青海德尔尼铜钴锌矿床地质构造背景与成因

The Derni large Cu-Co-Zn sulfide deposit is occurred in the Derni melange belt, which is located in the eastern section of the A'nyemaqen ophiolite melange belt. The Derni deposit is hosted in the mantle peridotites and is very special in the world. Because the studying area is of very bad natural environment and very low geological research, the geotectonic setting and genesis of the deposit have long been debated. This paper studied these two questions and answered them. The research is of great significance to reveal impotant information of deep geology, crust-mantle interaction and geotectonic evolution, to enrich theories in the study of mineral deposit and provide scientific basic data for exploration and exploit of this kind of deposit. Based on the series of new achievements and new cognitions, to start with the geologic setting of the Derni deposit, through detailed field, tectonics, petrology, geochemistry, isotopic geochronology, microfossil, and study of mineral deposit, belongs to a melange belt, including mantle peridotites slice with ore, Late Precambrian sandstone and slate slice, metamorphic rock slice. 2. Petrological and geochemical characteristics indicate that the Derni mantle peridotite is not ophiolite mantle peridotite, but is occurred under the continental crust. 3. The U-Pb isotopic age of single-grain zircon form the accumulative rock suggests that the Derni mantle peridotite were formed in 747±10Ma, and underwent a great period of metamorphic process in 441.5±2.5Ma. 4. Microfossil assemblage from the carbonaceous slate belongs to Late Precambrian. Through petrography and petrochemistry, sandstone and slate were formed in the continental margin. 5. Sideronitic texture, which is first discovered in this study, reveals the characteristics of magmatic liquation. 6. Fluid inclusion explosion temperature of pyrite is in the range of -6.15～+6.64‰, and Pb isotope is consistent with mantle peridotite, which suggest ore-forming materials are from the mantle. To sum up, the upper mantle was melting partially, when it was metasomated by the mantle fluids with abundant Cu, Co, Zn, S, Au and LREE etc. The pockets of magma became enlarged by mantle tenacity shearing, and the pockets of magma occurred magmatic differentiation in the stable field, then the magma and ore pulp together with mantle refractory remnant dirpired and crystallized in the shallow part of the crust.

