Stable oxygen, hydrogene and chlorine isotopes of mid-Atlantic abyssal peridotites

Serpentinized abyssal peridotites sampled by the Ocean Drilling Program Leg 209 along the mid-Atlantic Ridge near the 15°20'N Fracture Zone have been analyzed for oxygen, hydrogen, and chlorine isotope compositions in order to determine isotopic behavior under a wide range of serpentinization conditions and place constraints on fluid history. Oxygen and hydrogen thermometry suggests peak serpentinization temperatures of 300-500°C. Serpentine separates have low deltaD values possibly due to a magmatic fluid component or low-temperature exchange during seafloor weathering. Chlorine geochemistry focused on three holes: 1274A and 1272A (serpentinized peridotites) and 1268A (serpentinite locally altered to talc). Concentrations of both, water-soluble chloride (WSC) and structurally bound chloride (SBC) are significantly lower at Hole 1268A compared to Holes 1274A and 1272A. The delta37Cl values for WSC and SBC of serpentinites in Holes 1274A and 1272A are slightly positive (avg. WSC = 0.20 per mil, n = 22 and avg. SBC = 0.35 per mil, n = 22), representing typical seawater-hydration conditions commonly determined for abyssal peridotite. The SBC of serpentinites from Hole 1268A are also positive (avg. = 0.63 per mil); whereas, the SBC in talc-dominated samples is negative (avg. = -1.22 per mil). The WSC of both talc- and serpentine-dominated samples are also negative (avg. = -0.15 per mil). We interpret the chlorine isotope data to preserve a record of multiple fluid events. As seawater hydrated the peridotite, 37Cl was preferentially incorporated into the forming serpentine and water-soluble salts, yielding similar delta37Cl values on a regional scale as sampled by Holes 1268A, 1274A and 1272A. The resultant pore fluid was left depleted in 37Cl. Locally (Hole 1268A), this evolved fluid was remobilized possibly due to the initiation of hydrothermal circulation in response to emplacement of a mafic magma body. The low delta37Cl pore fluids attained elevated SiO2 and sulfur concentrations due to interaction with the gabbroic intrusion and, when ascending through the surrounding serpentinite, caused formation of isotopically negative talc. This secondary fluid also flushed the preserved serpentinite of its previously formed salts, resulting in negative delta37Cl WSC values. The delta37Cl SBC values of the serpentinite samples remained unmodified by reaction with the secondary fluid.

Geochemistry and Fe/(Ti + Ti), x, Curie temperature, and oxidation parameter z at DSDP Hole 597C

Electron microprobe and thermomagnetic analyses of selected basalt samples from Hole 597C were performed. The main purpose of this work was to investigate and estimate the degree of oxidation of the samples using the ratios of Fe to Ti and the Curie temperatures obtained from thermomagnetic curves. The results show that the magnetic properties of samples from Hole 597C change at a sub-bottom depth of 100 m, and that low-temperature and high-temperature oxidation processes prevailed above and below 100 m, respectively.

Chemistry of very young basalts from ODP Hole 106-648B

Basalts in Hole 648B, located in the rift valley of the Mid-Atlantic Ridge at 23°N in crust estimated to be less than 100,000 years old, are mainly fresh, but small amounts of secondary phases are found on fracture surfaces and in alteration halos within the rocks. The halos are defined by dark bands 1-4 mm thick that have developed parallel to fracture surfaces or pillow margins and which in some cases have migrated some centimeters into the rock. The dark bands are the principal locus of secondary phases. The secondary phases are olive-green and yellow protoceladonites, of composition and structure intermediate between celadonite and iron-rich saponite, red (Mn-poor) to opaque (Mn-rich) iron oxyhydroxides, mixtures of protoceladonite and iron oxyhydroxide, and rare manganese oxides. These phases occur mainly as linings or fillings of open spaces in the basalt within the dark bands. Sulfides and intersertal glass are the only primary phases that can be seen to have been altered. Where dark bands have migrated into the rock, the rock behind the advancing band is almost devoid of secondary phases, implying redissolution. The potassium and magnesium in the secondary phases could have been supplied from ambient seawater. The aluminum in the protoceladonites must have been derived from local reaction of intergranular glass. The source of iron and silica could have been intergranular glass or low temperature mineralizing solutions of the type responsible for the formation of deposits of manganese oxides and iron oxyhydroxides and silicates on the seafloor.

Very low temperatures, their attainment and uses : a survey of the physical principles underlying the attainment of extremely low temperatures and of their technical and scientific applications, as illustrated in a special exhibition held in the Science museum--March-May, 1936 /

"Chart of fixed points and temperature scales": p. [3] of cover.

