Diurnal variation of atmospheric CO2 concentration and delta C-13 in an urban atmosphere during winter-role of the Nocturnal Boundary Layer

The paper presents the importance of the Nocturnal Boundary Layer in driving the diurnal variability of the atmospheric CO2 mixing ratio and the carbon isotope ratio at ground level from an urban station in India. Our observations are the first of their kind from this region. The atmospheric CO2 mixing ratio and the carbon isotopic ratio were measured for both the morning (05:30-07:30 IST) and afternoon time (16:00-18:00 IST) air samples at 5 m above ground level in Bangalore city, Karnataka State (12 degrees 58' N, 77 degrees 38' E, masl = 920 m) for a 10 day period during the winter of 2008. We observed a change of similar to 7% the in CO2 mixing ratio between the morning and afternoon time air samples. A stable isotope analysis of CO2 from morning samples showed a depletion in the carbon isotope ratio by similar to 2 parts per thousand compared to the afternoon samples. Along with the ground-based measurement of air samples, data of radiosonde measurements were also obtained from the Indian Meteorological Department to identify the vertical atmospheric structure at different time in a day. We proposed the presence or absence of the NBL as a controlling factor for the observed variability in the mixing ratio as well as its isotopic composition. Here we used the Keeling model approach to find out the carbon isotope ratio for the local sources. The local sources have further been characterized as anthropogenic and biological respiration (in %) using a two-component mixing model. We also used a vertical mixing model based on the concept of the mixing of isotopically depleted (carbon isotope) ``polluted air'' (PA) with isotopically enriched ``free atmospheric air'' (FA) above. Using this modeling approach, the contribution of FA at ground level is being estimated for both the morning and afternoon time air samples.

In-situ measurements of concentration and temperature during transient solidification of aqueous solution of ammonium chloride using laser interferometry

The variation in temperature and concentration plays a crucial role in predicting the final microstructure during solidification of a binary alloy. Most of the experimental techniques used to measure concentration and temperature are intrusive in nature and affect the flow field. In this paper, the main focus is laid on in-situ, non-intrusive, transient measurement of concentration and temperature during the solidification of a binary mixture of aqueous ammonium chloride solution (a metal-analog system) in a top cooled cavity using laser based Mach-Zehnder Interferometric technique. It was found from the interferogram, that the angular deviation of fringe pattern and the total number of fringes exhibit significant sensitivity to refractive index and hence are functions of the local temperature and concentration of the NH4Cl solution inside the cavity. Using the fringe characteristics, calibration curves were established for the range of temperature and concentration levels expected during the solidification process. In the actual solidification experiment, two hypoeutectic solutions (5% and 15% NH4Cl) were chosen. The calibration curves were used to determine the temperature and concentration of the solution inside the cavity during solidification of 5% and 15% NH4Cl solution at different instants of time. The measurement was carried out at a fixed point in the cavity, and the concentration variation with time was recorded as the solid-liquid interface approached the measurement point. The measurement exhibited distinct zones of concentration distribution caused by solute rejection and Rayleigh Benard convection. Further studies involving flow visualization with laser scattering confirmed the Rayleigh Benard convection. Computational modeling was also performed, which corroborated the experimental findings. (C) 2011 Elsevier Ltd. All rights reserved.

Effect of doping concentration on the structural and optical properties of pure and tin doped zinc oxide thin films by nebulizer spray pyrolysis (NSP) technique

Pure and tin doped zinc oxide (Sn:ZnO) thin films were prepared for the first time by NSP technique using aqueous solutions of zinc acetate dehydrate, tin (IV) chloride fendahydrate and methanol. X-ray diffraction patterns confirm that the films are polycrystalline in nature exhibiting hexagonal wurtzite type, with (0 0 2) as preferred orientation. The structural parameters such as lattice constant ('a' and `c'), crystallite size, dislocation density, micro strain, stress and texture coefficient were calculated from X-ray diffraction studies. Surface morphology was found to be modified with increasing Sn doping concentration. The ZnO films have high transmittance 85% in the visible region, and the transmittance is found to be decreased with the increase of Sn doping concentration. The corresponding optical band gap decreases from 3.25 to 3.08 eV. Room temperature photoluminescence reveals the sharp emission of strong UV peak at 400 nm (3.10 eV) and a strong sharp green luminescence at 528 nm (2.34 eV) in the Sn doped ZnO films. The electrical resistivity is found to be 10(6) Omega-cm at higher temperature and 10(5) Omega-cm at lower temperature. (C) 2012 Elsevier Ltd. All rights reserved.