东海陆架盆地西南部烟囱构造与油气运聚关系研究

In recent years, chimney structure has been proved one of important indicators and a useful guide to major petroleum fields exploration through their exploration history both at home and abroad. Chimney structure, which has been called "gas chimney" or "seismic chimney", is the special fluid-filled fracture swarm, which results from the boiling of active thermal fluid caused by abruptly decreasing of high pressure and high temperature in sedimentary layers of upper lithosphere. Chimney structure is well developed in continental shelf basin of East China Sea, which indicates the great perspectives of petroleum resources there. However, the chimney structure also complicated the petroleum accumulation. So the study of chimney structure on its formation, its effect on occurrence and distribution of petroleum fields is very important not only on theoretical, but also on its applied research. It is for the first time to make a clear definition of chimney structure in this paper, and the existence and practical meaning of chimney structure are illustrated. Firstly, on the viewpoint of exploration, this will amplify exploration area or field, not only in marine, but also on continent. Secondly, this is very important to step-by-step exploration and development of petroleum fields with overpressure. Thirdly, this will provide reference for the study on complex petroleum system with multi-sources, commingled sources and accumulation, multi-stage accumulations, and multi-suits petroleum system in the overlay basin. Fourthly, when the thermal fluid enters the oceanic shallow layer, it can help form gas hydrate under favorable low-temperature and high-pressure conditions. Meanwhile, the thermal fluid with its particular component and thermal content will affect the physical, chemical and ecological environments, which will help solving the problem of global resources and environment. Beginning from the regional tectonic evolution characteristics, this paper discussed the tectonic evolution history of the Taibei depression, then made an dynamical analysis of the tectonic-sedimentary evolution during the Mesozoic and Cenozoic for the East China Sea basin. A numerical model of the tectonic-thermal evolution of the basin via the Basin-Mod technique was carried out and the subsidence-buried history and thermal history of the Taibei depression were inverse calculated: it had undergone a early rapid rift and sag, then three times of uplift and erosion, and finally depressed and been buried. The Taibei depression contains a huge thick clastic sedimentary rock of marine facies, transitional facies and continental facies on the complex basement of ante-Jurassic. It is a part of the back-arc rifting basins occurred during the Mesozoic and Cenozoic. The author analyzed the diagenesis and thermal fluid evolution of this area via the observation of cathodoluminescence, scanning electron microscope and thin section, taking advantage of the evidences of magma activities, paleo-geothermics and structural movement, the author concluded that there were at least three tectonic-thermal events and three epochs of thermal-fluid activities; and the three epochs of thermal-fluid activities were directly relative to the first two tectonic-thermal events and were controlled by the generation and expulsion of hydrocarbon in the source rock simultaneously. Based on these, this paper established the corresponding model between the tectonic-thermal events and the thermal-fluid evolution of the Taibei Depression, which becomes the base for the study on the chimney structures. According to the analyses of the gas-isotope, LAM spectrum component of fluid inclusion, geneses of CO_2 components and geneses of hydrocarbon gases, the author preliminarily verified four sources of the thermal fluid in the Taibei Depression: ① dehydration of mud shale compaction, ② expulsion of hydrocarbon in the source rock; ③ CO_2 gas hydro-thermal decomposition of carbonatite; ④magma-derived thermal fluid including the mantle magma water and volatile components (such as H_2O, CO_2, H_2S, SO_2, N_2 and He etc.). On the basis of the vitrinite reflectance (Ro), homogenization temperature of fluid inclusion, interval transit time of major well-logging, mud density of the wells, measured pressure data and the results of previous studies, this paper analyzed the characteristics of the geothermal fields and geo-pressure fields for the various parts in this area, and discussed the transversal distribution of fluid pressure. The Taibei depression on the whole underwent a temperature-loss process from hot basin to cold basin; and locally high thermal anomalies occurred on the regional background of moderate thermal structure. The seal was primarily formed during the middle and late Paleocene. The overpressured system was formed during the middle and late Eocene. The formation of overpressured system in Lishui Sag underwent such an evolutionary process as "form-weaken-strengthen-weaken". Namely, it was formed during the middle and late Eocene, then was weakened in the Oligocene, even partly broken, then strengthened after the Miocene, and finally weakened. The existence of the thermal fluid rich in volatile gas is a physical foundation for the boiling of the fluid, and sharply pressure depletion was the major cause for the boiling of the fluid, which suggests that there exists the condition for thermal fluid to boil. According to the results of the photoelastic simulation and similarity physical experiments, the geological condition and the formation mechanism of chimnestructures are summarized: well compartment is the prerequisite for chimney formation; the boiling of active thermal fluid is the original physical condition for chimney formation; The local place with low stress by tension fault is easy for chimney formation; The way that thermal fluid migrates is one of the important factors which control the types of chimney structures. Based on where the thermal fluid come from and geometrical characteristics of the chimney structures, this paper classified the genetic types of chimney structures, and concluded that there existed three types and six subtypes chimney structures: organic chimney structures generated by the hydrocarbon-bearing thermal fluid in middle-shallow layers, inorganic and commingling-genetic chimney structures generated by thermal fluid in middle-deep layers. According to the seismic profiles interpretations, well logging response analysis and mineralogical and petrological characteristics in the study area, the author summarized the comprehensive identification marks for chimney structures. Especially the horizon velocity analysis method that is established in this paper and takes advantage of interval velocity anomaly is a semi-quantitative and reliable method of chimney structure s identification. It was pointed out in this paper that the occurrence of the chimney structures in the Taibei depression made the mechanism of accumulation complicated. The author provided proof of episodic accumulation of hydrocarbon in this area: The organic component in the boiling inclusion is the trail of petroleum migration, showing the causality between the boiling of thermal fluid and the chimney structures, meanwhile showing the paroxysmal accumulation is an important petroleum accumulation model. Based on the evolutionary characteristics of various types of chimney structures, this paper discussed their relationships with the migration-accumulation of petroleum respectively. At the same time, the author summarized the accumulating-dynamical models associated with chimney structures. The author analyzed such accumulation mechanisms as the facies state, direction, power of petroleum migration, the conditions of trap, the accumulation, leakage and reservation of petroleum, and the distribution rule of petroleum. The author also provides explanation for such practical problems the existence of a lot of mantle-derived CO_2, and its heterogeneous distribution on plane. By study on and recognition for chimney structure, the existence and distribution of much mantle-derived CO_2 found in this area are explained. Caused by tectonic thermal activities, the deep magma with much CO_2-bearing thermal fluid migrate upward along deep fault and chimney structures, which makes two wells within relatively short distance different gas composition, such as in well LF-1 and well LS36-1-1. Meanwhile, the author predicted the distribution of petroleum accumulation belt in middle-shallow layer for this area, pointed out the three favorable exploration areas in future, and provided the scientific and deciding references for future study on the commingling-genetic accumulation of petroleum in middle-deep layer and the new energy-gas hydrate.

