A refined solution to Earth's hidden niobium: implications for evolution of continental crust and mode of core formation

New high-precision niobium (Nb) and tantalum (Ta) concentration data are presented for early Archaean metabasalts, metabasaltic komatiites and their erosion products (mafic metapelites) from SW Greenland and the Acasta gneiss complex, Canada. Individual datasets consistently show sub-chondritic Nb/Ta ratios averaging 15.1+/-11.6. This finding is discussed with regard to two competing models for the solution of the Nb-deficit that characterises the accessible Earth. Firstly, we test whether Nb could have sequestered into the core due to its slightly siderophile (or chalcophile) character under very reducing conditions, as recently proposed from experimental evidence. We demonstrate that troilite inclusions of the Canyon Diablo iron meteorite have Nb and V concentrations in excess of typical chondrites but that the metal phase of the Grant, Toluca and Canyon Diablo iron meteorites do not have significant concentrations of these lithophile elements. We find that if the entire accessible Earth Nb-deficit were explained by Nb in the core, only ca. 17% of the mantle could be depleted and that by 3.7 Ga, continental crust would have already achieved ca. 50% of its present mass. Nb/Ta systematics of late Archaean metabasalts compiled from the literature would further require that by 2.5 Ga, 90% of the present mass of continental crust was already in existence. As an alternative to this explanation, we propose that the average Nb/Ta ratio (15.1+/-11.6) of Earth's oldest mafic rocks is a valid approximation for bulk silicate Earth. This would require that ca. 13% of the terrestrial Nb resided in the Ta-free core. Since the partitioning of Nb between silicate and metal melts depends largely on oxygen fugacity and pressure, this finding could mean that metal/silicate segregation did not occur at the base of a deep magma ocean or that the early mantle was slightly less reducing than generally assumed. A bulk silicate Earth Nb/Ta ratio of 15.1 allows for depletion of up to 40% of the total mantle. This could indicate that in addition to the upper mantle, a portion of the lower mantle is depleted also, or if only the upper mantle were depleted, an additional hidden high Nb/Ta reservoir must exist. Comparison of Nb/Ta systematics between early and late Archaean metabasalts supports the latter idea and indicates deeply subducted high Nb/Ta eclogite slabs could reside in the mantle transition zone or the lower mantle. Accumulation of such slabs appears to have commenced between 2.5 and 2.0 Ga. Regardless of these complexities of terrestrial Nb/Ta systematics, it is shown that the depleted mantle Nb/Th ratio is a very robust proxy for the amount of extracted continental crust, because the temporal evolution of this ratio is dominated by Th-loss to the continents and not Nb-retention in the mantle. We present a new parameterisation of the continental crust volume versus age curve that specifically explores the possibility of lithophile element loss to the core and storage of eclogite slabs in the transition zone. (C) 2003 Elsevier Science B.V. All rights reserved.

Effect of addition of maltodextrin on drying kinetics and stickiness of sugar and acid-rich foods during convective drying: experiments and modelling

The effect of addition of maltodextrin on drying kinetics of drops containing fructose, glucose, sucrose and citric acid individually and in mixtures was studied experimentally using single drop drying experiments and numerically by solving appropriate mass and heat transfer equations. The numerical predictions agreed with the experimental moisture and temperature histories within 5-6% average relative (absolute) errors and average differences of +/- 1degreesC, respectively. The stickiness of these drops was determined using the glass transition temperature (T-g) of the drops' surface layer as an indicator. The experimental stickiness histories followed the model predictions with reasonable accuracy. A safe drying (non-sticky) regime in a spray drying environment has been proposed, and used to estimate the optimum amount of addition of maltodextrin for successful spray drying of 120 micron diameter droplets of fruit juices. (C) 2003 Elsevier Ltd. All rights reserved.