Multiwalled-carbon-nanotube-induced miscibility in near-critical PS/PVME blends: assessment through concentration fluctuations and segmental relaxation

The effects of multiwalled carbon nanotubes (MWNTs) on the concentration fluctuations, interfacial driven elasticity, phase morphology, and local segmental dynamics of chains for near-critical compositions of polystyrene/poly(vinyl to methyl ether) (PS/PVME) blends were systematically investigated using dynamic shear rheology and dielectric spectroscopy. The contribution of the correlation length (xi) of the concentration fluctuations to the evolving stresses was monitored in situ to probe the different stages of demixing in the blends. The classical upturn in the dynamic moduli was taken as the rheological demixing temperature (T-rheo), which was also observed to be in close agreement with those obtained using concentration fluctuation variance, <(delta phi)(2)>, versus temperature curves. Further, Fredrickson and Larson's approach involving the mean-field approximation and the double-reptation self-concentration (DRSC) model was employed to evaluate the spinodal decomposition temperature (T-s). Interestingly, the values of both T-rheo and T-s shifted upward in the blends in the presence of MWNTs, manifesting in molecular-level miscibility. These phenomenal changes were further observed to be a function of the concentration of MWNTs. The evolution of morphology as a function of temperature was studied using polarized optical microscopy (POM). It was observed that PVME, which evolved as an interconnected network during the early stages of demixing, coarsened into a matrix-droplet morphology in the late stages. The preferential wetting of PVME onto MWNTs as a result of physicochemical interactions retained the interconnected network of PVME for longer time scales, as supported by POM and atomic force microscopy (AFM) images. Microscopic heterogeneity in macroscopically miscible systems was studied by dielectric relaxation spectroscopy. The slowing of segmental relaxations in PVME was observed in the presence of both ``frozen'' PS and MWNTs interestingly at temperatures much below the calorimetric glass transition temperature (T-g). This phenomenon was observed to be local rather than global and was addressed by monitoring the evolution of the relaxation spectra near and above the demixing temperature.

Using long time series of agricultural-derived nitrates for estimating catchment transit times

The estimation of water and solute transit times in catchments is crucial for predicting the response of hydrosystems to external forcings (climatic or anthropogenic). The hydrogeochemical signatures of tracers (either natural or anthropogenic) in streams have been widely used to estimate transit times in catchments as they integrate the various processes at stake. However, most of these tracers are well suited for catchments with mean transit times lower than about 4-5 years. Since the second half of the 20th century, the intensification of agriculture led to a general increase of the nitrogen load in rivers. As nitrate is mainly transported by groundwater in agricultural catchments, this signal can be used to estimate transit times greater than several years, even if nitrate is not a conservative tracer. Conceptual hydrological models can be used to estimate catchment transit times provided their consistency is demonstrated, based on their ability to simulate the stream chemical signatures at various time scales and catchment internal processes such as N storage in groundwater. The objective of this study was to assess if a conceptual lumped model was able to simulate the observed patterns of nitrogen concentration, at various time scales, from seasonal to pluriannual and thus if it was relevant to estimate the nitrogen transit times in headwater catchments. A conceptual lumped model, representing shallow groundwater flow as two parallel linear stores with double porosity, and riparian processes by a constant nitrogen removal function, was applied on two paired agricultural catchments which belong to the Research Observatory ORE AgrHys. The Global Likelihood Uncertainty Estimation (GLUE) approach was used to estimate parameter values and uncertainties. The model performance was assessed on (i) its ability to simulate the contrasted patterns of stream flow and stream nitrate concentrations at seasonal and inter-annual time scales, (ii) its ability to simulate the patterns observed in groundwater at the same temporal scales, and (iii) the consistency of long-term simulations using the calibrated model and the general pattern of the nitrate concentration increase in the region since the beginning of the intensification of agriculture in the 1960s. The simulated nitrate transit times were found more sensitive to climate variability than to parameter uncertainty, and average values were found to be consistent with results from others studies in the same region involving modeling and groundwater dating. This study shows that a simple model can be used to simulate the main dynamics of nitrogen in an intensively polluted catchment and then be used to estimate the transit times of these pollutants in the system which is crucial to guide mitigation plans design and assessment. (C) 2015 Elsevier B.V. All rights reserved.

