Geochemistry of the sheeted dike complex at Pito Deep

Alteration of sheeted dikes exposed along submarine escarpments at the Pito Deep Rift (NE edge of the Easter microplate) provides constraints on the crustal component of axial hydrothermal systems at fast spreading mid-ocean ridges. Samples from vertical transects through the upper crust constrain the temporal and spatial scales of hydrothermal fluid flow and fluid-rock reaction. The dikes are relatively fresh (average extent of alteration is 27%), with the extent of alteration ranging from 0 to >80%. Alteration is heterogeneous on scales of tens to hundreds of meters and displays few systematic spatial trends. Background alteration is amphibole-dominated, with chlorite-rich dikes sporadically distributed throughout the dike complex, indicating that peak temperatures ranged from <300°C to >450°C and did not vary systematically with depth. Dikes locally show substantial metal mobility, with Zn and Cu depletion and Mn enrichment. Amphibole and chlorite fill fractures throughout the dike complex, whereas quartz-filled fractures and faults are only locally present. Regional variability in alteration characteristics is found on a scale of <1-2 km, illustrating the diversity of fluid-rock interaction that can be expected in fast spreading crust. We propose that much of the alteration in sheeted dike complexes develops within broad, hot upwelling zones, as the inferred conditions of alteration cannot be achieved in downwelling zones, particularly in the shallow dikes. Migration of circulating cells along rides axes and local evolution of fluid compositions produce sections of the upper crust with a distinctive character of alteration, on a scale of <1-2 km and <5-20 ka.

Petrology of mafic and ultramafic intrusions from the Portneuf-Mauricie Domain, Grenville Province, Canada

The Portneuf-Mauricie Domain (PMD), located in the south-central part of the Grenville Province, comprises several mafic and ultramafic intrusions hosting Ni-Cu ± platinum-group element (PGE) prospects and a former small mining operation (Lac Édouard mine). These meter- to kilometer-scale, sulfide-bearing intrusions display diverse forms, such as layered and tabular bodies with no particular internal structure, and zoned plutons. They were injected ~ 1.40 Ga into a mature oceanic arc, before and during accretion of the arc to the Laurentian margin. The pressure-temperature conditions of the magmas at the beginning of their emplacement were 3 kbar and 1319-1200 °C (according to the petrologic modeling results from this study). The PMD mineralized intrusions are interpreted to represent former magma chambers or magma conduits in the roots of the oceanic arc. The parent magmas of the mineralized intrusions resulted mainly from the partial melting of a mantle source composed of spinel-bearing lherzolite. Petrologic modeling and the occurrence of primary amphibole in the plutonic rocks indicate that these parent melts were basaltic and hydrous. In addition, fractional crystallization modeling and Mg/Fe ratios suggest that most of the intrusions may have formed from evolved magmas, with Mg# = 60, resulting from the fractionation of more primitive magmas (primary magmas, with Mg# = 68). Petrologic modeling demonstrates that 30% fractional crystallization resulted in the primitive to evolved characteristics of the studied intrusive rocks (as indicated by the crystallization sequences and mineral chemistry). Exceptions are the Réservoir Blanc, Boivin, and Rochette West parent magmas, which may have undergone more extensive fractional crystallization, since these intrusions contain pyroxenes that are more iron rich and have lower Mg numbers than pyroxenes in the other PMD intrusions. The PMD mafic and ultramafic intrusions were intruded into an island arc located offshore from the Laurentian continent. Thus, their presence confirms the existence of a well-developed magmatic network (responsible of the fractionation processes) beneath the Proterozoic arc, which resulted in the wide range of compositions observed in the various plutons.

New data on the ophiolitic VMS deposits of Moeche (Cabo Ortegal Complex, NW Spain)

As a result of the variscan collision, several allochtonous complexes were emplaced on the Iberian margin in Devonian times, among them the Cabo Ortegal Complex comprising the Moeche ophiolitic sequence. Copper has been won from several mines (Piquitos I & II, Barqueira, Maruxa) from disseminated ores and thin massive sulphide layers in the Moeche Unit, a strongly deformed meta-volcanic sequence comprising mainly quartz-chlorite schists and mylonites, which defines the top of the ophiolite. The ores were metamorphosed and strongly deformed under brittle conditions (for pyrite), but their textures are often apparently post-deformational, due to very common solution-transfer processes; they are composed mostly of pyrite and chalcopyrite, with minor sphalerite, pyrrhotite, etc., and with traces of native gold and PGE. The geology, mineralogy, and geochemistry of the orebodies relate closely to VMS of the Cu-Zn (Cyprus) type. Fluid inclusion studies allowed an estimation of metamorphic conditions at pressures of 2/2’5 kb and T 325/350ºC. New determinations using the chlorite geothermometer yield temperatures around 320 ºC, corresponding to pressures near 2 kb according to the isochores deduced from the fluid inclusion study, although in the Barqueira mine higher temperatures, up to 350 ºC, are found, corresponding to presssures up to 2’5 kb. Pb isotopic compositions of pyrite point to a double source of Pb, i.e. a main mantle and a subordinate crustal source. The values for 87SR/86Sr in pyrite support this interpretation, but some results suggest later mobilization in an open system, corresponding to solution-transfer. Age determinations of pyrite deduced from the Pb isotope uranogenic graph, ≈ 480 Ma, do not fit with the metamorphic ages published for the Moeche Unit, and might point to the age of Pb extraction from the mantle.