地幔对流理论及其在解释地球物理观测的应用

With the improving of mantle convection theory, the developing of computing method and increasing of the measurement data, we can numerically simulate more clearly about the effects on some geophysical observed phenomenons such as the global heat flow and global lithospheric stress field in the Earth's surface caused by mantle convection, which is the primary mechanism for the transport of heat from the Earth's deep interior to its surface and the underlying force mechanism of dynamics in the Earth.Chapter 1 reviews the historical background and present research state of mantle convection theory.In Chapter 2, the basic conception of thermal convection and the basic theory about mantle flow.The effects on generation and distribution of global lithospheric stres s field induced by mantle flow are the subject of Chapter 3. Mantle convection causes normal stress and tangential stresses at the bottom of the lithosphere, and then the sublithospheric stress field induces the lithospheric deformation as sixrface force and results in the stress field within the lithosphere. The simulation shows that the agreement between predictions and observations is good in most regions. Most of subduction zones and continental collisions are under compressive. While ocean ridges, such as the east Pacific ridge, the Atlantic ridge and the east African rift valley, are under tensile. And most of the hotspots preferentially occur in regions where calculated stress is tensile. The calculated directions of the most compressive principal horizontal stress are largely in accord with that of the observation except for some regions such as the NW-Pacifie subduction zone and Qinghai-Tibet Plateau, in which the directions of the most compressive principal horizontal stress are different. It shows that the mantel flow plays an important role in causing or affecting the large-scale stress field within the lithosphere.The global heat flow simulation based on a kinematic model of mantle convection is given in Chapter 4. Mantle convection velocities are calculated based on the internal loading theory at first, the velocity field is used as the input to solve the thermal problem. Results show that calculated depth derivatives of the near surface temperature are closely correlated to the observed surface heat flow pattern. Higher heat flow values around midocean ridge systems can be reproduced very well. The predicted average temperature as a function of function of depth reveals that there are two thermal boundary layers, one is close to the surface and another is close to the core-mantle boundary, the rest of the mantle is nearly isothermal. Although, in most of the mantle, advection dominates the heat transfer, the conductive heat transfer is still locally important in the boundary layers and plays an important role for the surface heat flow pattern. The existence of surface plates is responsible for the long wavelength surface heat flow pattern.In Chapter 5, the effects on present-day crustal movement in the China Mainland resulted from the mantle convection are introduced. Using a dynamic method, we present a quantitative model for the present-day crustal movement in China. We consider not only the effect of the India-Eurasia collision, the gravitational potential energy difference of the Tibet Plateau, but also the contribution of the shear traction on the bottom of the lithosphere induced by the global mantle convection. The comparison between our results and the velocity field obtained from the GPS observation shows that our model satisfactorily reproduces the general picture of crustal deformation in China. Numerical modeling results reveal that the stress field on the base of the lithosphere induced by the mantle flow is probably a considerable factor that causes the movement and deformation of the lithosphere in continental China with its eflfcet focuing on the Eastern China A numerical research on the small-scale convection with variable viscosity in the upper mantle is introduced in Chapter 6. Based on a two-dimensional model, small-scale convection in the mantle-lithosphere system with variable viscosity is researched by using of finite element method. Variation of viscosity in exponential form with temperature is considered in this paper The results show that if viscosity is strongly temperature-dependent, the upper part of the system does not take a share in the convection and a stagnant lid, which is identified as lithosphere, is formed on the top of system because of low temperature and high viscosity. The calculated surface heat flow, topography and gravity anomaly are associated well with the convection pattern, namely, the regions with high heat flow and uplift correspond to the upwelling flow, and vice versa.In Chapter 7, we give a brief of future research subject: The inversion of lateral density heterogeneity in the mantle by minimizing the viscous dissipation.