A cyclopropabenzenylidenethenone (Propadienone) via a new route to alkylidenecycloproparenes

Reaction of 1,1-dichloro-2,5-diphenylcyclopropabenzene 6 with Meldrum's acid 8 in the presence of pyridine leads to coupling of the cycloproparenyl cation 7 with the stabilized diketo anion 9. Subsequent, spontaneous, base-induced dehydrochlorination gives the alkylidenecyclopropabenzene 11 in a one-pot reaction. Flash vacuum thermolysis of 11 at 650 degreesC ejects acetone and carbon dioxide, giving cyclopropabenzenylldenethenone 12 that is isolated in an Ar matrix at 20 K and characterized by a strong ketene band at 2107 cm(-1) in the IR spectrum.

Effect of seasonal variation and storage temperature on leaf chlorophyll fluorescence and vase life of cut roses

Low temperature injury (LTI) of roses (Rosa hybrida L.) is difficult to assess by visual observation. Relative chlorophyll fluorescence (CF; F-v/F-m) is a non-invasive technique that provides an index of stress effects on photosystem 11 (PS 11) activity. This instrumental technique allows determination of the photosynthetic efficiency of plant tissues containing chloroplasts, such as rose leaves. In the present study, pre- and Post-Storage measurements of F-v/F-m were carried out to assess LTI in 'First Red' and 'Akito' roses harvested year round. Relationships between the pre-harvest environment conditions of temperature, relative humidity and photon flux density (PFD), F-v/F-m, and, vase life duration after storage are reported. After harvest, roses were stored at 1, 5 and 10 degrees C for 10 days. Non-stored roses were the control treatment. F-v/F-m ratios were reduced following storage, suggesting LTI of roses. However, reductions in F-v/F-m were not closely correlated with reduced vase life duration and were seasonally dependent. Only during winter experiments was F-v/F-m of roses stored at 1 degrees C significantly (P <= 0.001) lower compared to F-v/F-m of non-stored control roses and roses stored at 5 and 10 degrees C. Thus, the fall of F-v/F-m was due to an interaction of growing season and storage at 1 degrees C. Vase lives of roses grown during winter were significantly (P <= 0.001) shorter compared to roses grown during summer. Length of vase life was intermediate for roses grown during autumn and spring. Because of the lack of correlation between F-v/F-m and post-storage vase life it is concluded that the CF parameter F-v/F-m is nota practical index for assessing LTI in cold-stored roses. Higher PFD and temperature in summer were positively and significantly correlated with maintenance of post-storage FvIF ratios and longer vase life. It is suggested that shorter vase lives and lower post-storage F-v/F-m values after storage at 1 degrees C are consequences of reduced photosynthesis and smaller carbohydrate pools in winter-harvested roses. (c) 2004 Elsevier B.V All rights reserved.

The interaction of nitrogen application and temperature during reproductive stage on spikelet sterility in field-grown rice

Increased grain yield in response to high rates of application of nitrogen (N) fertiliser is often limited by increased spikelet sterility, particularly under low temperature conditions in the New South Wales ( NSW) rice industry. In 3 field experiments, different N rates were applied for different sowing dates to investigate the interaction between N rate and temperature during microspore development on spikelet sterility and grain yield. In one experiment the effect of water depth on spikelet sterility was also investigated. Engorged pollen production, spikelet sterility, and yield and its components were recorded. Application of N affected a few different processes that lead into spikelet sterility. Application of N at both pre-flood (PF) and panicle initiation ( PI) significantly reduced the number of engorged pollen grains per anther, which was negatively correlated with spikelet sterility. Application of N and low temperature during microspore development with the absence of deep water also decreased pollen engorgement efficiency ( the percentage of pollen grains that were engorged). Application of N further increased spikelet density, which, in turn, increased both spikelet sterility and grain yield. The combined effect of spikelet density and low temperature during microspore development explained the 44% of variation in the number of engorged pollen grains per anther. Grain yield was decreased by low temperature during microspore development in the shallow water when N was applied. Spikelet sterility as a result of late sowing was strongly correlated with minimum temperature during flowering. It is concluded that N application reduced pollen number per anther as a result of increased spikelet density, and this made the spikelets more susceptible to low temperature, causing increased spikelet sterility.

