The full-spectrum correlated k method for longwave atmospheric radiative transfer: treatment of gaseous overlap

The correlated k-distribution (CKD) method is widely used in the radiative transfer schemes of atmospheric models, and involves dividing the spectrum into a number of bands and then reordering the gaseous absorption coefficients within each one. The fluxes and heating rates for each band may then be computed by discretizing the reordered spectrum into of order 10 quadrature points per major gas, and performing a pseudo-monochromatic radiation calculation for each point. In this paper it is first argued that for clear-sky longwave calculations, sufficient accuracy for most applications can be achieved without the need for bands: reordering may be performed on the entire longwave spectrum. The resulting full-spectrum correlated k (FSCK) method requires significantly fewer pseudo-monochromatic calculations than standard CKD to achieve a given accuracy. The concept is first demonstrated by comparing with line-by-line calculations for an atmosphere containing only water vapor, in which it is shown that the accuracy of heating-rate calculations improves approximately in proportion to the square of the number of quadrature points. For more than around 20 points, the root-mean-squared error flattens out at around 0.015 K d−1 due to the imperfect rank correlation of absorption spectra at different pressures in the profile. The spectral overlap of m different gases is treated by considering an m-dimensional hypercube where each axis corresponds to the reordered spectrum of one of the gases. This hypercube is then divided up into a number of volumes, each approximated by a single quadrature point, such that the total number of quadrature points is slightly fewer than the sum of the number that would be required to treat each of the gases separately. The gaseous absorptions for each quadrature point are optimized such they minimize a cost function expressing the deviation of the heating rates and fluxes calculated by the FSCK method from line-by-line calculations for a number of training profiles. This approach is validated for atmospheres containing water vapor, carbon dioxide and ozone, in which it is found that in the troposphere and most of the stratosphere, heating-rate errors of less than 0.2 K d−1 can be achieved using a total of 23 quadrature points, decreasing to less than 0.1 K d−1 for 32 quadrature points. It would be relatively straightforward to extend the method to include other gases.

On the performance of near-far resistant CDMA detectors in the presence of synchronization errors

Little has so far been reported on the performance of the near-far resistant CDMA detectors in the presence of the synchronization errors. Starting with the general mathematical model of matched filters, this paper examines the effects of three classes of synchronization errors (i.e. time-delay errors, carrier phase errors, and carrier frequency errors) on the performance (bit error rate and near-far resistance) of an emerging type of near-far resistant coherent DS/SSMA detectors, i.e. the linear decorrelating detector (LDD). For comparison, the corresponding results for the conventional detector are also presented. It is shown that the LDD can still maintain a considerable performance advantage over the conventional detector even when some synchronization errors exist. Finally, several computer simulations are carried out to verify the theoretical conclusions.

Power control requirements in linear decorrelating detectors for CDMA

This paper addresses the effects of synchronisation errors (time delay, carrier phase, and carrier frequency) on the performance of linear decorrelating detectors (LDDs). A major effect is that all LDDs require certain degree of power control in the presence of synchronisation errors. The multi-shot sliding window algorithm (SLWA) and hard decision method (HDM) are analysed and their power control requirements are examined. Also, a more efficient one-shot detection scheme, called “hard-decision based coupling cancellation”, is proposed and analysed. These schemes are then compared with the isolation bit insertion (IBI) approach in terms of power control requirements.

Performance analysis of near-far resistant CDMA detectors-influence of system parameter estimation errors

Little has been reported on the performance of near-far resistant CDMA detectors in the presence of system parameter estimation errors (SPEEs). Starting with the general mathematical model of matched filters, the paper examines the effects of three classes of SPEEs, i.e., time-delay, carrier phase, and carrier frequency errors, on the performance (BER) of an emerging type of near-far resistant coherent DS/SSMA detector, i.e., the linear decorrelating detector. For comparison, the corresponding results for the conventional detector are also presented. It is shown that the linear decorrelating detector can still maintain a considerable performance advantage over the conventional detector even when some SPEEs exist.