An empirical equation for the calculation of retention time with extrapolation of temperature in gas chromatography

An empirical equation is proposed to accurately correlate isothermal data over a wide range of temperature With the equation ln k = A* + B*/T-lambda the retention times of different solutes tested on OV-101, SE-54 and PEG 20M capillary columns have been achieved even when lambda is assigned a constant value of 1.7 Comparison with ln k = A + B/T and in k = c + d/T+ h/T-2, shows that the proposed equation is of higher accuracy and is applicable to extrapolation calculation, especially from data at high temperature to those at low temperature. Parameters A* and B* as well as A and B are also discussed. The linear correlation of A* and B* is weaker than that of A and B.

Study of the carbonaceous deposits formed on a Mo/HZSM-5 catalyst in methane dehydro-aromatization by using TG and temperature-programmed techniques

Carbonaceous deposits formed during the temperature-programmed surface reaction (TPSR) of methane dehydro-aromatization (MDA) over Mo/HZSM-5 catalysts have been investigated by TPH, TPCO2 and TPO, in combination with thermal gravimetric analysis (TG). The TPO profiles of the coked catalyst after TPSR of MDA show two temperature peaks: one is at about 776 K and the other at about 865 K. The succeeding TPH experiments only resulted in the diminishing of the area of the high-temperature peak, and had no effect on the area of the low-temperature peak. On the other hand, the TPO profiles of the coked catalyst after succeeding TPCO2 experiments exhibited obvious reduction in the areas of both the high-and low-temperature peaks, particularly in the area of the low-temperature peak. On the basis of TPSR, TPR and TPCO2 experiments and the corresponding TG analysis, quantitative analysis of the coke and the kinetics of its burning-off process have been studied. (C) 2001 Elsevier Science B.V. All rights reserved.

Heat capacity and thermodynamic properties of myclobutanil

The low-temperature heat capacities of myclobutanil (C15H17CIN4) were precisely measured with an automated adiabatic calorimeter over the temperature range from 78 to 368 K. The sample was observed to melt at (348.800 +/- 0.06) K. The molar enthalpy and entropy of the melting as well as the chemical purity of the substance were determined to be Delta(fus)H(m) = (30931 +/- 11) J.mol(-1), Delta(fus)S(m) = (88.47 +/- 0.02) J.mol(-1).K-1 and 99.41%, respectively. Further research of the melting process for this compound was carried out by means of DSC technique. The result was in agreement with that obtained from the measurements of heat capacities.

Computational modeling of defects in nanoscale device materials

This PhD thesis concerns the computational modeling of the electronic and atomic structure of point defects in technologically relevant materials. Identifying the atomistic origin of defects observed in the electrical characteristics of electronic devices has been a long-term goal of first-principles methods. First principles simulations are performed in this thesis, consisting of density functional theory (DFT) supplemented with many body perturbation theory (MBPT) methods, of native defects in bulk and slab models of In0.53Ga0.47As. The latter consist of (100) - oriented surfaces passivated with A12O3. Our results indicate that the experimentally extracted midgap interface state density (Dit) peaks are not the result of defects directly at the semiconductor/oxide interface, but originate from defects in a more bulk-like chemical environment. This conclusion is reached by considering the energy of charge transition levels for defects at the interface as a function of distance from the oxide. Our work provides insight into the types of defects responsible for the observed departure from ideal electrical behaviour in III-V metal-oxidesemiconductor (MOS) capacitors. In addition, the formation energetics and electron scattering properties of point defects in carbon nanotubes (CNTs) are studied using DFT in conjunction with Green’s function based techniques. The latter are applied to evaluate the low-temperature, low-bias Landauer conductance spectrum from which mesoscopic transport properties such as the elastic mean free path and localization length of technologically relevant CNT sizes can be estimated from computationally tractable CNT models. Our calculations show that at CNT diameters pertinent to interconnect applications, the 555777 divacancy defect results in increased scattering and hence higher electrical resistance for electron transport near the Fermi level.

