Redox-dependent activation of CO dehydrogenase from Rhodospirillum rubrum

Studies of initial activities of carbon monoxide dehydrogenase (CODH) from Rhodospirillum rubrum show that CODH is mostly inactive at redox potentials higher than −300 mV. Initial activities measured at a wide range of redox potentials (0–500 mV) fit a function corresponding to the Nernst equation with a midpoint potential of −316 mV. Previously, extensive EPR studies of CODH have suggested that CODH has three distinct redox states: (i) a spin-coupled state at −60 to −300 mV that gives rise to an EPR signal termed Cred1; (ii) uncoupled states at <−320 mV in the absence of CO2 referred to as Cunc; and (iii) another spin-coupled state at <−320 mV in the presence of CO2 that gives rise to an EPR signal termed Cred2B. Because there is no initial CODH activity at potentials that give rise to Cred1, the state (Cred1) is not involved in the catalytic mechanism of this enzyme. At potentials more positive than −380 mV, CODH recovers its full activity over time when incubated with CO. This reductant-dependent conversion of CODH from an inactive to an active form is referred to hereafter as “autocatalysis.” Analyses of the autocatalytic activation process of CODH suggest that the autocatalysis is initiated by a small fraction of activated CODH; the small fraction of active CODH catalyzes CO oxidation and consequently lowers the redox potential of the assay system. This process is accelerated with time because of accumulation of the active enzyme.

Difference schemes for time-dependent heat conduction models with delay

Different non-Fourier models of heat conduction, that incorporate time lags in the heat flux and/or the temperature gradient, have been increasingly considered in the last years to model microscale heat transfer problems in engineering. Numerical schemes to obtain approximate solutions of constant coefficients lagging models of heat conduction have already been proposed. In this work, an explicit finite difference scheme for a model with coefficients variable in time is developed, and their properties of convergence and stability are studied. Numerical computations showing examples of applications of the scheme are presented.

An Ecological Model for Predicting Behaviour of Mediterranean Shrublands

In order to build dynamic models for prediction and management of degraded Mediterranean forest areas was necessary to build MARIOLA model, which is a calculation computer program. This model includes the following subprograms. 1) bioshrub program, which calculates total, green and woody shrubs biomass and it establishes the time differences to calculate the growth. 2) selego program, which builds the flow equations from the experimental data. It is based on advanced procedures of statistical multiple regression. 3) VEGETATION program, which solves the state equations with Euler or Runge-Kutta integration methods. Each one of these subprograms can act as independent or as linked programs.

Fire behaviour of tabique walls

This paper present a study on the behaviour of tabique walls, concerning its fire resistance. This work is based on the experimental analysis of real scale tabique panels. Such walls were made in pine wood with an earth-based mortar finishing. In order to assess the earth-based mortar thickness effect on the fire resistance of the wall, three specimens were tested with three different mortar thicknesses of 15 mm, 10 mm and 5 mm. The earth-based mortar was previously analysed in the laboratory. The wooden structures were constructed based on traditional tabique technique. The experimental models were tested in a fire-resistance furnace, according to the ISO 834 standard fire. Temperatures were recorded using two data acquisition systems (spot measuring and field measuring). Fire resistance of test elements is expressed as the time during which the appropriate criteria have been satisfied so that one can predict the time before collapse, increasing both people and property safety. The obtained results are of great importance as they allow to improve the knowledge on tabique walls behaviour subjected to fire conditions. Two performance criteria were verified: the integrity criteria and the insulation criteria.

Mineral, chemical and isotopic compositions of altered rocks at ODP Sites 193-1188 and 193-1189

