the section of channel proper to the section of levées is calculated and the distance the front will have moved at any time t_x can be determined once the amount of lava available to the front is known. Assuming that the velocity function of the front {G(t)} during the collapsing stage is proportional to the entrance pressure of the lava at the channel-front boundary, an exponential decrease of velocity through time is predicted, which shows good agreement with actual frontal velocity measurements taken on two flows. Local variations in slope have a secondary effect on frontal velocities.Under conditions of constant volume the frontal zone can be considered as a machine that consumes energy brought in by the lava to perform work (front advancement). While the front will use its potential energy to run the process, the velocity at which it occurs is controlled by the activation energy that enters the system as the kinetic energy of the lava flowing into the front. A relation for the energy contribution due to frontal acceleration is also derived. Finally the entrance pressure, that permits the front to deform, is calculated. Its small value confirms that the lava behaves very much like a Bingham plastic.     

Persistent organic pollutants (POPs) in a small, herbivorous, arctic marine zooplankton (Calanus hyperboreus): trends from April to July and the influence of lipids and trophic transfer

Samples of Calanus hyperboreus, a herbivorous copepod, were collected (n = 20) between April and July 1998, and water samples (n = 6) were collected in May 1998, in the Northwater Polynya (NOW) to examine persistent organic pollutants (POPs) in a high Arctic marine zooplankton. Lipid content (dry weight) doubled, water content (r2 = 0.88) and delta15N (r2 = 0.54) significantly decreased, and delta13C significantly increased (r2 = 0.30) in the C. hyperboreus over the collection period allowing an examination of the role of these variables in POP dynamics in this small pelagic zooplankton. The rank and concentrations of POP groups in C. hyperboreus over the entire sampling was sum of PCB (30.1 +/- 4.03 ng/g, dry weight) > sum of HCH (11.8 +/- 3.23) > sum of DDT (4.74 +/- 0.74), sum of CHLOR (4.44 +/- 1.0) > sum of CIBz (2.42 +/- 0.18), although these rankings varied considerably over the summer. The alpha- and gamma-HCH and lower chlorinated PCB congeners were the most common POPs in C. hyperboreus. The relationship between bioconcentration factor (BCF) and octanol-water partition coefficient (Kow) observed for the C. hyperboreus was linear and near 1:1 (slope = 0.72) for POPs with a log Kow between 3 and 6 but curvilinear when hydrophobic POPs (log Kow > 6) were included. Concentrations of sum of HCH. Sum of CHLOR and sum of CIBz increased over the sampling period, but no change in sum of PCB or sum of DDT was observed. After removing the effects of time, the variables lipid content, water content, delta15N and delta13C did not describe POP concentrations in C. hyperboreus. These results suggest that hydrophobic POP (log Kow = 3.86.0) concentrations in zooplankton are likely to reflect water concentrations and that POPs do not biomagnify in C. hyperboreus or likely in other small, herbivorous zooplankton.