Global Rates of Free Hydrogen (H2) Production by Serpentinization and other Abiogenic Processes within Young Ocean Crust

The main conclusion of this dissertation is that global H2 production within young ocean crust (<10 Mya) is higher than currently recognized, in part because current estimates of H2 production accompanying the serpentinization of peridotite may be too low (Chapter 2) and in part because a number of abiogenic H2-producing processes have heretofore gone unquantified (Chapter 3). The importance of free H2 to a range of geochemical processes makes the quantitative understanding of H2 production advanced in this dissertation pertinent to an array of open research questions across the geosciences (e.g. the origin and evolution of life and the oxidation of the Earth’s atmosphere and oceans).

The first component of this dissertation (Chapter 2) examines H2 produced within young ocean crust [e.g. near the mid-ocean ridge (MOR)] by serpentinization. In the presence of water, olivine-rich rocks (peridotites) undergo serpentinization (hydration) at temperatures of up to ~500°C but only produce H2 at temperatures up to ~350°C. A simple analytical model is presented that mechanistically ties the process to seafloor spreading and explicitly accounts for the importance of temperature in H2 formation. The model suggests that H2 production increases with the rate of seafloor spreading and the net thickness of serpentinized peridotite (S-P) in a column of lithosphere. The model is applied globally to the MOR using conservative estimates for the net thickness of lithospheric S-P, our least certain model input. Despite the large uncertainties surrounding the amount of serpentinized peridotite within oceanic crust, conservative model parameters suggest a magnitude of H2 production (~1012 moles H2/y) that is larger than the most widely cited previous estimates (~1011 although previous estimates range from 1010-1012 moles H2/y). Certain model relationships are also consistent with what has been established through field studies, for example that the highest H2 fluxes (moles H2/km2 seafloor) are produced near slower-spreading ridges (<20 mm/y). Other modeled relationships are new and represent testable predictions. Principal among these is that about half of the H2 produced globally is produced off-axis beneath faster-spreading seafloor (>20 mm/y), a region where only one measurement of H2 has been made thus far and is ripe for future investigation.

In the second part of this dissertation (Chapter 3), I construct the first budget for free H2 in young ocean crust that quantifies and compares all currently recognized H2 sources and H2 sinks. First global estimates of budget components are proposed in instances where previous estimate(s) could not be located provided that the literature on that specific budget component was not too sparse to do so. Results suggest that the nine known H2 sources, listed in order of quantitative importance, are: Crystallization (6x1012 moles H2/y or 61% of total H2 production), serpentinization (2x1012 moles H2/y or 21%), magmatic degassing (7x1011 moles H2/y or 7%), lava-seawater interaction (5x1011 moles H2/y or 5%), low-temperature alteration of basalt (5x1011 moles H2/y or 5%), high-temperature alteration of basalt (3x1010 moles H2/y or <1%), catalysis (3x108 moles H2/y or <<1%), radiolysis (2x108 moles H2/y or <<1%), and pyrite formation (3x106 moles H2/y or <<1%). Next we consider two well-known H2 sinks, H2 lost to the ocean and H2 occluded within rock minerals, and our analysis suggests that both are of similar size (both are 6x1011 moles H2/y). Budgeting results suggest a large difference between H2 sources (total production = 1x1013 moles H2/y) and H2 sinks (total losses = 1x1011 moles H2/y). Assuming this large difference represents H2 consumed by microbes (total consumption = 9x1011 moles H2/y), we explore rates of primary production by the chemosynthetic, sub-seafloor biosphere. Although the numbers presented require further examination and future modifications, the analysis suggests that the sub-seafloor H2 budget is similar to the sub-seafloor CH4 budget in the sense that globally significant quantities of both of these reduced gases are produced beneath the seafloor but never escape the seafloor due to microbial consumption.