The effect of Yb addition in Bi2Sr2Ca1-x,YbxU2Oy partial melted thick films

To study the phase relations in the Bi-2212 and Yb2O3 system, Bi2Sr2Ca1-xYbxCu2Oy thick films are prepared by partial melt processing via an intermediate reaction between Bi-2212 and Yb2O3. When Bi-2212 and Yb2O3 are partially melted and then slowly cooled, solid solutions of Bi2Sr2Ca1-xYbxCu2Oy form by reactions between liquid and solid phases which contain Yb. Following these reactions, Ca is partially replaced in Bi-2212 matrix and participates in the formation of secondary phases, such as Bi-free, (Ca, Sr)O-x and CaO. Variation of the Bi-2212-Yb2O3 ratios and processing parameters changes the balance between the phases and leads to different Yb:Ca ratios in the Bi-2212 matrix of processed thick films. When the partial melting process is optimized for each sample to minimize the growth of secondary phases, x = 0.42-0.46 for the samples prepared at pO(2) = 0.01 atm, x = 0.24-0.29 for the samples prepared at pO(2) = 0.21 atm, x = 0.18-0.23 for the samples prepared at pO(2) = 0.99 atm are obtained regardless to the starting compositions. It is found that superconducting properties of Bi2Sr2Ca1-xYbxCu2Oy thick films strongly depend on the processing conditions, because the conditions result in different Yb content in the Bi-2212 matrix and the volume fraction of the secondary phases. The highest T-c(0) of 77, 90 and 91 K were obtained for the samples processed at 0.01, 0.21 and 0.99 atm of O-2, respectively.

Accessing chain length dependent termination rate coefficients of methyl methacrylate (MMA) via the reversible addition fragmentation chain transfer (RAFT) process

The RAFT-CLD-T methodology is demonstrated to be not only applicable to 1-substituted monomers such as styrene and acrylates, but also to 1,1-disubstituted monomers such as MMA. The chain length of the terminating macromolecules is controlled by CPDB in MMA bulk free radical polymerization at 80 degrees C. The evolution of the chain length dependent termination rate coefficient, k(t)(i,i), was constructed in a step-wise fashion, since the MMA/CPDB system displays hybrid behavior (between conventional and living free radical polymerization) resulting in initial high molecular weight polymers formed at low RAFT agent concentrations. The obtained CLD of k(t) in MMA polymerizations is compatible with the composite model for chain length dependent termination. For the initial chain-length regime, up to a degree of polymerization of 100, k(t) decreases with alpha (in the expression k(t)(i,i) = k(t)(0) . i(-alpha)) being close to 0.65 at 80 degrees C. At chain lengths exceeding 100, the decrease is less pronounced (affording an alpha of 0.15 at 80 degrees C). However, the data are best represented by a continuously decreasing nonlinear functionality implying a chain length dependent alpha.

Modeling the molecular weight distribution of block copolymer formation in a reversible addition-fragmentation chain transfer mediated living radical polymerization

Block copolymers have become an integral part of the preparation of complex architectures through self-assembly. The use of reversible addition-fragmentation chain transfer (RAFT) allows blocks ranging from functional to nonfunctional polymers to be made with predictable molecular weight distributions. This article models block formation by varying many of the kinetic parameters. The simulations provide insight into the overall polydispersities (PDIs) that will be obtained when the chain-transfer constants in the main equilibrium steps are varied from 100 to 0.5. When the first dormant block [polymer-S-C(Z)=S] has a PDI of 1 and the second propagating radical has a low reactivity to the RAFT moiety, the overall PDI will be greater than 1 and dependent on the weight fraction of each block. When the first block has a PDI of 2 and the second propagating radical has a low reactivity to the RAFT moiety, the PDI will decrease to around 1.5 because of random coupling of two broad distributions. It is also shown how we can in principle use only one RAFT agent to obtain block copolymers with any desired molecular weight distribution. We can accomplish this by maintaining the monomer concentration at a constant level in the reactor over the course of the reaction. (c) 2005 Wiley Periodicals, Inc.