Control of ordered structure and morphology of large-pore periodic mesoporous organosilicas by inorganic salt

Highly ordered rodlike periodic mesoporous organosilicas (PMO) were successfully synthesized using 1.2-bis(trimethoxysilyl)ethane as an precursor and triblock copolymer P123 as a template at low acid concentration and in the presence of inorganic salts (KCl). The role of acid and salt as well as the effects of synthesis temperature and reactant mole ratio in the control of morphology and the formation of ordered mesostructure was systematically examined. It was found that the addition of inorganic salt can dramatically expand the range of the synthesis parameters to produce highly ordered PMO structure and improve the quality of PMO materials. The morphology of PMOs was significantly dependent on the induction time for precipitation. The uniform PMO rods can only be synthesized in a narrow range of acid and salt concentrations. The results also show that the optimized salt concentration (I M) and low acidity (0.167 M) were beneficial to the formation of not only highly ordered mesostructure but also rodlike morphology. Increasing acidity resulted in fast hydrolysis reaction and short rod or plate-like particles. Highly ordered rod can also be prepared at low temperature (35 degrees C) with high salt amount (1.5 M) or high temperature (45 degrees C) with low salt amount (0.5 M). Optimum reactant molar composition at 40 degrees C is 0.035P123:8KCl:1.34HCI:444H(2)O:1.0bis(trimethoxysilyl)ethane. Lower or higher SiO2/PI23 ratio led to the formation of uniform meso-macropores or pore-blocking effect. (c) 2005 Elsevier Inc. All rights reserved.

Finite-connectivity spin-glass phase diagrams and low-density parity check codes

We obtain phase diagrams of regular and irregular finite-connectivity spin glasses. Contact is first established between properties of the phase diagram and the performance of low-density parity check (LDPC) codes within the replica symmetric (RS) ansatz. We then study the location of the dynamical and critical transition points of these systems within the one step replica symmetry breaking theory (RSB), extending similar calculations that have been performed in the past for the Bethe spin-glass problem. We observe that the location of the dynamical transition line does change within the RSB theory, in comparison with the results obtained in the RS case. For LDPC decoding of messages transmitted over the binary erasure channel we find, at zero temperature and rate R=14, an RS critical transition point at pc 0.67 while the critical RSB transition point is located at pc 0.7450±0.0050, to be compared with the corresponding Shannon bound 1-R. For the binary symmetric channel we show that the low temperature reentrant behavior of the dynamical transition line, observed within the RS ansatz, changes its location when the RSB ansatz is employed; the dynamical transition point occurs at higher values of the channel noise. Possible practical implications to improve the performance of the state-of-the-art error correcting codes are discussed. © 2006 The American Physical Society.

Studies in the anionic polymerization of methyl methacrylate

A study has been made of the anionic polymerization of methyl methacrylate using butyllithium and polystyryl lithium as initiators and using aluminium triisobutyl as a cocatalyst. The aspects of the polymerization that were examined were the effect of changing the order of addition of reagents, the temperature at which polymerization takes place and the polarity of the solvent. Trends were assessed in terms of molecular weight, molecular weight distribution and tacticity. In addition, a second monomer addition test was carried out to verify that the polymerization was truly a living one, and a kinetic study was attempted. Studies to investigate the effect of changing the order of addition of reagents showed that polymer with similar polydispersities and tacticities are produced whether the pre-mixing (mixing initiator and cocatalyst before addition of monomer) or the post-mixing (mixing monomer and cocatalyst before addition of initiator) method were used. However, polymerizations using the post-mixing mixing method demonstrated lower initiator efficiencies, possibly indicating a different initiating species. Investigations into the effect of changing the polymerization temperature show the molecular weight distribution to narrow as the temperature decreases, although a small amount of low molecular weight tailing was also observed at low temperature. A clear relationship between tacticity and temperature was observed with syndiotacticity increasing with decreasing temperature. Changes in solvent polarity were achieved by using mixtures of the standard solvent, toluene, with varying amounts of cyclohexane, tetrahydrofuran or dichloromethane. Experiments at low solvent polarity (using toluene/cyclohexane mixtures) showed problems with initiator solubility but produced polymer with lower polydispersity and higher syndiotacticity than in toluene alone. Experiments using toluene/THF mixtures yielded no polymer, thought to be owing to a side reaction between THF and aluminium triisobutyl. Increased solvent polarity, achieved using toluene/dichloromethane mixtures produced polymer with higher polydispersity and at lower yields than the conventional system, but also with higher syndiotacticity. Second monomer addition reactions demonstrated that the polymerization was 'living' since an increase in molecular weight was observed with no increase in polydispersity. Kinetic studies demonstrated the high speed of the polymerization but yielded no useful data.