Convergence analysis of chip- and fractionally spaced LMS adaptive multiuser CDMA detectors

This paper analyzes the convergence behavior of the least mean square (LMS) filter when used in an adaptive code division multiple access (CDMA) detector consisting of a tapped delay line with adjustable tap weights. The sampling rate may be equal to or higher than the chip rate, and these correspond to chip-spaced (CS) and fractionally spaced (FS) detection, respectively. It is shown that CS and FS detectors with the same time-span exhibit identical convergence behavior if the baseband received signal is strictly bandlimited to half the chip rate. Even in the practical case when this condition is not met, deviations from this observation are imperceptible unless the initial tap-weight vector gives an extremely large mean squared error (MSE). This phenomenon is carefully explained with reference to the eigenvalues of the correlation matrix when the input signal is not perfectly bandlimited. The inadequacy of the eigenvalue spread of the tap-input correlation matrix as an indicator of the transient behavior and the influence of the initial tap weight vector on convergence speed are highlighted. Specifically, a initialization within the signal subspace or to the origin leads to very much faster convergence compared with initialization in the a noise subspace.

Variable step-size LMS blind CDMA multiuser detectors

Adaptive least mean square (LMS) filters with or without training sequences, which are known as training-based and blind detectors respectively, have been formulated to counter interference in CDMA systems. The convergence characteristics of these two LMS detectors are analyzed and compared in this paper. We show that the blind detector is superior to the training-based detector with respect to convergence rate. On the other hand, the training-based detector performs better in the steady state, giving a lower excess mean-square error (MSE) for a given adaptation step size. A novel decision-directed LMS detector which achieves the low excess MSE of the training-based detector and the superior convergence performance of the blind detector is proposed.

A mathematical approach to chemical equilibrium theory for gaseous systems—I: theory

Equilibrium theory occupies an important position in chemistry and it is traditionally based on thermodynamics. A novel mathematical approach to chemical equilibrium theory for gaseous systems at constant temperature and pressure is developed. Six theorems are presented logically which illustrate the power of mathematics to explain chemical observations and these are combined logically to create a coherent system. This mathematical treatment provides more insight into chemical equilibrium and creates more tools that can be used to investigate complex situations. Although some of the issues covered have previously been given in the literature, new mathematical representations are provided. Compared to traditional treatments, the new approach relies on straightforward mathematics and less on thermodynamics, thus, giving a new and complementary perspective on equilibrium theory. It provides a new theoretical basis for a thorough and deep presentation of traditional chemical equilibrium. This work demonstrates that new research in a traditional field such as equilibrium theory, generally thought to have been completed many years ago, can still offer new insights and that more efficient ways to present the contents can be established. The work presented here can be considered appropriate as part of a mathematical chemistry course at University level.

A mathematical approach to chemical equilibrium theory for gaseous systems—II: extensions and applications

Straightforward mathematical techniques are used innovatively to form a coherent theoretical system to deal with chemical equilibrium problems. For a systematic theory it is necessary to establish a system to connect different concepts. This paper shows the usefulness and consistence of the system by applications of the theorems introduced previously. Some theorems are shown somewhat unexpectedly to be mathematically correlated and relationships are obtained in a coherent manner. It has been shown that theorem 1 plays an important part in interconnecting most of the theorems. The usefulness of theorem 2 is illustrated by proving it to be consistent with theorem 3. A set of uniform mathematical expressions are associated with theorem 3. A variety of mathematical techniques based on theorems 1–3 are shown to establish the direction of equilibrium shift. The equilibrium properties expressed in initial and equilibrium conditions are shown to be connected via theorem 5. Theorem 6 is connected with theorem 4 through the mathematical representation of theorem 1.

Flow synthesis using gaseous ammonia in a Teflon AF-2400 tube-in-tube reactor: Paal–Knorr pyrrole formation and gas concentration measurement by inline flow titration

Using a simple and accessible Teflon AF-2400 based tube-intube reactor, a series of pyrroles were synthesised in flow using the Paal–Knorr reaction of 1,4-diketones with gaseous ammonia. An inline flow titration technique allowed measurement of the ammonia concentration and its relationship to residence time and temperature.

Continuous-flow processing of gaseous ammonia using a Teflon AF-2400 tube-in-tube reactor: synthesis of thioureas and in-line titrations

A simple tube-in-tube reactor based on the gas-permeable membrane Teflon AF-2400 was used in the continuous flow reaction of gaseous ammonia with isothiocyanates and one isocyanate. A colourimetric in-line titration technique is also reported as a simple method to quantify the amount of ammonia taken up by the solvent in the system.

Triple- and quadruple-escape peaks in HPGe detectors: Experimental observation and Monte Carlo simulation

The triple- and quadruple-escape peaks of 6.128 MeV photons from the (19)F(p,alpha gamma)(16)O nuclear reaction were observed in an HPGe detector. The experimental peak areas, measured in spectra projected with a restriction function that allows quantitative comparison of data from different multiplicities, are in reasonably good agreement with those predicted by Monte Carlo simulations done with the general-purpose radiation-transport code PENELOPE. The behaviour of the escape intensities was simulated for some gamma-ray energies and detector dimensions; the results obtained can be extended to other energies using an empirical function and statistical properties related to the phenomenon. (C) 2010 Elsevier B.V. All rights reserved.