During ODP Leg 193, 4 sites were drilled in the active PACMANUS hydrothermal field on the crest of the felsic Pual Ridge to examine the vertical and lateral variations in mineralization and alteration patterns. We present new data on clay mineral assemblages, clay and whole rock chemistry and clay mineral strontium and oxygen isotopic compositions of altered rocks from a site of diffuse low-temperature venting (Snowcap, Site 1188) and a site of high-temperature venting (Roman Ruins, Site 1189) in order to investigate the water-rock reactions and associated elemental exchanges. The volcanic succession at Snowcap has been hydrothermally altered, producing five alteration zones: (1) chlorite+/-illite-cristobalite-plagioclase alteration apparently overprinted locally by pyrophyllite bleaching at temperatures of 260-310°C; (2) chlorite+/-mixed-layer clay alteration at temperatures of 230°C; (3) chlorite and illite alteration; (4) illite and chlorite+/-illite mixed-layer alteration at temperatures of 250-260°C; and (5) illite+/-chlorite alteration at 290-300°C. Felsic rocks recovered from two holes (1189A and 1189B) at Roman Ruins, although very close together, show differing alteration features. Hole 1189A is characterized by a uniform chlorite-illite alteration formed at ~250°C, overprinted by quartz veining at 350°C. In contrast, four alteration zones occur in Hole 1189B: (1) illite+/-chlorite alteration formed at ~300°C; (2) chlorite+/-illite alteration at 235°C; (3) chlorite+/-illite and mixed layer clay alteration; and (4) chlorite+/-illite alteration at 220°C. Mass balance calculations indicate that the chloritization, illitization and bleaching (silica-pyrophyllite assemblages) alteration stages are accompanied by different chemical changes relative to a calculated pristine precursor lava. The element Cr appears to have a general enrichment in the altered samples from PACMANUS. The clay concentrate data show that Cr and Cu are predominantly present in the pyrophyllites. Illite shows a significant enrichment for Cs and Cu relative to the bulk altered samples. Considerations of mineral stability allow us to place some constraints on fluid chemistry. Hydrothermal fluid pH for the chloritization and illitization was neutral to slightly acidic and relatively acidic for the pyrophyllite alteration. In general the fluids, especially from Roman Ruins and at intermediate depths below Snowcap, show only a small proportion of seawater mixing (<10%). Fluids in shallow and deep parts of the Snowcap holes, in contrast, show stronger seawater influence.

Rb-Sr systematics of volcanic rocks and alteration minerals of ODP Hole 104-642E

Subaerially erupted tholeiites at Hole 642E were never exposed to the high-temperature seawater circulation and alteration conditions that are found at subaqueous ridges. Alteration of Site 642 rocks is therefore the product of the interaction of rocks and fluids at low temperatures. The alteration mineralogy can thus be used to provide information on the geochemical effects of low temperature circulation of seawater. Rubidium-strontium systematics of leached and unleached tholeiites and underlying, continentally-derived dacites reflect interactions with seawater in fractures and vesicular flow tops. The secondary mineral assemblage in the tholeiites consists mainly of smectite, accompanied in a few flows by the assemblage celadonite + calcite (+/- native Cu). Textural relationships suggest that smectites formed early and that celadonite + calcite, which are at least in part cogenetic, formed later than and partially at the expense of smectite. Smectite precipitation occurred under variable, but generally low, water/rock conditions. The smectites contain much lower concentrations of alkali elements than has been reported in seafloor basalts, and sequentially leached fractions of smectite contain Sr that has not achieved isotopic equilibrium. 87Sr/86Sr results of the leaching experiments suggest that Sr was mostly derived from seawater during early periods of smectite precipitation. The basalt-like 87Sr/86Sr of the most readily exchangeable fraction seems to suggest a late period of exposure to very low water /rock. Smectite formation may have primarily occurred in the interval between the nearly 58-Ma age given by the lower series dacites and the 54.5 +/- 0.2 Ma model age given by a celadonite from the top of the tholeiitic section. The 54.5 +/- 0.2 Ma Rb-Sr model age may be recording the timing of foundering of the Voring Plateau. Celadonites precipitated in flows below the top of the tholeiitic section define a Rb-Sr isochron with a slope corresponding to an age of 24.3 +/- 0.4 Ma. This isochron may be reflecting mixing effects due to long-term chemical interaction between seawater and basalts, in which case the age provides only a minimum for the timing of late alteration. Alternatively, inferrential arguments can be made that the 24.3 +/- 0.4 isochron age reflects the timing of the late Oligocene-early Miocene erosional event that affected the Norwegian-Greenland Sea. Correlation of 87Sr/86Sr and 1/Sr in calcites results in a two-component mixing model for late alteration products. One end-member of the mixing trend is Eocene or younger seawater. Strontium from the nonradiogenic endmember can not, however, have been derived directly from the basalts. Rather, the data suggest that Sr in the calcites is a mixture of Sr derived from seawater and from pre-existing smectites. For Site 642, the reaction involved can be generalized as smectite + seawater ++ celadonite + calcite. The geochemical effects of this reaction include net gains of K and CO2 by the secondary mineral assemblage. The gross similarity of the reactions involved in late, low-temperature alteration at Site 642 to those observed in other sea floor basalts suggests that the transfer of K and C02 to the crust during low-temperature seawater-ocean crust interactions may be significant in calculations of global fluxes.