The third and final component of this dissertation (Chapter 4) explores the self-organization of barchan sand dune fields. In nature, barchan dunes typically exist as members of larger dune fields that display striking, enigmatic structures that cannot be readily explained by examining the dynamics at the scale of single dunes, or by appealing to patterns in external forcing. To explore the possibility that observed structures emerge spontaneously as a collective result of many dunes interacting with each other, we built a numerical model that treats barchans as discrete entities that interact with one another according to simplified rules derived from theoretical and numerical work, and from field observations: Dunes exchange sand through the fluxes that leak from the downwind side of each dune and are captured on their upstream sides; when dunes become sufficiently large, small dunes are born on their downwind sides (“calving”); and when dunes collide directly enough, they merge. Results show that these relatively simple interactions provide potential explanations for a range of field-scale phenomena including isolated patches of dunes and heterogeneous arrangements of similarly sized dunes in denser fields. The results also suggest that (1) dune field characteristics depend on the sand flux fed into the upwind boundary, although (2) moving downwind, the system approaches a common attracting state in which the memory of the upwind conditions vanishes. This work supports the hypothesis that calving exerts a first order control on field-scale phenomena; it prevents individual dunes from growing without bound, as single-dune analyses suggest, and allows the formation of roughly realistic, persistent dune field patterns.

Ultra-fine pitch flip-chip assembly using isotropic conductive adhesives

This paper discusses results from a highly interdisciplinary research project which investigated different packaging options for ultra-fine pitch, low temperature and low cost flip-chip assembly. Isotropic Conductive Adhesives (ICAs) are stencil printed to form the interconnects for the package. ICAs are utilized to ensure a low temperature assembly process of flip-chip copper column bumped packages. Results are presented on the structural integrity of novel electroformed stencils. ICA deposits at sub-100 micron pitch and the subsequent thermo-mechanical behaviour of the flip-chip ICA joints are analysed using numerical modelling techniques. Optimal design rules for enhanced performance and thermomechanical reliability of ICA assembled flip-chip packages are formulated.

Interaction Effects of Light, Temperature and Nutrient Limitations (N, P and Si) on Growth, Stoichiometry and Photosynthetic Parameters of the Cold-Water Diatom Chaetoceros wighamii

Light (20-450 μmol photons m^-2 s^-1), temperature (3-11°C) and inorganic nutrient composition (nutrient replete and N, P and Si limitation) were manipulated to study their combined influence on growth, stoichiometry (C:N:P:Chl a) and primary production of the cold water diatom Chaetoceros wighamii. During exponential growth, the maximum growth rate (~0.8 d^-1) was observed at high temperture and light; at 3°C the growth rate was ~30% lower under similar light conditions. The interaction effect of light and temperature were clearly visible from growth and cellular stoichiometry. The average C:N:P molar ratio was 80:13:1 during exponential growth, but the range, due to different light acclimation, was widest at the lowest temperature, reaching very low C:P (~50) and N:P ratios (~8) at low light and temperature. The C:Chl a ratio had also a wider range at the lowest temperature during exponential growth, ranging 16-48 (weight ratio) at 3°C compared with 17-33 at 11°C. During exponential growth, there was no clear trend in the Chl a normalized, initial slope (α*) of the photosynthesis-irradiance (PE) curve, but the maximum photosynthetic production (P_m) was highest for cultures acclimated to the highest light and temperature. During the stationary growth phase, the stoichiometric relationship depended on the limiting nutrient, but with generally increasing C:N:P ratio. The average photosynthetic quotient (PQ) during exponential growth was 1.26 but decreased to <1 under nutrient and light limitation, probably due to photorespiration. The results clearly demonstrate that there are interaction effects between light, temperature and nutrient limitation, and the data suggests greater variability of key parameters at low temperature. Understanding these dynamics will be important for improving models of aquatic primary production and biogeochemical cycles in a warming climate.