Nitrogen implantation of tool steels and engineering coatings

Ion implantation modifies the surface composition and properties of materials by bombardment with high energy ions. The low temperature of the process ensures the avoidance of distortion and degradation of the surface or bulk mechanical properties of components. In the present work nitrogen ion implantation at 90 keV and doses above 1017 ions/cm2 has been carried out on AISI M2, D2 and 420 steels and engineering coatings such as hard chromium, electroless Ni-P and a brush plated Co-W alloy. Evaluation of wear and frictional properties of these materials was performed with a lubricated Falex wear test at high loads up to 900 N and a dry pin-on-disc apparatus at loads up to 40 N. It was found that nitrogen implantation reduced the wear of AISI 420 stainless steel by a factor of 2.5 under high load lubricated conditions and by a factor of 5.5 in low load dry testing. Lower but significant reductions in wear were achieved for AISI M2 and D2 steels. Wear resistance of coating materials was improved by up to 4 times in lubricated wear of hard Cr coatings implanted at the optimum dose but lower improvements were obtained for the Co-W alloy coating. However, hardened electroless Ni-P coatings showed no enhancement in wear properties. The benefits obtained in wear behaviour for the above materials were generally accompanied by a significant decrease in the running-in friction. Nitrogen implantation hardened the surface of steels and Cr and Co-W coatings. An ultra-microhardness technique showed that the true hardness of implanted layers was greater than the values obtained by conventional micro-hardness methods, which often result in penetration below the implanted depth. Scanning electron microscopy revealed that implantation reduced the ploughing effect during wear and a change in wear mechanism from an abrasive-adhesive type to a mild oxidative mode was evident. Retention of nitrogen after implantation was studied by Nuclear Reaction Analysis and Auger Electron Spectroscopy. It was shown that maximum nitrogen retention occurs in hard Cr coatings and AISI 420 stainless steel, which explains the improvements obtained in wear resistance and hardness. X-ray photoelectron spectroscopy on these materials revealed that nitrogen is almost entirely bound to Cr, forming chromium nitrides. It was concluded that nitrogen implantation at 90 keV and doses above 3x1017 ions/cm2 produced the most significant improvements in mechanical properties in materials containing nitride formers by precipitation strengthening, improving the load bearing capacity of the surface and changing the wear mechanism from adhesive-abrasive to oxidative.

High temperature gas cleaning for advanced syngas utilization:Paper # 95

Biofuels and chemicals from biomass mean the gasification of biogenic feedstocks and the synthesis via methanol, dimethylester (DME) or Fischer-Tropsch products. To prevent the sensitive synthesis catalysts from poisoning the syngas must be free of tar and particulates. The trace concentrations of S-, C1-, N-species, alkali and heavy metals must be of the order of a few ppb. Moreover maximum conversion efficiency will be achieved performing the gas cleaning above the synthesis conditions. The concept of an innovative dry HTHP syngas cleaning is presented. Based on the HT particle filtration and suitable sorption and catalysis processes for the relevant contaminants a total concept will be derived, which leads to a syngas quality required for synthesis catalysts in only 2 combined stages. The experimental setup for the HT gas cleaning behind the 60 kWtherm entrained flow gasifier REGA of the institute is described. Results from HT filter experiments in pilot scale are presented. The performance of 2 natural minerals for HC1 and H2S sorption is discussed with respect to the parameters temperature, surface and residence time. Results from lab scale investigations on low temperature tar catalysts' performance (commercial and proprietary development) are discussed finally.

Abnormal systemic and ocular vascular response to temperature provocation in primary open-angle glaucoma patients:a case for autonomic failure?

PURPOSE. To assess systemic and ocular vascular reactivity in response to warm and cold provocation in untreated patients with primary open-angle glaucoma and normal control subjects. METHODS. Twenty-four patients with primary open-angle glaucoma and 22 normal control subjects were subjected to a modified cold pressor test involving immersion of the right hand in 40°C warm water followed by 4°C cold water exposure, and finger and ocular blood flow were assessed by means of peripheral laser Doppler flowmetry and retinal flowmetry, respectively. Finger and body temperature as well as intraocular pressure, systemic blood pressure, systemic pulse pressure, heart rate, and ocular perfusion pressure were also monitored. RESULTS. The patients with glaucoma demonstrated an increase in diastolic blood pressure (P = 0.023), heart rate (P = 0.010), and mean ocular perfusion pressure (P = 0.039) during immersion of the tested hand in 40°C water. During cold provocation, the patients demonstrated a significant decrease in finger (P = 0.0003) and ocular blood flow (the parameter velocity measured at the temporal neuroretinal rim area; P = 0.021). Normal subjects did not demonstrate any blood flow or finger temperature changes during immersion of the tested hand in 40°C water (P > 0.05); however, they exhibited increases in systolic blood pressure (P = 0.034) and pulse pressure (P = 0.0009) and a decrease in finger blood flow (P = 0.0001) during cold provocation. In normal subjects, the ocular blood flow was unchanged during high- and low-temperature challenge. CONCLUSIONS. Cold provocation elicits a different blood pressure, and ocular blood flow response in patients with primary open-angle glaucoma compared with control subjects. These findings suggest a systemic autonomic failure and ocular vascular dysregulation in POAG patients.