Residual effect of organic zinc complexes in acid and calcareous soils on navy bean (phaseolus vulgaris l.) and flax (linum usitatissimum l.) crops under greenhouse conditions. Influence of the moisture conditions = Efecto residual de complejos orgánicos de zinc en suelos ácido y calizo en cultivos de judía (phaseolus vulgaris l.) y lino (linum usitatissimum l.) Realizados en condiciones de invernadero. Influencia de las diferentes condiciones de humedad

El Zn es un elemento esencial para el crecimiento saludable y reproducción de plantas, animales y humanos. La deficiencia de Zn es una de las carencias de micronutrientes más extendidas en muchos cultivos, afectando a grandes extensiones de suelos en diferentes áreas agrícolas. La biofortificación agronómica de diferentes cultivos, incrementando la concentración de micronutriente Zn en la planta, es un medio para evitar la deficiencia de Zn en animales y humanos. Tradicionalmente se han utilizado fertilizantes de Zn inorgánicos, como el ZnSO4, aunque en los últimos años se están utilizado complejos de Zn como fuentes de este micronutriente, obteniéndose altas concentraciones de Zn soluble y disponible en el suelo. Sin embargo, el envejecimiento de la fuente en el suelo puede causar cambios importantes en su disponibilidad para las plantas. Cuando se añaden al suelo fuentes de Zn inorgánicas, las formas de Zn más solubles pierden actividad y extractabilidad con el paso del tiempo, transformándose a formas más estables y menos biodisponibles. En esta tesis se estudia el efecto residual de diferentes complejos de Zn de origen natural y sintético, aplicados en cultivos previos de judía y lino, bajo dos condiciones de riego distintas (por encima y por debajo de la capacidad de campo, respectivamente) y en dos suelos diferentes (ácido y calizo). Los fertilizantes fueron aplicados al cultivo previo en tres dosis diferentes (0, 5 y 10 mg Zn kg-1 suelo). El Zn fácilmente lixiviable se estimó con la extracción con BaCl2 0,1M. Bajo condiciones de humedad por encima de la capacidad de campo se obtuvieron mayores porcentajes de Zn lixiviado en el suelo calizo que en el suelo ácido. En el caso del cultivo de judía realizado en condiciones de humedad por encima de la capacidad de campo se compararon las cantidades extraídas con el Zn lixiviado real. El análisis de correlación entre el Zn fácilmente lixiviable y el estimado sólo fue válido para complejos con alta movilidad y para cada suelo por separado. Bajo condiciones de humedad por debajo de la capacidad de campo, la concentración de Zn biodisponible fácilmente lixiviable presentó correlaciones positivas y altamente significativas con la concentración de Zn disponible en el suelo. El Zn disponible se estimó con varios métodos de extracción empleados habitualmente: DTPA-TEA, DTPA-AB, Mehlich-3 y LMWOAs. Estas concentraciones fueron mayores en el suelo ácido que en el calizo. Los diferentes métodos utilizados para estimar el Zn disponible presentaron correlaciones positivas y altamente significativas entre sí. La distribución del Zn en las distintas fracciones del suelo fue estimada con diferentes extracciones secuenciales. Las extracciones secuenciales mostraron un descenso entre los dos cultivos (el anterior y el actual) en la fracción de Zn más lábil y un aumento en la concentración de Zn asociado a fracciones menos lábiles, como carbonatos, óxidos y materia orgánica. Se obtuvieron correlaciones positivas y altamente significativas entre las concentraciones de Zn asociado a las fracciones más lábiles (WSEX y WS+EXC, experimento de la judía y lino, respectivamente) y las concentraciones de Zn disponible, estimadas por los diferentes métodos. Con respecto a la planta se determinaron el rendimiento en materia seca y la concentración de Zn en planta. Se observó un aumento del rendimiento y concentraciones con el efecto residual de la dosis mayores (10 mg Zn kg-1) con respecto a la dosis inferior (5 mg Zn 12 kg-1) y de ésta con respecto a la dosis 0 (control). El incremento de la concentración de Zn en todos los tratamientos fertilizantes, respecto al control, fue mayor en el suelo ácido que en el calizo. Las concentraciones de Zn en planta indicaron que, en el suelo calizo, serían convenientes nuevas aplicaciones de Zn en posteriores cultivos para mantener unas adecuadas concentraciones en planta. Las mayores concentraciones de Zn en la planta de judía, cultivada bajo condiciones de humedad por encima de la capacidad de campo, se obtuvieron en el suelo ácido con el efecto residual del Zn-HEDTA a la dosis de 10 mg Zn kg-1 (280,87 mg Zn kg-1) y en el suelo calizo con el efecto residual del Zn-DTPA-HEDTA-EDTA a la dosis de 10 mg Zn kg-1 (49,89 mg Zn kg-1). En el cultivo de lino, cultivado bajo condiciones de humedad por debajo de la capacidad de campo, las mayores concentraciones de Zn en planta ese obtuvieron con el efecto residual del Zn-AML a la dosis de 10 mg Zn kg-1 (224,75 mg Zn kg-1) y en el suelo calizo con el efecto residual del Zn-EDTA a la dosis de 10 mg Zn kg-1 (99,83 mg Zn kg-1). El Zn tomado por la planta fue determinado como combinación del rendimiento y de la