Fe–Mg diffusion in olivine II: point defect chemistry,change of diffusion mechanisms and a model for calculation of diffusion coefficients in natural olivine

Analysis of existing data and models on point defects in pure (Fe,Mg)-olivine (Phys Chem Miner 10:27–37,1983; Phys Chem Miner 29:680–694, 2002) shows that it is necessary to consider thermodynamic non-ideality of mixing to adequately describe the concentration of point defects over the range of measurement. In spite of different sources of uncertainties, the concentrations of vacancies in octahedral sites in (Fe,Mg)-olivine are on the order of 10⁻⁴ per atomic formula unit at 1,000–1,200 °C according to both the studies. We provide the first explicit plots of vacancy concentrations in olivine as a function of temperature and oxygen fugacity according to the two models. It is found that in contrast to absolute concentrations at ∼1,100 °C and dependence on fO₂, there is considerable uncertainty in our knowledge of temperature dependence of vacancy concentrations. This needs to be considered in discussing the transport properties such as diffusion coefficients. Moreover, these defect models in pure (Fe,Mg)-olivine need to be extended by considering aliovalent impurities such as Al, Cr to describe the behavior of natural olivine. We have developed such a formulation, and used it to analyze the considerable database of diffusion coefficients in olivine from Dohmen et al. (Phys Chem Miner this volume, 2007) (Part - I) and older data in the literature. The analysis documents unequivocally for the first time a change of diffusion mechanism in a silicate mineral—from the transition metal extrinsic (TaMED) to the purely extrinsic (PED) domain, at fO₂ below 10⁻¹⁰  Pa, and consequently, temperatures below 900 °C. The change of diffusion mechanism manifests itself in a change in fO₂ dependence of diffusivity and a slight change in activation energy of diffusion—the activation energy increases at lower temperatures. These are consistent with the predictions of Chakraborty (J Geophys Res 102(B6):12317–12331, 1997). Defect formation enthalpies in the TaMED regime (distinct from intrinsic defect formation) lie between −66 and + 15 kJ/mol and migration energies of octahedral cations in olivine are most likely ∼ 260 kJ/mol, consistent with previous inferences (Phys Chem 207:147–162, 1998). Plots are shown for diffusion at various constant fO₂ as well as along fO₂ buffers, to highlight the difference in behavior between the two. Considering all the diffusion data and constraints from the point defect models, (Fe–Mg) diffusion in olivine along [001] is best described by the Master equations: (1) At oxygen fugacities greater than 10⁻¹⁰ Pa:

Design of a High Efficiency Acoustic Phased Array Antenna for an Acoustic Wind Profiler

Summary Improvements to the performance of acoustic wind profilers necessitate designing efficient acoustic antennas for the profilers, so that weak echoes can be received to enhance data availability. An efficient acoustic antenna needs to optimize electrical to acoustic and acoustic to electrical conversion efficiency as measured at the antenna axis. It also needs to provide a good directional response, and be able to handle increased electrical power. Phased array antennas, designed using piezo-electric transducers, should provide better characteristics in this regard. In the present study several different transducer elements were characterized with respect to their relative efficiencies. On the basis of this characterization, measurement of acoustic background noise at the expected site of antenna location and comparative study of atmospheric molecular absorption at the element peak efficiency frequencies, it is concluded that Motorola KSN 1025 A transducer is the best speaker element for the array antennas for profilers up to around 500 meters. The present array antenna has been designed using 104 KSN 1025 A piezo-electric transducer elements. The corner elements were removed from a 16 × 8 element speaker matrix, yielding an irregular octagonal pattern. Before installing the elements in the array, each element was individually characterized for its transmit and receive conversion efficiency, and variations in the product of these efficiencies (conversion gain) amongst the different elements, has been usefully employed to taper the array gain from centre to periphery. The antenna was systematically characterized, in an acoustic anechoic chamber, with respect to its axial transmit and receive conversion efficiencies and directional response. Received October 14, 1998 Revised March 1, 1999     

