Quantitative analysis of triazine herbicides in environmental samples by using high performance liquid chromatography and diode array detection combined with second-order calibration based on an alternating penalty trilinear decomposition algorithm

A novel application of second-order calibration method based on an alternating penalty trilinear decomposition (APTLD) algorithm is presented to treat the data from high performance liquid chromatography-diode array detection (HPLC-DAD). The method makes it possible to accurately and reliably analyze atrazine (ATR), ametryn (AME) and prometryne (PRO) contents in soil, river sediment and wastewater samples. Satisfactory results are obtained although the elution and spectral profiles of the analytes are heavily overlapped with the background in environmental samples. The obtained average recoveries for ATR, AME and PRO are 99.7 ± 1.5, 98.4 ± 4.7 and 97.0 ± 4.4% in soil samples, 100.1 ± 3.2, 100.7 ± 3.4 and 96.4 ± 3.8% in river sediment samples, and 100.1 ± 3.5, 101.8 ± 4.2 and 101.4 ± 3.6% in wastewater samples, respectively. Furthermore, the accuracy and precision of the proposed method are evaluated with the elliptical joint confidence region (EJCR) test. It lights a new avenue to determine quantitatively herbicides in environmental samples with a simple pretreatment procedure and provides the scientific basis for an improved environment management through a better understanding of the wastewater-soil-river sediment system as a whole.     

Matrix-free analysis of aflatoxins in pistachio nuts using parallel factor modeling of liquid chromatography diode-array detection data

In the present study a second-order calibration strategy for high performance liquid chromatography with diode-array detection (HPLC-DAD) has been developed using parallel factor analysis (PARAFAC) and has been applied for simultaneous determination of aflatoxins B₁, B₂, G₁ and G₂ in pistachio nuts in the presence of matrix interferences. Sample preparation was based on solvent extraction (SE) followed by solid phase extraction (SPE) on Bond Elut C18 cartridges. Since the sample preparation procedure was not selective to the analytes of interest, exploiting second-order advantage to obtain concentrations of individual analytes in the presence of uncalibrated interfering compounds seemed necessary. Appropriate pre-processing steps have been applied to correct background signals and the effect of retention time shifts. Transferred calibration data set obtained from standardization of solvent based calibration data has been used in prediction step. The results of PARAFAC on a set of spiked and naturally contaminated pistachio nuts indicated that the four aflatoxins could be successfully determined. The method was validated and multivariate analytical figures of merit were calculated. The advantages of the proposed method are using a low-cost SPE step relative to standard method of aflatoxin analysis (immune affinity column assay), a unique and simple isocratic elution program for all samples and a calibration transfer for saving both chemicals and time of analysis. This study show that coupling of SPE-HPLC-DAD with PARAFAC as a powerful second-order calibration method can be considered as an alternative method for resolution and quantification of aflatoxins in the presence of unknown interferences obtained through analysis of highly complex matrix of pistachio samples and cost per analysis can be reduced significantly.     

Physalis method for heterogeneous mixtures of dielectrics and conductors: Accurately simulating one million particles using a PC