concentración en planta. Bajo condiciones de humedad por encima de capacidad de campo, con lixiviación, el Zn tomado por la judía disminuyó en el cultivo actual con respecto al cultivo anterior. Sin embargo, en el cultivo de lino, bajo condiciones de humedad por debajo de la capacidad de campo, se obtuvieron cantidades de Zn tomado superiores en el cultivo actual con respecto al anterior. Esta tendencia también se observó, en ambos casos, con el porcentaje de Zn usado por la planta. Summary Zinc is essential for healthy growth and reproduction of plants, animals and humans. Zinc deficiency is one of the most widespread micronutrient deficiency in different crops, and affect different agricultural areas. Agronomic biofortification of crops produced by an increased of Zn in plant, is one way to avoid Zn deficiency in animals and humans Sources with inorganic Zn, such as ZnSO4, have been used traditionally. Although, in recent years, Zn complexes are used as sources of this micronutrient, the provide high concentrations of soluble and available Zn in soil. However, the aging of the source in the soil could cause significant changes in their availability to plants. When an inorganic source of Zn is added to soil, Zn forms more soluble and extractability lose activity over time, transforming into forms more stable and less bioavailable. This study examines the residual effect of different natural and synthetic Zn complexes on navy bean and flax crops, under two different moisture conditions (above and below field capacity, respectively) and in two different soils (acid and calcareous). Fertilizers were applied to the previous crop in three different doses (0, 5 y 10 mg Zn kg-1 soil). The easily leachable Zn was estimated by extraction with 0.1 M BaCl2. Under conditions of moisture above field capacity, the percentage of leachable Zn in the calcareous soil was higher than in acid soil. In the case of navy bean experiment, performed in moisture conditions of above field capacity, amounts extracted of easily leachable Zn were compared with the real leachable Zn. Correlation analysis between the leachable Zn and the estimate was only valid for complex with high mobility and for each soil separately. Under moisture conditions below field capacity, the concentration of bioavailable easily leachable Zn showed highly significant positive correlations with the concentration of available soil Zn. The available Zn was estimated with several commonly used extraction methods: DTPA-TEA, AB-DTPA, Mehlich-3 and LMWOAs. These concentrations were higher in acidic soil than in the calcareous. The different methods used to estimate the available Zn showed highly significant positive correlations with each other. The distribution of Zn in the different fractions of soil was estimated with different sequential extractions. The sequential extractions showed a decrease between the two crops (the previous and current) at the most labile Zn fraction and an increase in the concentration of Zn associated with the less labile fractions, such as carbonates, oxides and organic matter. A positive and highly significant correlation was obtained between the concentrations of Zn associated with more labile fractions (WSEX and WS + EXC, navy bean and flax experiments, respectively) and available Zn concentrations determined by the different methods. Dry matter yield and Zn concentration in plants were determined in plant. Yield and Zn concentration in plant were higher with the residual concentrations of the higher dose applied (10 mg Zn kg-1) than with the lower dose (5 mg Zn kg-1), also these parameters showed higher values with application of this dose than with not Zn application. The increase of Zn concentration in plant with Zn treatments, respect to the control, was greater in the acid soil than in the calcareous. The Zn concentrations in plant indicated that in the calcareous soil, new applications of Zn are desirable in subsequent crops to maintain suitable concentrations in plant. 15 The highest concentrations of Zn in navy bean plant, performed under moisture conditions above the field capacity, were obtained with the residual effect of Zn-HEDTA at the dose of 10 mg Zn kg-1 (280.87 mg Zn kg-1) in the acid soil, and with the residual effect of Zn- DTPA-HEDTA-EDTA at a dose of 10 mg Zn kg-1 (49.89 mg Zn kg-1) in the calcareous soil. In the flax crop, performed under moisture conditions below field capacity, the highest Zn concentrations in plant were obtained with the residual effect of Zn-AML at the dose of 10 mg Zn kg-1 (224.75 Zn mg kg-1) and with the residual effect of Zn-EDTA at a dose of 10 mg Zn kg-1 (99.83 mg Zn kg-1) in the calcareous soil. The Zn uptake was determined as a combination of yield and Zn concentration in plant. Under moisture conditions above field capacity, with leaching, Zn uptake by navy bean decreased in the current crop, respect to the previous crop. However, in the flax crop, under moisture conditions below field capacity, Zn uptake was higher in the current crop than in the previous. This trend is also observed in both cases, with the percentage of Zn used by the plant