Controlled Radical Polymerization of Styrene and Methyl Acrylate in the Presence of Reversible Addition-Fragmentation Chain Transfer Agents, Phenylethyl Phenyl Dithioacetate and Phenyldithioacetic Acid

The use of phenyldithioacetic acid (PDA) in homopolymerizations of styrene or methyl acrylate produced only a small fraction of chains with dithioester end groups. The polymerizations using 1-phenylentyl phenyldithioacetate (PEPDTA) and PDA in the same reaction showed that PDA had little or no influence on the rate or molecular weight distribution even when a 1:1 ratio is used. The mechanistic pathway for the polymerizations in the presence of PDA seemed to be different for each monomer. Styrene favors addition of styrene to PDA via a Markovnikov type addition to form a reactive RAFT agent. The polymer was shown by double detection SEC to contain dithioester end groups over the whole distribution. This polymer was then used in a chain extension experiment and the M-n was close to theory. A unique feature of this work was that PDA could be used to form a RAFT agent in situ by heating a mixture of styrene and PDA for 24 h at 70 degrees C and then polymerizing in the presence of AIBN to give a linear increase in Mn and low values of PDI (< 1.14). In the case of the polymerization of MA with PDA, the mechanism was proposed to be via degradative chain transfer. (c) 2005 Wiley Periodicals, Inc.

Design strategies for controlling the molecular weight and rate using reversible addition-fragmentation chain transfer mediated living radical polymerization

Living radical polymerization has allowed complex polymer architectures to be synthesized in bulk, solution, and water. The most versatile of these techniques is reversible addition-fragmentation chain transfer (RAFT), which allows a wide range of functional and nonfunctional polymers to be made with predictable molecular weight distributions (MWDs), ranging from very narrow to quite broad. The great complexity of the RAFT mechanism and how the kinetic parameters affect the rate of polymerization and MWD are not obvious. Therefore, the aim of this article is to provide useful insights into the important kinetic parameters that control the rate of polymerization and the evolution of the MWD with conversion. We discuss how a change in the chain-transfer constant can affect the evolution of the MWD. It is shown how we can, in principle, use only one RAFT agent to obtain a poly-mer with any MWD. Retardation and inhibition are discussed in terms of (1) the leaving R group reactivity and (2) the intermediate radical termination model versus the slow fragmentation model. (c) 2005 Wiley Periodicals, Inc.

Effect of carbon/noncarbon addition on hydrogen storage behaviors of magnesium hydride

Various Mg/carbon and Mg/noncarbon composite systems were prepared by mechanical milling and their hydrogen storage behaviors were investigated. It was found that all the carbon additives exhibited prominent advantage over the noncarbon additives, such as BN nanotubes (BNNTs) or asbestos in improving the hydrogen capacity and dehydriding/hydriding kinetics of Mg. And among the various carbon additives, purified single-walled carbon nanotubes (SWNTs) exhibited the most prominent catalytic effect on the hydrogen storage properties of Mg. The hydrogen capacities of all Mg/C composites at 573 K reached more than 6.2 wt.% within 10 min, about 1.5 wt.% higher than that of pure MgH2 at the identical operation conditions. Under certain operation temperatures, H-absorption/desorption rates of Mg/carbon systems were over one order of magnitude higher than that of pure Mg. Furthermore, the starting temperature of the desorption reaction of MgH2 has been lowered to 60 K by adding SWNTs. On the basis of the hydrogen storage behavior and structure/phase investigations, the possible mechanism involved in the property improvement of Mg upon adding carbon materials was discussed. (c) 2005 Elsevier B.V. All rights reserved.