Mode coupling theory analysis of electrolyte solutions: Time dependent diffusion, intermediate scattering function, and ion solvation dynamics

A self-consistent mode coupling theory (MCT) with microscopic inputs of equilibrium pair correlation functions is developed to analyze electrolyte dynamics. We apply the theory to calculate concentration dependence of (i) time dependent ion diffusion, (ii) intermediate scattering function of the constituent ions, and (iii) ion solvation dynamics in electrolyte solution. Brownian dynamics with implicit water molecules and molecular dynamics method with explicit water are used to check the theoretical predictions. The time dependence of ionic self-diffusion coefficient and the corresponding intermediate scattering function evaluated from our MCT approach show quantitative agreement with early experimental and present Brownian dynamic simulation results. With increasing concentration, the dispersion of electrolyte friction is found to occur at increasingly higher frequency, due to the faster relaxation of the ion atmosphere. The wave number dependence of intermediate scattering function, F(k, t), exhibits markedly different relaxation dynamics at different length scales. At small wave numbers, we find the emergence of a step-like relaxation, indicating the presence of both fast and slow time scales in the system. Such behavior allows an intriguing analogy with temperature dependent relaxation dynamics of supercooled liquids. We find that solvation dynamics of a tagged ion exhibits a power law decay at long times-the decay can also be fitted to a stretched exponential form. The emergence of the power law in solvation dynamics has been tested by carrying out long Brownian dynamics simulations with varying ionic concentrations. The solvation time correlation and ion-ion intermediate scattering function indeed exhibit highly interesting, non-trivial dynamical behavior at intermediate to longer times that require further experimental and theoretical studies. (c) 2015 AIP Publishing LLC.

Influence of deposition time on the properties of electrodeposited Cu(In,Al)Se-2 thin films

Cu(In,Al)Se-2 films are grown using single step electrodeposition technique. The film properties are studied by varying the deposition time from 500 to 2000 s. Peaks corresponding to elemental Se and Cu2Se phase started appearing from 1200 s of deposition. The composition is changed significantly after 1500 S. Se concentration increased from 57 to 68% with the increase in the deposition time. The Cu2Se phase is dominant in the films deposited for a duration of 2000 s and the grain size increased from 1.12 to 2.15 mu m in this film. Raman analysis confirmed the presence of Se and Cu2Se phase in C1200. In C1500 and C2000 the spectra showed prominent mode corresponding to Cu2Se. The thickness of the film increased from 0.85 to 2.3 mu m with the increase in the deposition time. All the films showed p-type conductivity and resistivity reduced with increased thickness. (C) 2015 Elsevier Ltd. All rights reserved.

Real-Time Stress Measurements in Germanium Thin Film Electrodes during Electrochemical Lithiation/Delithiation Cycling

An in situ study of stress evolution and mechanical behavior of germanium as a lithium-ion battery electrode material is presented. Thin films of germanium are cycled in a half-cell configuration with lithium metal foil as counter/reference electrode, with 1M LiPF6 in ethylene carbonate, diethyl carbonate, dimethyl carbonate solution (1:1:1, wt%) as electrolyte. Real-time stress evolution in the germanium thin-film electrodes during electrochemical lithiation/delithiation is measured by monitoring the substrate curvature using the multi-beam optical sensing method. Upon lithiation a-Ge undergoes extensive plastic deformation, with a peak compressive stress reaching as high as -0.76 +/- 0.05 GPa (mean +/- standard deviation). The compressive stress decreases with lithium concentration reaching a value of approximately -0.3 GPa at the end of lithiation. Upon delithiation the stress quickly became tensile and follows a trend that mirrors the behavior on compressive side; the average peak tensile stress of the lithiated Ge samples was approximately 0.83 GPa. The peak tensile stress data along with the SEM analysis was used to estimate a lower bound fracture resistance of lithiated Ge, which is approximately 5.3 J/m(2). It was also observed that the lithiated Ge is rate sensitive, i.e., stress depends on how fast or slow the charging is carried out. (C) The Author(s) 2015. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. All rights reserved.