Low-pressure synthesis and characterisation of hydroxyapatite derived from mineralise red algae

There is a great need to design functional bioactive substitute materials capable of surviving harsh and diverse conditions within the human body. Calcium-phosphate ceramics, in particular hydroxyapatite are well established substitute materials for orthopaedic and dental applications. The aim of this study was to develop a bioceramic from alga origins suitable for bone tissue application. This was achieved by a novel synthesis technique using ambient pressure at a low temperature of 100 degrees C in a highly alkaline environment. The algae was characterised using SEM, BET, XRD and Raman Spectroscopy to determine its physiochemical properties at each stage. The results confirmed the successful conversion of mineralised red alga to hydroxyapatite, by way of this low-pressure hydrothermal process. Furthermore, the synthesised hydroxyapatite maintained the unique micro-porous structure of the original algae, which is considered beneficial in bone repair applications. (C) 2007 Elsevier B.V. All rights reserved.

Low energy C-13(+) and C-13(2+) ion irradiation of water ice

In this paper we report the results of the first experimental study of the irradiation of low temperature water ice (30 and 90 k) using low energy (4keV) C-13(+) and C-(2+) ions. (CO2)-C-13 and H2o2 were readily formed within the H2O ice with the product ion yield and grwoth rate observed to be highly dependent on both the sample temperature and the ion charge state.

On the complexity of the water-gas shift reaction mechanism over a Pt/CeO2 catalyst: Effect of the temperature on the reactivity of formate surface species studied by operando DRIFT during isotopic transient at chemical steady-state

The present report investigates the role of formate species as potential reaction intermediates for the WGS reaction (CO + H2O -> CO2 + H-2) over a Pt-CeO2 catalyst. A combination of operando techniques, i.e., in situ diffuse reflectance FT-IR (DRIFT) spectroscopy and mass spectrometry (MS) during steady-state isotopic transient kinetic analysis (SSITKA), was used to relate the exchange of the reaction product CO2 to that of surface formate species. The data presented here suggest that a switchover from a non-formate to a formate-based mechanism could take place over a very narrow temperature range (as low as 60 K) over our Pt-CeO2 catalyst. This observation clearly stresses the need to avoid extrapolating conclusions to the case of results obtained under even slightly different experimental conditions. The occurrence of a low-temperature mechanism, possibly redox or Mars van Krevelen-like, that deactivates above 473 K because of ceria over-reduction is suggested as a possible explanation for the switchover, similarly to the case of the CO-NO reaction over Cu, I'd and Rh-CeZrOx (see Kaspar and co-workers [1-3]). (c) 2006 Elsevier B.V. All rights reserved.

Relaxation processes in room temperature ionic liquids: The case of 1-butyl-3-methyl imidazolium hexafluorophosphate

A detailed investigation on the nature of the relaxation processes occurring in a typical room temperature ionic liquid (RTIL), namely, 1-butyl-3-methyl imidazolium hexafluorophosphate ([bmim][PF6]), is reported. The study was conducted using both elastic and inelastic neutron scattering over a wide temperature range from 10 to 400 K, accessing the dynamic features of both the liquid and glassy amorphous states. In this study, the inelastic fixed energy scan technique has been applied for the first time to this class of materials. Using this technique, the existence of two relaxation processes below the glass transition and a further diffusive process occurring above the glass-liquid transition are observed. The low temperature processes are associated with methyl group rotation and butyl chain relaxation in the glassy state and have been modeled in terms of two Debye-like, Arrhenius activated processes. The high temperature process has been modeled in terms of a Kohlraush-Williams-Watts relaxation, with a distinct Vogel-Fulcher-Tamman temperature dependence. These results provide novel information that will be useful in rationalizing the observed structural and dynamical behavior of RTILs in the amorphous state.

Solutes determine the temperature windows for microbial survival and growth

Microbial cells, and ultimately the Earth's biosphere, function within a narrow range of physicochemical conditions. For the majority of ecosystems, productivity is cold-limited, and it is microbes that represent the failure point. This study was carried out to determine if naturally occurring solutes can extend the temperature windows for activity of microorganisms. We found that substances known to disorder cellular macromolecules (chaotropes) did expand microbial growth windows, fungi preferentially accumulated chaotropic metabolites at low temperature, and chemical activities of solutes determined microbial survival at extremes of temperature as well as pressure. This information can enhance the precision of models used to predict if extraterrestrial and other hostile environments are able to support life; furthermore, chaotropes may be used to extend the growth windows for key microbes, such as saprotrophs, in cold ecosystems and manmade biomes.