Vasilios A. Sakkas

Photocatalytic degradation using design of experiments: A review and example of the Congo red degradation

The use of chemometric methods such as response surface methodology (RSM) based on statistical design of experiments (DOEs) is becoming increasingly widespread in several sciences such as analytical chemistry, engineering and environmental chemistry. Applied catalysis, is certainly not the exception. It is clear that photocatalytic processes mated with chemometric experimental design play a crucial role in the ability of reaching the optimum of the catalytic reactions. The present article reviews the major applications of RSM in modern experimental design combined with photocatalytic degradation processes. Moreover, the theoretical principles and designs that enable to obtain a polynomial regression equation, which expresses the influence of process parameters on the response are thoroughly discussed. An original experimental work, the photocatalytic degradation of the dye Congo red (CR) using TiO(2) suspensions and H(2)O(2), in natural surface water (river water) is comprehensively described as a case study, in order to provide sufficient guidelines to deal with this subject, in a rational and integrated way.

Developments on chemometric approaches to optimize and evaluate microextraction

Chemometric experimental design in microextraction plays a crucial role in sustaining the highest quality of analytical data. Making use of the main significant points of chemometric experimental design and microextraction in analytical chemistry we formed the core of this review article. A step-by-step chemometric approach is provided to optimize and validate microextraction-based analytical processes. Significant applications are reported with developments related to microextraction combined with chemometric optimization processes. As it appears from the numerous examples provided in this review, a great number of researchers give credit to the combination of microextraction and chemometrics recognizing that it significantly streamlines sample processing. Moreover, the combination of microextraction with chemometrics addresses problems relating to improvement in detectability and method validation. A worked example on the microextraction of polychlorinated biphenyls is incorporated into the relevant sections of this article and comprehensively provides in a rational and integrated way guidance to people dealing with this subject.

Application of solid-phase microextraction in the monitoring of priority pesticides in the Kalamas River (N.W. Greece)

A solid-phase microextraction (SPME) method was applied to an extended monitoring survey of priority pesticides for the European Union for a period of 12 months in water of the Kalamas River (Epirus region of northwestern Greece) in order to determine their concentrations and seasonal variations. Polydimethylsiloxane-coated fiber (100 microm) was used. The samples were screened using gas chromatography with flame thermionic detection. Detection was confirmed by gas chromatographymass spectroscopy. The most frequently detected pesticides were some of the more commonly used herbicides, such as S-ethyl-N,N-di-n-propylthiol carbamate (EPTC), trifluralin, atrazine, deethylatrazine, terbuthylazine and alachlor, and insecticides, such as carbofuran, diazinon, disulfoton, parathion methyl, parathion ethyl, fenthion and ethion. Concentrations of individual compounds ranged from 0.020 to 0.3 microg/L. Greater pesticide concentrations occurred during the seasons of application. A comparison with a well-established solid-phase extraction (C18 disks) procedure was performed for samples of high-season application (May-September) in order to confirm the effectiveness of the SPME technique. The results demonstrate the suitability of the SPME method for routine screening multiresidue analysis in natural waters.

Study of chlorothalonil photodegradation in natural waters and in the presence of humic substances

Photodegradation of chlorothalonil was studied in different natural waters (sea, river and lake) as well as in distilled water under natural and simulated solar irradiation. The effect of dissolved organic matter (DOM) such as humic and fulvic substances on the photodegradation rate of chlorothalonil was also studied in simulated sunlight. The presence of DOM enhanced the photodegradation of chlorothalonil with the exception of seawater. The kinetics were determined through gas chromatography electron capture detection (GC/ECD) and the photodegradation proceeds via pseudo-first-order reaction in all cases. Half-life ranged from 1 to 48 h. In natural and humic water chlorothalonil photodegradation gave rise to two different intermediates compared to distilled water demonstrating that the transformation of chlorothalonil depend on the constitution of the irradiated media and especially from DOM. The byproducts identified by GC/MS techniques were: chloro-1,3-dicyanobenzene, dichloro-1,3-dicyanobenzene, trichloro-1,3-dicyanobenzene and benzamide.

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 microL 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).

Application of statistical design of experiment with desirability function for the removal of organophosphorus pesticide from aqueous solution by low-cost material

This paper deals with the multiple response optimization for the removal of organophosphorus pesticide quinalphos [QP: O,O-diethyl O-2-quinoxalinyl phosphorothioate] from the aqueous solution onto low-cost material and tried to overcome the drawbacks of univariate optimization. Used tea leaves were used as low-cost adsorbent and batch equilibration method was followed for this study. A Box-Behnken design was used to develop response model and desirability function was then used for simultaneous optimization of all affecting parameters in order to achieve the highest removal% of quinalphos. The optimum conditions of factors predicted for quinalphos removal% were found to be: pH 8.83, concentration 7 mg L(-1) and dose 0.40 g. Under these conditions, maximum removal% of quinalphos was obtained 96.31%. Considering the above optimum conditions, the adsorption isotherms were developed and provided adsorption capacity of 196.07 microg g(-1) by using Langmuir equation, indicating that used tea leaves may be applied as a low-cost material for pesticides removal from aqueous matrices.