The two mooring dolphin concept for exposed tanker terminals

The conventional design for a tanker terminal provides for two or more mooring dolphins on each side of the breasting dolphins. Head and stern lines are attached to the outer mooring dolphins and breast lines to the inner mooring dolphins. In exposed locations, the expense of construction may be significantly reduced if a way can be found to reduce the number of mooring dolphins required for the safe mooring of ships at a fixed berth.This paper, based on studies for a proposed terminal for tankers from 25,000 to 100,000 DWT in the Bay of Fundy in Eastern Canada, discusses the possibility of reducing the total number of mooring dolphins from four to two. Results of a static analysis of mooring loads due to wind and current and a hydraulic model test for mooring loads due to waves are presented.Operational aspects of the two mooring dolphin layout are discussed. It is concluded that the two mooring dolphin concept is an efficient mooring arrangement which will reduce the cost of fixed berth terminals. It is noted, however, that many of the smaller, older tankers in the world fleet do not have adequate mooring equipment to use such a berth and it is recommended that the necessary change in deck equipment be made to allow for such an arrangement. It is also recommended that ship personnel acquaint themselves with mooring procedures using breast and spring lines alone.     

Understanding plot‐scale hydrology of Lesser Himalayan watershed—A field study and HYDRUS‐2D modelling approach

Soil moisture dynamics have a significant effect on overland flow generation. Catchment aspect is one of the major controlling factors of overland flow and soil moisture behaviour. A few experimental studies have been carried out in the uneven topography of the Himalayas. This study presents plot‐scale experiments using portable rainfall simulator at an altitude of 1,230 m above mean sea level and modelling of overland flow using observed datasets. Two plots were selected in 2 different aspects of Aglar watershed of Lesser Himalaya; the agro‐forested (AF) plot was positioned at the north aspect whereas the degraded (DE) plot was located at the south aspect of the hillslope. HS flumes and rain gauges were installed to measure the runoff at the outlet of the plot and the rainfall depth during rainfall simulation experiments. Moreover, 10 soil moisture sensors were installed at upslope and downslope locations of both the plots at 5, 15, 25, 35, and 45 cm depth from ground level to capture the soil moisture dynamics. The tests were conducted at intensities of 79.8 and 75 mm/hr in AF plot and 82.2 and 72 mm/hr in the DE plot during Test 1 and Test 2, respectively. The observed data indicate the presence of reinfiltration process only in the AF plot. The high water holding capacity and the presence of reinfiltration process results in less runoff volume in the AF plot compared with the DE plot. The Hortonian overland flow mechanism was found to be the dominant overland flow mechanism as only a few layers of top soil get saturated during all of the rainfall–runoff experiments. The runoff, rainfall, and soil moisture data were subsequently used to calibrate the parameters of HYDRUS‐2D overland flow module to simulate the runoff hydrograph and soil moisture. The components of hydrograph were evaluated in terms of peak discharge, runoff volume and time of concentration, the results were found to be within the satisfactory range. The goodness of fit of simulated hydrographs were more than 0.85 and 0.95 for AF and DE plot, respectively. The model produced satisfactory simulation results of soil moisture for all of the rainfall–runoff experiments. The HYDRUS‐2D overland flow module was found promising to simulate the runoff hydrograph and soil moisture in plot‐scale research.     

Seasonal variation in the biochemical composition of red seaweed (<Emphasis Type="Italic">Catenella repens</Emphasis>) from Gangetic delta,northeast coast of India

The biochemical composition of red seaweeds, Catenella repens was investigated in this present study along with subsequent analysis of relevant physico-chemical variables. In this study, the relationship between the nutritive components of this species and the ambient environmental parameters was established. Protein content varied from 2.78 ± 0.30% of dry weight (stn.3) to 16.03 ± 0.96% of dry weight (stn.1) with highest values during monsoon. The protein levels were positively correlated with dissolved nitrate content and negatively correlated with water temperature (except stn.3) and salinity. Carbohydrate content of this species varied significantly (p < 0.05) during pre-monsoon between stations and the values showed positive relationship with salinity and surface water temperature. In contrast to carbohydrate, lipid concentration was lowest in values and varied very slightly between seasons and stations. Astaxanthin content of the seaweed species was greater in pre-monsoon than monsoon and post-monsoon in all the selected stations. Compared with the three seasons, samples of red seaweed collected in pre-monsoon has high carbohydrate-astaxanthin in contrast to protein-lipid which showed high values during monsoon. Statistical analysis computed among the environmental and biochemical parameters suggests the potential role played by the abiotic parameters on biosynthetic pathways of seaweed. This paper also highlights the influence of the nutritional quality of water that can be used for mass cultivation of Catenella repens.     