Effect of polymer concentration on stabilized large-tilt-angle flexoelectro-optic switching

In this letter, the uniform lying helix (ULH) liquid crystal texture, required for the flexoelectro-optic effect, is polymer stabilized by the addition of a small percentage of reactive mesogen to a high-tilt-angle (φ>60°) bimesogenic chiral nematic host. The electro-optic response is measured for a range of reactive mesogen concentration mixtures, and compared to the large-tilt-angle switch of the pure chiral nematic mixture. The optimum concentration of reactive mesogen, which is found to provide ample stabilization of the texture with minimal impact on the electro-optic response, is found to be approximately 3%. Our results indicate that polymer stabilization of the ULH texture using a very low concentration of reactive mesogen is a reliable way of ruggedizing flexoelectro-optic devices without interfering significantly with the electro-optics of the effect, negating the need for complicated surface alignment patterns or surface-only polymerization. The polymer stabilization is shown to reduce the temperature dependence of the flexoelectro-optic response due to "pinning" of the chiral nematic helical pitch. This is a restriction of the characteristic thermochromic behavior of the chiral nematic. Furthermore, selection of the temperature at which the sample is ultraviolet cured allows the tilt angle to be optimized for the entire chiral nematic temperature range. The response time, however, remains more sensitive to operating temperature than curing temperature. This allows the sample to be cured at low temperature and operated at high temperature, providing simultaneous optimization of these two previously antagonistic performance aspects. © 2006 American Institute of Physics.

Integration of holographic sensors into microfluidics for the real-time pH sensing of L. casei metabolism

We describe developments in the integration of analyte specific holographic sensors into PDMS-based microfluidic devices for the purpose of continuous, low-impact monitoring of extra-cellular change in micro-bioreactors. Holographic sensors respond to analyte concentration via volume change, which makes their reduction in size and integration into spatially confined fluidics difficult. Through design and process modification many of these constraints have been addressed, and a microfluidics-based device capable of real-time monitoring of the pH change caused by Lactobacillus casei fermentation is presented as a general proof-of-concept for a wide array of possible devices.

The Real-Time Mach-Zehnder Interferometer Used In Space Experiment

The optical interference method is a promising technique for measuring temperature, density, and concentration in fluids. The non-intrusive and non-invasive nature of its optical techniques to the measured section are its most outstanding features. However, the adverse experiment environment, especially regarding shaking and vibrating, greatly restricts the application of the interferometer. In the present work, an optical diagnostic system consisting of a Mach-Zehnder interferometer (named after physicists Ludwig Mach) and an image processor has been developed that increases the measuring sensitivity compared to conventional experimental methods in fluid mechanics. An image processor has also been developed for obtaining quantitative results by using Fourier transformation. The present facility has been used in observing and measuring the mass transfer process of a water droplet in EAFP protein solution under microgravity condition provided by the satellite Shi Jian No. 8.

A study on stratification of concentration in crystal-growth of alpha-liio3 by holographic-interferometry

A new thermoplastic-photoconductor laser holographic recording system has been used for real-time and in situ observation of alpha-LiIO3 crystal growth. The influence of crystallization-driven convection on the concentration stratification in solution has been studied under gravity field. It is found that the stratification is closely related to the seed orientation of alpha-LiIO3 crystal. When the optical axis of crystal seed C is parallel to the gravity vector g, the velocity of the concentration stratification is two times larger than that in the case of C perpendicular-to g. It needs 40 h for the crystalline system of alpha-LiIO3 to reach stable concentration distribution (expressed as tau) at 47.6-degrees-C. The time tau is not sensitive to the seed orientation. Our results provide valuable data for designing the crystal growth experiments ia space.