Computational modeling of intermediate temperature proton exchange membrane (PEM) fuel cells

A two-phase three-dimensional computational model of an intermediate temperature (120--190°C) proton exchange membrane (PEM) fuel cell is presented. This represents the first attempt to model PEM fuel cells employing intermediate temperature membranes, in this case, phosphoric acid doped polybenzimidazole (PBI). To date, mathematical modeling of PEM fuel cells has been restricted to low temperature operation, especially to those employing Nafion ® membranes; while research on PBI as an intermediate temperature membrane has been solely at the experimental level. This work is an advancement in the state of the art of both these fields of research. With a growing trend toward higher temperature operation of PEM fuel cells, mathematical modeling of such systems is necessary to help hasten the development of the technology and highlight areas where research should be focused.^ This mathematical model accounted for all the major transport and polarization processes occurring inside the fuel cell, including the two phase phenomenon of gas dissolution in the polymer electrolyte. Results were presented for polarization performance, flux distributions, concentration variations in both the gaseous and aqueous phases, and temperature variations for various heat management strategies. The model predictions matched well with published experimental data, and were self-consistent.^ The major finding of this research was that, due to the transport limitations imposed by the use of phosphoric acid as a doping agent, namely low solubility and diffusivity of dissolved gases and anion adsorption onto catalyst sites, the catalyst utilization is very low (∼1--2%). Significant cost savings were predicted with the use of advanced catalyst deposition techniques that would greatly reduce the eventual thickness of the catalyst layer, and subsequently improve catalyst utilization. The model also predicted that an increase in power output in the order of 50% is expected if alternative doping agents to phosphoric acid can be found, which afford better transport properties of dissolved gases, reduced anion adsorption onto catalyst sites, and which maintain stability and conductive properties at elevated temperatures.^

Developing a high density platinum/alumina hermetic feedthrough

Typically, hermetic feedthroughs for implantable devices, such as pacemakers, use a alumina ceramic insulator brazed to a platinum wire pin. This combination of material has a long history in implantable devices and has been approved by the FDA for implantable hermetic feedthroughs. The growing demand for increased input/output (I/O) hermetic feedthroughs for implantable neural stimulator applications could be addressed by developing a new, cofired platinum/alumina multilayer ceramic technology in a configuration that supports 300 plus I/Os, which is not commercially available. Seven platinum powders with different particle sizes were used to develop different conductive cofire inks to control the densification mismatch between platinum and alumina. Firing profile (ramp rate, burn- out and holding times) and firing atmosphere and concentrations (hydrogen (wet/dry), air, neutral, vacuum) were also optimized. Platinum and alumina exhibit the alloy formation reaction in a reduced atmosphere. Formation of any compound can increase the bonding of the metal/ceramic interface, resulting in enhanced hermeticity. The feedthrough fabricated in a reduced atmosphere demonstrated significantly superior performance than that of other atmospheres. A composite structure of tungsten/platinum ratios graded thru the via structure (pure W, 50/50 W/Pt, 80/20 Pt/W and pure Pt) exhibited the best performance in comparison to the performance of other materials used for ink metallization. Studies on the high temperature reaction of platinum and alumina, previously unreported, showed that, at low temperatures in reduced atmosphere, Pt 3Al or Pt8Al21 with a tetragonal structure would be formed. Cubic Pt3Al is formed upon heating the sample to temperatures above 1350 °C. This cubic structure is the equilibrium state of Pt-Al alloy at high temperatures. The alumina dissolves into the platinum ink and is redeposited as a surface coating. This was observed on both cofired samples and pure platinum thin films coated on a 99.6 Wt% alumina and fired at 1550 °C. Different mechanisms are proposed to describe this behavior based on the size of the platinum particle