Analytical solutions of tracer transport in fractured rock associated with precipitation-dissolution reactions

Precipitation-dissolution reactions are important for a number of applications such as isotopic tracer transport in the subsurface. Analytical solutions have been developed for tracer transport in both single-fracture and multiple-fracture systems associated with these reactions under transient and steady-state transport conditions. These solutions also take into account advective transport in fractures and molecular diffusion in the rock matrix. For studying distributions of disturbed tracer concentration (the difference between actual concentration and its equilibrium value), effects of precipitation-dissolution reactions are mathematically equivalent to a “decay” process with a decay constant proportional to the corresponding bulk reaction rate. This important feature significantly simplifies the derivation procedure by taking advantage of the existence of analytical solutions for tracer transport associated with radioactive decay in fractured rock. It is also useful for interpreting tracer breakthrough curves, because the impact of a decay process is relatively easy to analyze. Several illustrative examples are presented, which show that the results are sensitive to fracture spacing, matrix diffusion coefficient (fracture surface area), and bulk reaction rate (or “decay” constant), indicating that the relevant flow and transport parameters may be estimated by analyzing tracer signals.     

Timescales of disequilibrium melting in the crust: constraints from modelling the distribution of multiple trace elements and a case study from the Lesser Himalayan rocks of Sikkim

A numerical code has been developed to track the distribution of trace elements in crustal rocks undergoing melting. The model handles diffusion with moving boundaries and accounts for the processes of diffusion, dissolution and precipitation in a partially molten system. Among the various input parameters for modelling, source composition (i.e. modal abundance) variations, diffusion coefficients and partition coefficients are found to exert a significant control on the melt chemistry. The other inputs such as melt reaction stoichiometry, kinetics of melting and grain size of protolith have lesser influence. Exploration of the general behaviour indicates that for systems in which disequilibrium melting of the kind considered in this paper occurs, trace element concentrations may be used to constrain the composition of the protolith or the timescales of melting, depending on the specific circumstances. After exploring some general features of melting in a pelitic system, the model is applied to calculate trace element distributions in migmatites from the Lesser Himalayan rocks in Sikkim, India. We focus on the distribution of trace elements during the initial stages of melt formation. These partially molten rocks show disequilibrium distribution of trace elements, and the numerical code is capable of quantitatively reproducing many of the observed patterns. The results of the modelling indicate that the observed melts in this zone were formed within 50,000 years and that segregation of melts (into leucosome and restite) was complete between 50,000 and 250,000 years. These short timescales may point to deformation-enhanced melt segregation at least on a hand specimen scale. It is important to distinguish between timescales of segregation over these scales and timescales of removal of melt on an outcrop scale to form plutons—the latter, requiring higher degrees of melting and larger distances of migration, take longer.     

Runoff generation mechanisms in pastures of the Sand Mountain region of Alabama—a field investigation

Excessive application of poultry litter to pastures in the Sand Mountain region of north Alabama has resulted in phosphorus (P) contamination of surface water bodies and buildup of P in soils of this region. Since surface runoff is recognized as the primary mechanism of P transport, understanding surface runoff generation mechanisms are crucial for alleviating water quality problems in this region. Identification of surface runoff generation mechanisms is also important for delineation of hydrologically active areas (HAAs). Therefore, the specific objective of this study was to identify surface runoff generation mechanisms (infiltration excess versus saturation excess) using distributed surface and subsurface sensors and rain gauge. Results from three rainfall events (2·13–3·43 cm) of differing characteristics, and sensor data at four locations with differing soil hydraulic properties along the hillslope showed that the main surface runoff generation mechanism in this region is infiltration excess. Because of this, rainfall intensity and soil hydraulic conductivity were found to play dominant roles in surface runoff generation in this region. Further, only short periods of a few rainfall events during which the rainfall intensity is high produce surface runoff. This study indicates that perhaps subsurface flows and transport of P in subsurface flows need to be quantified to reduce P contamination of surface water bodies in this region. Current studies at this location are identifying spatial and temporal distribution of HAAs, quantifying rainfall characteristics that generate runoff, and estimating runoff volume that results from connected HAAs. Copyright © 2008 John Wiley & Sons, Ltd.