Specific T cell recognition of kinetic isomers in the binding of peptide to class II major histocompatibility complex

Helper T cells are triggered by molecular complexes of antigenic peptides and class II proteins of the major histocompatibility complex . The formation of stable complexes between class II major histocompatibility complex proteins and antigenic peptides is often accompanied by the formation of a short-lived complex. In this report, we describe T cell recognition of two distinct complexes, one short-lived and the other long-lived, formed during the binding of an altered myelin basic protein peptide to I-Ak. One myelin basic protein-specific T cell clone is triggered by only the short-lived complex, and another is triggered by only the stable complex. Thus, a single peptide bound to a particular class II molecule can activate different T cells depending on the conditions of the binding reaction.

Probing the assembly of transcription initiation complexes through changes in σN protease sensitivity

The alternative bacterial σN RNA polymerase holoenzyme binds promoters as a transcriptionally inactive complex that is activated by enhancer-binding proteins. Little is known about how sigma factors respond to their ligands or how the responses lead to transcription. To examine the liganded state of σN, the assembly of end-labeled Klebsiella pneumoniae σN into holoenzyme, closed promoter complexes, and initiated transcription complexes was analyzed by enzymatic protein footprinting. V8 protease-sensitive sites in free σN were identified in the acidic region II and bordering or within the minimal DNA binding domain. Interaction with core RNA polymerase prevented cleavage at noncontiguous sites in region II and at some DNA binding domain sites, probably resulting from conformational changes. Formation of closed complexes resulted in further protections within the DNA binding domain, suggesting close contact to promoter DNA. Interestingly, residue E36 becomes sensitive to proteolysis in initiated transcription complexes, indicating a conformational change in holoenzyme during initiation. Residue E36 is located adjacent to an element involved in nucleating strand separation and in inhibiting polymerase activity in the absence of activation. The sensitivity of E36 may reflect one or both of these functions. Changing patterns of protease sensitivity strongly indicate that σN can adjust conformation upon interaction with ligands, a property likely important in the dynamics of the protein during transcription initiation.

Phosphorylation of the immunosuppressant FK506-binding protein FKBP52 by casein kinase II: Regulation of HSP90-binding activity of FKBP52

FKBP52 (HSP56, p59, HBI) is the 59-kDa immunosuppressant FK506-binding protein and has peptidyl prolyl isomerase as well as a chaperone-like activity in vitro. FKBP52 associates with the heat shock protein HSP90 and is included in the steroid hormone receptor complexes in vivo. FKBP52 possesses a well conserved phosphorylation site for casein kinase II (CK2) that was previously shown to be associated with HSP90. Here we examined whether FKBP52 is phosphorylated by CK2 both in vivo and in vitro. Recombinant rabbit FKBP52 was phosphorylated by purified CK2. We expressed and purified deletion mutants of FKBP52 to determine the site(s) phosphorylated by CK2. Thr-143 in the hinge I region was identified as the major phosphorylation site for CK2. A synthetic peptide corresponding to this region was phosphorylated by CK2, and the peptide competitively inhibited the phosphorylation of other substrates by CK2. The [32P]phosphate labeling of FKBP52-expressing cells revealed that the same site is also phosphorylated in vivo. FK506 binding to FKBP52 did not affect the phosphorylation by CK2 and, conversely, the FK506-binding activity of FKBP52 was not affected by the phosphorylation. Most importantly, CK2-phosphorylated FKBP52 did not bind to HSP90. These results indicate that CK2 phosphorylates FKBP52 both in vitro and in vivo and thus may regulate the protein composition of chaperone-containing complexes such as those of steroid receptors and certain protein kinases.