Addition of cue exposure to cognitive-behaviour therapy for alcohol misuse: a randomized trial with dysphoric drinkers

Aim To test whether addition of moderation-orientated cue exposure (CE) or CE after dysphoric mood induction ( emotional CE, ECE) improved outcomes above those from cognitive-behaviour therapy alone (CBT) in people who drank when dysphoric. Design Multi-site randomized controlled trial comparing CBT with CBT + CE and CBT + ECE. Setting Out-patient rooms in academic treatment units in Brisbane and Sydney, Australia. Participants People with alcohol misuse and problems controlling consumption when dysphoric (n = 163). Those with current major depressive episode were excluded. Intervention Eight weekly 75-minute sessions of individual treatment for alcohol problems were given to all participants, with CBT elements held constant across conditions. From session 2, CBT + CE participants resisted drinking while exposed to alcohol cues, with two priming doses of their preferred beverage being given in some sessions. After an initial CE session, CBT + ECE participants recalled negative experiences before undertaking CE, to provide exposure to emotional cues of personal relevance. Measurements Alcohol consumption, related problems, alcohol expectancies, self-efficacy and depression. Results Average improvements were highly significant across conditions, with acceptable maintenance of effects over 12 months. Both treatment retention and effects on alcohol consumption were progressively weaker in CBT + CE and CBT + ECE than in CBT alone. Changes in alcohol dependence and depression did not differ across conditions. Conclusions These data do not indicate that addition of clinic-based CE to standard CBT improves outcomes. A different approach to the management of craving may be required.

Effects of solids concentration, pH and carbon addition on the production rate and composition of volatile fatty acids in prefermenters using primary sewage sludge

Increasing evidence is emerging that the performance of enhanced biological phosphorus removal (EBPR) systems relies on not only the total amount but also the composition of volatile fatty acids (VFAs). Domestic wastewater often contains limited amounts of VFAs with acetic acid typically being the dominating species. Consequently, prefermenters are often employed to generate additional VFAs to meet the demand for carbon by EBPR and/or denitrification processes. Limited knowledge is currently available on the effects of operational conditions on the production rate and composition of VFAs in prefermenters. In this study, a series of controlled batch experiments were conducted with sludge from a full-scale prefermenter to determine the impact of solids concentration, pH and addition of molasses on prefermentation processes. It was found that an increase in solids concentration enhanced total VFA production with an increased propionic acid fraction. The optimal pH for prefermentation was in the range of 6-7 with significant productivity loss when pH was below 5.5. Molasses addition significantly increased the production of VFAs particularly the propionic acid. However, the fermentation rate was likely limited by the biological activity of the sludge rather than by the amount of molasses added.

The effect of Cu addition and milling contaminations on the microstructure evolution of ball milled Al-Pb alloy during sintering

Al-10 wt.%Pb and Al-10 wt.%Pb-x wt.%Cu (x = 0-7.0) bulk alloys were prepared by sintering the mechanically alloyed powders at various temperatures. The microstructure changes of the as consolidated powders in the course of sintering were analyzed by differential scanning calorimetry, scanning electron microscopy, X-ray diffraction analysis and transmission electron microscopy. It has been found that, with respect to the Al-10 wt.%Pb-x wt.%Cu alloy, CuAl2 and Cu9Al4 phases formed in the milling process, and the amount of CuAl2 phase increased while the Cu9Al4 phase disappeared gradually in the sintering process. In both Al-10 wt.%Pb and Al-10 wt.%Pb-x wt.%Cu alloys, the sintering process results in the coarsening of Pb phase and the growth rate of Pb phase fulfills the Lifshitz-Slyozov-Wagner equation even though the size of the Pb phase was in nanometer range. The Pb particle exhibits cuboctahedral morphology and has a cubic to cubic orientation relationship with the Al matrix. The addition of Cu strongly depressed the growth rate of Pb. Contamination induced by milling has apparent influence on the microstructure of the sintered alloys. Al7Cu2Fe and aluminium oxide phases were identified in the sintered alloys. The cuboctahedral morphology of Pb particles was broken up by the presence of the oxide phase. (c) 2006 Elsevier B.V. All rights reserved.