An examination of fluctuations in the “concentration index” of purse seiners and baitboats in the fishery for tropical tunas in the Eastern Pacific, 1951-1961

ENGLISH: In the eastern Pacific Ocean nearly all of the commercial catches of yellowfin tuna (Thunnus albacares) and skipjack (Katsuwonus pelamis) are taken by two types of vessels, baitboats, which use pole and line in conjunction with live-bait, and purse-seiners. From its inception until very recently (1959), this fishery was dominated by baitboats. This method of fishing has been described by Godsil (1938) and Shimada and Schaefer (1956). From 1951 through 1958 baitboats caught between 66.4 and 90.8 per cent of the yellowfin and between 87.2 and 95.3 per cent of the skipjack landed by the California-based fleet. These vessels fished for tuna throughout the year and covered virtually all of the area from southern California to northern Chile. The purse-seine fishery for tunas developed out of the round-haul net fisheries for California sardines and other species. Scofield (1951) gives a detailed description of the development of gear and fishing methods. Prior to 1959 many of the seiners engaged in other fisheries during the fall and early winter months and consequently most of the fishing effort for tuna occurred in the period February-August. The vessels were quite small, averaging approximately 120 tons carrying capacity (Broadhead and Marshall, 1960), in comparison to the baitboats, of which the most numerous size-class was 201-300 tons. The seiners were naturally more restricted in range than the baitboats and most of their effort was restricted to the northern grounds. During the period 1959-61 most of the large baitboats were converted for purse-seining and the existing seiner fleet was modernized. These developments increased the range of the seiner fleet and resulted in a wider and more nearly even spatial and temporal distribution of effort. By the early part of 1961, the purse-seine fleet approximated the level of the preconversion baitboat fleet in amount of effort applied and area covered. The changes in the purse-seine fishery and the fishing methods employed in the modernized fleet are described by Orange and Broadhead (1959), Broadhead and Marshall (1960), McNeely (1961) and Broadhead (1962). The change in the relative importance of the two gears is illustrated by the decline in the proportion of the total logged tonnage landed by California-based baitboats, in comparison to the proportion landed by seiners. In 1959 baitboats landed 49.5 per cent of the yellowfin and 87.8 per cent of the skipjack. In 1960 these percentages were 22.9 and 74.7 respectively and in 1961 the decline continued to 12.6 per cent of the yellowfin and 30.0 per cent of the skipjack (Schaefer, 1962). In previous Bulletins of this Commission (Griffiths, 1960; Calkins, 1961) the baitboat catch and effort statistics were used to compute two indices of population density and an index of concentration of fishing effort and the fluctuations of these indices were analyzed in some detail. Due to the change in the relative importance of the two gears it is appropriate to extend this investigation to include the purse-seine data. The objectives of this paper are to compute two indices of population density and an index of concentration of fishing effort and to examine the fluctuations in these indices before and after the changes in the fishery. A further objective is to compare the purse-seine indices with those of the baitboats for the same time periods. SPANISH: En el Océano Pacífico Oriental casi todas las capturas comerciales del atún aleta amarilla (Thunnus albacares) y del barrilete (Katsuwonus pelamis) son efectuadas por dos tipos de barcos, los barcos de carnada que emplean la caña y el anzuelo en conjunto con la carnada viva, y los barcos rederos. Desde su comienzo hasta hace poco tiempo (1959), esta pesquería estaba dominada por los barcos de carnada. El método de pesca usado por estos barcos ha sido descrito por Godsil (1938) y por Shimada y Schaefer (1956). De 1951 a 1958, los barcos de carnada pescaron entre el 66.4 y el 90.8 por ciento del atún aleta amarilla y entre el 87.2 y el 95.3 por ciento del barrilete descargados por la flota que tiene su base en California. Estos barcos pescaron atún durante todo el año y cubrieron virtualmente toda el área de California meridional hasta la parte norte de Chile. La pesquería del atún con redes de cerco se originó en las pesquerías de las sardinas de California