Versatile microanalytical system with porous polypropylene capillary membrane for calibration gas generation and trace gaseous pollutants sampling applied to the analysis of formaldehyde, formic acid, acetic acid and ammonia in outdoor air

The analytical determination of atmospheric pollutants still presents challenges due to the low-level concentrations (frequently in the mu g m(-3) range) and their variations with sampling site and time In this work a capillary membrane diffusion scrubber (CMDS) was scaled down to match with capillary electrophoresis (CE) a quick separation technique that requires nothing more than some nanoliters of sample and when combined with capacitively coupled contactless conductometric detection (C(4)D) is particularly favorable for ionic species that do not absorb in the UV-vis region like the target analytes formaldehyde formic acid acetic acid and ammonium The CMDS was coaxially assembled inside a PTFE tube and fed with acceptor phase (deionized water for species with a high Henry s constant such as formaldehyde and carboxylic acids or acidic solution for ammonia sampling with equilibrium displacement to the non-volatile ammonium ion) at a low flow rate (8 3 nLs(-1)) while the sample was aspirated through the annular gap of the concentric tubes at 25 mLs(-1) A second unit in all similar to the CMDS was operated as a capillary membrane diffusion emitter (CMDE) generating a gas flow with know concentrations of ammonia for the evaluation of the CMDS The fluids of the system were driven with inexpensive aquarium air pumps and the collected samples were stored in vials cooled by a Peltier element Complete protocols were developed for the analysis in air of NH(3) CH(3)COOH HCOOH and with a derivatization setup CH(2)O by associating the CMDS collection with the determination by CE-C(4)D The ammonia concentrations obtained by electrophoresis were checked against the reference spectrophotometric method based on Berthelot s reaction Sensitivity enhancements of this reference method were achieved by using a modified Berthelot reaction solenoid micro-pumps for liquid propulsion and a long optical path cell based on a liquid core waveguide (LCW) All techniques and methods of this work are in line with the green analytical chemistry trends (C) 2010 Elsevier B V All rights reserved

Nickel hydroxide electrodes as amperometric detectors for carbohydrates in flow injection analysis and liquid chromatography

The present paper describes the utilization of nickel hydroxide modified electrodes toward the catalytic oxidation of carbohydrates (glucose, fructose, lactose and sucrose) and their utilization as electrochemical sensor. The modified electrodes were employed as a detector in flow injection analysis for individual carbohydrate detection, and to an ionic column chromatography system for multi-analyte samples aiming a prior separation step. Kinetic studies were performed on a rotating disk electrode (RDE) in order to determine both the heterogeneous rate constant and number of electrons transferred for each carbohydrate. Many advantages were found for the proposed system including fast and easy handling of the electrode modification, low cost procedure, a wide range of linearity (0.5-50 ppm), low detection limits (ppb level) and high sensitivities. (C) 2009 Elsevier B.V. All rights reserved.

Modified LPE system used to diffuse Cd to obtain InSb infrared detectors

We are presenting here p/n junctions obtained with a modified opened liquid-phase epitaxy (LPE) system, used to diffuse indium antimonide (InSb) doped with Cd over InSb doped with Te wafers, in order to make InSb infrared (IR) sensors. This technique has several advantages: the diffusion can be performed in bigger substrate areas improving the device production; this method decreases the device manipulation, decreasing human mistakes and increasing the process reproducibility. The opened LPE in this work produced sensors in the first case with vapor of the diffusion material, coming from a microholed carbon boat full of the diffusion material, over which is positioned the substrate at atmospheric pressure. In the second, the diffusion material is on the bottom of a quartz recipient, and the InSb/Te wafer works as its cover, and vacuum was used. The IR sensors produced with the first method measured 8.9 x 10(7) cm Hz(1/2)/W as detectivity value and higher IR spectral response at 4.6 mu m, and those produced with the second 2.8 x 10(9) cm Hz(1/2)/W, at 4.4 mu m. Besides the electrical-optical properties, the structural properties of diffused layers were investigated by X-ray diffraction (XRD), scanning electron and atomic force microscopy (SEM, AFM), energy-dispersive and secondary ion mass spectroscopy (EDS, SIMS). (C) 2007 Elsevier B.V. All rights reserved.