Prosperetti’s seminal Physalis method, an Immersed Boundary/spectral method, had been used extensively to investigate fluid flows with suspended solid particles. Its underlying idea of creating a cage and using a spectral general analytical solution around a discontinuity in a surrounding field as a computational mechanism to enable the accommodation of physical and geometric discontinuities is a general concept, and can be applied to other problems of importance to physics, mechanics, and chemistry. In this paper we provide a foundation for the application of this approach to the determination of the distribution of electric charge in heterogeneous mixtures of dielectrics and conductors. The proposed Physalis method is remarkably accurate and efficient. In the method, a spectral analytical solution is used to tackle the discontinuity and thus the discontinuous boundary conditions at the interface of two media are satisfied exactly. Owing to the hybrid finite difference and spectral schemes, the method is spectrally accurate if the modes are not sufficiently resolved, while higher than second-order accurate if the modes are sufficiently resolved, for the solved potential field. Because of the features of the analytical solutions, the derivative quantities of importance, such as electric field, charge distribution, and force, have the same order of accuracy as the solved potential field during postprocessing. This is an important advantage of the Physalis method over other numerical methods involving interpolation, differentiation, and integration during postprocessing, which may significantly degrade the accuracy of the derivative quantities of importance. The analytical solutions enable the user to use relatively few mesh points to accurately represent the regions of discontinuity. In addition, the spectral convergence and a linear relationship between the cost of computer memory/computation and particle numbers results in a very efficient method. In the present paper, the accuracy of the method is numerically investigated by example computations using one dielectric particle, one isolated conductor particle, one conductor particle connected to an external source with imposed voltage, and two conductor/dielectric particles with strong interactions. The efficiency of the method is demonstrated with one million particles, which suggests that the method can be used for many important engineering applications of broad interest.     

Second-harmonic pressure generation of a non-diffracting acoustical high-order Bessel vortex beam of fractional type α

Background and motivation

Generalized Bessel vortex beams are regaining interest from the standpoint of acoustic scattering and radiation force theories for applications in particle rotation, mixing and manipulation. Other possible applications may include medical and nondestructive imaging. To manipulate heavy particles in a host medium, a minimum threshold of the incident sound field intensity is required at relatively high wave amplitudes such that nonlinear wave propagation occurs and the generation of harmonics may be detected. Thus, predictions of the harmonics generation become crucial from the standpoint of experimental design, and the present analysis should assist in the development of more complete models related to the (nonlinear) scattering and radiation forces under such circumstances. The purpose of this research is to construct a theoretical model for the second-harmonic pressure generation associated with a category of non-diffracting Bessel vortex beams known as high-order Bessel vortex beams of fractional typeα (HOBVBs-Fα).

Method

The weakly nonlinear wave propagation of a HOBVB-Fα is investigated based on Lighthill’s formalism. Analytical solutions up to the second-order level of approximation are derived and discussed. Closed-form solutions are obtained, which are expressed as a function of first-order quantities available from the classical linear theory. Lateral profiles of the HOBVB-Fα are computed and compared.

Results and conclusion

The results show that the beam’s width reduces and becomes narrower, the side-lobes decrease in magnitude, and the hollow region diameter (or null in magnitude) increases as the order of nonlinearity increases. Furthermore, the nonlinearity of the medium preserves the non-diffracting feature of the beam’s second-harmonic generation within the pre-shock range.     

Nonstandard second-order arithmetic and Riemannʼs mapping theorem

In this paper, we introduce systems of nonstandard second-order arithmetic which are conservative extensions of systems of second-order arithmetic. Within these systems, we do reverse mathematics for nonstandard analysis, and we can import techniques of nonstandard analysis into analysis in weak systems of second-order arithmetic. Then, we apply nonstandard techniques to a version of Riemannʼs mapping theorem, and show several different versions of Riemannʼs mapping theorem.     

Existence of Positive Solutions for Singular Second-order<Emphasis Type="Italic">m</Emphasis>-Point Boundary Value Problems

Abstract   The singular second-order m-point boundary value problem

A generalization of a conservativity theorem for classical versus intuitionistic arithmetic

A basic result in intuitionism is Π⁰₂‐conservativity. Take any proof p in classical arithmetic of some Π⁰₂‐statement (some arithmetical statement ?x.?y.P(x, y), with P decidable). Then we may effectively turn p in some intuitionistic proof of the same statement. In a previous paper [1], we generalized this result: any classical proof p of an arithmetical statement ?x.?y.P(x, y), with P of degree k, may be effectively turned into some proof of the same statement, using Excluded Middle only over degree k formulas. When k = 0, we get the original conservativity result as particular case. This result was a by‐product of a semantical construction. J. Avigad of Carnegie Mellon University, found a short, direct syntactical derivation of the same result, using H. Friedman's A‐translation. His proof is included here with his permission. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)