y otras especies, con redes que se remolcaban circularmente. Scofield (1951) dá una descripción detallada del desarrollo de los métodos y del equipo de pesca. Antes de 1959 muchos de los rederos se dedicaban a otras pesquerías durante los meses del otoño y a principios del invierno y consecuentemente, la mayor parte del esfuerzo depesca para la producción del atún ocurría en el período febrero-agosto. Las embarcaciones eran bastante pequeñas, con un promedio de aproximadamente 120 toneladas de capacidad para el transporte (Broadhead y Marshall, 1960) en comparación con los barcos de carnada, de los cuales la clase de tamaño más numerosa era de 201 a 300 toneladas. Los rederos estaban naturalmente más restringidos en su radio de acción que los barcos de carnada y la mayor parte de su esfuerzo se limitaba a las localidades del norte. Durante el período 1959-61, la mayoría de los grandes barcos de carnada fueron convertidos al sistema de pesca con redes de cerco, y se modernizó la flota existente de los rederos. Estos cambios aumentaron el alcance de la flota de los barcos rederos dando como resultado una distribución más amplia y casi más uniforme del esfuerzo espaciado y temporal. En la primera parte del año 1961, la flota de rederos se aproximó al nivel de la preconversión de la flota de clipers, en la cantidad de esfuerzo aplicado y al área comprendida. Los cambios en la pesquería con red y los métodos de pesca empleados en la flota modernizada, han sido descritos por Orange y Broadhead (1959), Broadl1ead y Marshall (1960), McNeely (1961) y Broadhead (1962). El cambio en la importancia relativa de los dos sistemas de pesca está ilustrado por la declinación en la proporción del tonelaje total registrado, como descargado por los barcos de carnada que tienen su base en California, comparado con la proporción desembarcada por los barcos rederos. En 1959 los clipers descargaron el 49.5 por ciento del atún aleta amarilla y el 87.8 por ciento del barrilete. En 1960 estos porcentajes fueron del 22.9 y 74.7 respectivamente, y en 1961 continuó la reducción hasta el 12.6 por ciento del atún aleta amarilla y el 30.0 por ciento del barrilete (Schaefer, 1962). En Boletines anteriores de la Comisión (Griffiths, 1960; Calkins, 1961) las estadísticas de la pesca y el esfuerzo de los clipers se utilizaron para computar dos índices de la densidad de población y un índice de la concentración del esfuerzo de pesca, y se analizaron algo detalladamente las fluctuaciones de estos índices. Debido al cambio en la importancia relativa de los dos sistemas de pesca, es conveniente extender esta investigación para incluir los datos correspondientes a los barcos rederos. Los objetivos del presente estudio son de computar dos índices de la densidad de población y un índice de la concentración del esfuerzo de pesca, y examinar las fluctuaciones en estos índices, antes y después de los cambios en la pesquería. Otro objetivo es de comparar los índices de los barcos rederos, con aquellos de los clipers en los mismos períodos de tiempo.

The effect of sublethal concentration of DimilinR (TH6040) on the larval development of the mud-crab Rhithropanopeus harrisii (Gould)

Sublethal DimilinR (insecticide) concentration significantly decreased the percentage survival of larval R. harrisii . This decrease was marked at low salinities, when it may have become toxic. This was true for both 25 and 30 C. Duration of larval development did not seem to be affected by sublethal DimilinR concentrations even in extremely low or high salinities. High temperature, however, shortened the time of development. No anatomical abnormality was observed. These findings are only tentative as more replicates of the experiments are needed before definite conclusions can be reached. It will be desirable to work with more salinity-temperature combinations to get a complete picture of sublethal effects under different environmental conditions.

Time series analyses of biological and environmental variables for Suisun Bay and the Sacramento and San Joaquin rivers

EXTRACT (SEE PDF FOR FULL ABSTRACT): Arima analysis was used to compute cross-correlations between principal component axes that described environmental variables, chlorophyll concentration and zooplankton density for the Sacramento and San Joaquin rivers and Suisun Bay. ... Cross-correlations among the time series may provide information about links between environmental and biological variables within the estuary and the possible influence of climate.