Sensitive trace enrichment of environmental andiandrogen vinclozolin from natural waters and sediment samples using hollow-fiber liquid-phase microextraction

The presence of vinclozolin in the environment as far as the endocrine disruption effects in biota are concerned has raised interest in the environmental fate of this compound. In this respect, the present study attempts to investigate the feasibility of applying a novel quantitative method, liquid-phase microextraction (LPME), so as to determine this environmental andiandrogen in environmental samples such as water and sediment samples. The technique involved the use of a small amount (3 microL) of organic solvent impregnated in a hollow fiber membrane, which was attached to the needle of a conventional GC syringe. The extracted samples were analyzed by gas chromatography coupled with electron-capture detection. Experimental LPME conditions such as extraction solvent, stirring rate, content of NaCl and pH were tested. Once LPME was optimized, the performance of the proposed technique was evaluated for the determination of vinclozolin in different types of natural water samples. The recovery of spiked water samples was from 80 to 99%. The procedure was adequate for quantification of vinclozolin in waters at levels of 0.010 to 50 microg/L (r> 0.994) with a detection limit of 0.001 microg/L (S/N= 3). Natural sediment samples from the Aliakmonas River area (Macedonia, Greece) spiked with the target andiandrogen compound were liquid-liquid extracted and analyzed by the methodology developed in this work. No significant interferences from the samples matrix were noticed, indicating that the reported methodology is an innovative tactic for sample preparation in sediment analysis, with a considerable improvement in the achieved detection limits. The results demonstrated that apart from analyte enrichment, the proposed LPME procedure also serves as clean-up method and could be successfully performed to determine trace amounts of vinclozolin in water and sediment samples.     

Carob pod: A new substrate for citric acid production by Aspergillus niger

The production of citric acid from carob pod extract byA. niger in surface fermentation was investigated. A maximum citric acid concentration (85.5 g/L), citric acid productivity (4.07 g/L/d), specific citric acid production rate (0.18 g/g/d), and specific sugar uptake rate (0.358 g/g/d) was achieved at an initial sugar concentration of 200 g/L, pH of 6.5, and a temperature of 30°C. Other kinetic parameters, namely, citric acid yield, biomass yield, specific biomass production rate, and fermentation efficiency were maximum at pH 6.5, temperature 30°C, and initial sugar concentration 100 g/L. The external addition of methanol into the carob pod extract at a concentration up to 4% (v/v) improved the production of citric acid.     

Determination of Herbicides in Natural Waters Using Solid Phase Microextraction (SPME) and Gas Chromatography Coupled with Flame Thermionic and Mass Spectrometric Detection

Abstract

This study develops a method for solid phase microextraction (SPME) of ten widespread herbicides from water. The selected herbicides belong to different chemical groups are EPTC, molinate, propachlor, trifluralin, atrazine, propazine, terbuthylazine, prometryne, alachlor. Their determination was carried out by gas chromatography with flame thermionic and mass spectrometric detection. To perform the SPME, two types of fibre have been assayed: Carbowax-divinylbenzene (CW-DVB) of 65 μm thickness and polydimethylsiloxane-divinylbenzene (PDMS-DVB) of 65 μm thickness. The main factors affecting the SPME process such as pH, ionic strength, methanol content, memory effect, stirring rate and adsorption-time profile were studied. The method was applied to spiked natural waters such as ground water, sea water, lake water and river water in a concentration range of 0.1 to 10 μg/L. Limits of detection with each of the detectors were determined to be 1 – 20 ng/L in PDMS-DVB and 2–20 ng/L CW-DVB fibres. The recoveries of herbicides compared to distilled water were in relatively high levels 78.3–127.3 % and the average r² values of the calibration curves were above 0.99 for all the analytes. The SPME conditions were finally optimized in order to obtain maximum sensitivity and samples were applied for the trace-level determination in river water samples originating from Ioannina region (Greece).     

A New Organophosphorus Insecticides Removal Process Using Fly ASH

Abstract

Fly ash and soil mixtures with a range of fly ash content from 1 to 100% were used to study adsorption and desorption of four organophosphorus insecticides, ethyl parathion, methyl parathion, fenitrothion and fenthion, in batch experiments. The object of the study was to develop a treatment process using fly ash as sorbent material to isolate/immobilize organic contaminants from aqueous solutions. The adsorption isotherms fit the Freundlich equation x/m=K_dC^1/n. The K_d values increase with the increase of the fly ash content. The isotherms seem to fit the S type, in mixtures of soil with a fly ash content from 0 to 10%, which implies that adsorption becomes easier as the concentration in the liquid phase increases. In mixtures of soil with a fly ash content from 25 to 50% the isotherms become L type and correspond to a decrease of site availability as the solution concentration increases. Finally in mixtures of soil with a fly ash content over 50%, C type adsorption was observed which correspond to a constant partition of the insecticides between the bulk solution and the adsorbent. Mass balance estimations show that the mean percent amounts of insecticides for a range of concentration 0.5–15 mg/l, removed by adsorption in the soil sample are 81.56 % for ethyl parathion, 48.97 % for methyl parathion, 67.06 % for fenitrothion and 86.65 % for fenthion. The adsorption increases as the fly ash content increased and reach the 100% in the “pure” fly ash. The adsorbed amounts of insecticides in mixtures of soils with >50% fly ash content, are up to 99%. In contrast, the amounts of desorption in water decrease as the fly ash content increase.

The results of this research demonstrate that the fly ash shows a significant capacity for adsorption of organophosphorus compounds from aqueous solution and can be used for pesticide removal process.     

Asymptotics for Hessenberg Matrices for the Bergman Shift Operator on Jordan Regions

Let $G$ be a bounded Jordan domain in the complex plane. The Bergman polynomials $\{p_n\}_{n=0}^\infty $ of $G$ are the orthonormal polynomials with respect to the area measure over $G$ . They are uniquely defined by the entries of an infinite upper Hessenberg matrix $M$ . This matrix represents the Bergman shift operator of $G$ . The main purpose of the paper is to describe and analyze a close relation between $M$ and the Toeplitz matrix with symbol the normalized conformal map of the exterior of the unit circle onto the complement of $\overline{G}$ . Our results are based on the strong asymptotics of $p_n$ . As an application, we describe and analyze an algorithm for recovering the shape of $G$ from its area moments.     

On the theory and application of a domain decomposition method for computing conformal modules

We consider the theory and application of a domain decomposition method for computing the conformal modules of long quadrilaterals. The method has been studied already by us and also by Gaier and Hayman. Our main purpose here is to extend its area of application and, in the same time, improve some of our earlier error estimates.     

Approximation of conformal mappings of annular regions

Summary. In this paper we examine the convergence rates in an adaptive version of an orthonormalization method for approximating the conformal mapping of an annular region onto a circular annulus. In particular, we consider the case where has an analytic extension in compl() and, for this case, we determine optimal ray sequences of approximants that give the best possible geometric rate of uniform convergence. We also estimate the rate of uniform convergence in the case where the annular region has piecewise analytic boundary without cusps. In both cases we also give the corresponding rates for the approximations to the conformal module of . Received February 2, 1996     

On a domain decomposition method for the computation of conformal modules

We consider a domain decomposition method for approximating the conformal modules of a certain class of long quadrilaterals.     

Bergman polynomials on an archipelago: Estimates, zeros and shape reconstruction

Growth estimates of complex orthogonal polynomials with respect to the area measure supported by a disjoint union of planar Jordan domains (called, in short, an archipelago) are obtained by a combination of methods of potential theory and rational approximation theory. The study of the asymptotic behavior of the roots of these polynomials reveals a surprisingly rich geometry, which reflects three characteristics: the relative position of an island in the archipelago, the analytic continuation picture of the Schwarz function of every individual boundary and the singular points of the exterior Green function. By way of explicit example, fine asymptotics are obtained for the lemniscate archipelago |z^m−1|<r^m, 0<r<1, which consists of m islands. The asymptotic analysis of the Christoffel functions associated to the same orthogonal polynomials leads to a very accurate reconstruction algorithm of the shape of the archipelago, knowing only finitely many of its power moments. This work naturally complements a 1969 study by H. Widom of Szegő orthogonal polynomials on an archipelago and the more recent asymptotic analysis of Bergman orthogonal polynomials unveiled by the last two authors and their collaborators.     

Application of chemometric assisted dispersive liquid-liquid microextraction to the determination of personal care products in natural waters

A rapid and simple method for the determination of two phthalates and five polycyclic musks in water samples using dispersive liquid-liquid microextraction (DLLME) mated to chemometrics and coupled to GC-MS was developed. Volume of extraction (CCl₄) and disperser solvent (MeOH), pH, ionic strength, extraction time, centrifugation time as well as centrifugation speed were optimized in a 2^7-4 Plackett-Burman design. The obtained significant factors were optimized by using a central composite design (CCD) and the quadratic model between the dependent and the independent variables was built. The optimum experimental conditions of the proposed method were: 250 μL carbon tetrachloride, 0.62 mL methanol, 7.5 min centrifugation time, natural pH containing 0% (w/v) NaCl, while keeping centrifugation speed fixed at 4000 rpm.The calculated calibration curves gave high-level linearity for all target analytes with correlation coefficients ranging between 0.9970 and 0.9992. The repeatability and reproducibility of the proposed method, expressed as relative standard deviation, varied between 2.6% to 9.7% and 5.7% to 12.2%, respectively. The obtained LOD values were in the range of 8-63 ng L⁻¹.