Photocatalytic degradation of propachlor in aqueous TiO2 suspensions. Determination of the reaction pathway and identification of intermediate products by various analytical methods

The light-induced degradation of propachlor (2-chloro-N-isopropylacetanilide) under simulated solar irradiation has been investigated in aqueous solutions containing TiO2 suspensions as photocatalysts. The study focuses on the identification of possible intermediate products and the determination of inorganic ions formed during the process, using several powerful analytical techniques such as gas chromatography mass-spectrometry (GC-MS) and ion chromatography. The primary degradation of propachlor has been a fast process with a half-live time of 2.3 min and followed pseudo-first-order kinetics according to the Langmuir-Hinshelwood model. The mineralization of the organic carbon to CO2 after 240 min of irradiation was found to be < 63%. The corresponding stoichiometric transformation of organic chlorine into chloride ion was reached in 30 min, whereas oxidation of nitrogen to nitrate ions took place at delayed irradiation times. Various aromatic intermediates have been identified by GC/MS techniques during the treatment, which were involved into three tentative degradation routes. One, was based on the dechlorination through positive holes or solvated electrons to form the hydroxy or aliphatic derivative. The second route consists of the rupture of amide bond or the N-C bond via nitrogen ionization by positive holes and through the ring hydroxylation, respectively. Finally, the third possible degradation route was based on hydrogen abstraction by the hydroxyl radicals or positive holes, followed either by the addition of oxygen to the alkyl radical or the decomposition of the peroxyl radical formed. From the analytical data, a possible multi-step degradation scheme was proposed. This work points to the necessity of extended knowledge of the successive steps in a solar-assisted detoxification process.

Survey for the occurrence of antifouling paint booster biocides in the aquatic environment of Greece

Since the restriction imposed by European Union regulations on the use of TBT-based antifouling paints on boats below 25 m in length, new terms have been introduced in the ‘small boat’ market. Replacement products are generally based on copper metal oxides and organic biocides. Several studies have demonstrated the presence of these biocides in European ports and marinas of Spain, France, Germany and the United Kingdom. An extended survey of the antifouling biocides chlorothalonil, dichlofluanid, irgarol 1051 and sea-nine 211 was carried out in Greek ports and marinas of high boating activities from October 1999 to September 2000. The sampling sites were: Piraeus, Elefsina, Thessaloniki, Patras, Chalkida, Igoumenitsa, and Preveza (Aktio). The extraction of these compounds from the seawater samples was performed off-line with C18 solid phase extraction (SPE) disks while the determination was carried out with gas chromatography coupled to electron capture (ECD), thermionic (FTD) and mass spectroscopy (MS) detectors. The concentration levels of biocides were higher during the period from April to October. This seasonal impact depends on the application time of antifouling paints and mimic trends in the seasonal distribution of biocides in other European sites.

An experimental design approach employing artificial neural networks for the determination of potential endocrine disruptors in food using matrix solid-phase dispersion.

Matrix solid-phase dispersion (MSPD) as a sample preparation method for the determination of two potential endocrine disruptors, linuron and diuron and their common metabolites, 1-(3,4-dichlorophenyl)-3-methylurea (DCPMU), 1-(3,4-dichlorophenyl) urea (DCPU) and 3,4-dichloroaniline (3,4-DCA) in food commodities has been developed. The influence of the main factors on the extraction process yield was thoroughly evaluated. For that purpose, a 3 fractional factorial design in further combination with artificial neural networks (ANNs) was employed. The optimal networks found were afterwards used to identify the optimum region corresponding to the highest average recovery displaying at the same time the lowest standard deviation for all analytes. Under final optimal conditions, potato samples (0.5 g) were mixed and dispersed on the same amount of Florisil. The blend was transferred on a polypropylene cartridge and analytes were eluted using 10 ml of methanol. The extract was concentrated to 50 microl of acetonitrile/water (50:50) and injected in a high performance liquid chromatography coupled to UV-diode array detector system (HPLC/UV-DAD). Recoveries ranging from 55 to 96% and quantification limits between 5.3 and 15.2 ng/g were achieved. The method was also applied to other selected food commodities such as apple, carrot, cereals/wheat flour and orange juice demonstrating very good overall performance.

Sensitive determination of pesticides residues in wine samples with the aid of single-drop microextraction and response surface methodology.

The multi-residue trace-level determination of six pesticides (diazinon, dimethoate, chlorpyrifos, vinclozolin, fenthion and quinalphos) in wine samples, after their single-drop microextraction (SDME) is presented herein. The extraction procedure was optimized using the multivariate optimization approach following a two-stage process. The first screening experimental design brought out the significant parameters and was followed by a central composite design (CCD) experiment, which revealed the simultaneous effect of the significant factors affecting the SDME process. High level of linearity for all target analytes was recorded with r(2) ranging between 0.9978 and 0.9999 while repeatability (intra-day) and reproducibility (inter-day) varied from 5.6% to 7.4% and 4.9% to 12.5%, respectively. Limits of detection (LODs) and limits of quantification (LOQs) were found to range in the low microg L(-1) level. In general, the developed methodology presented simplicity and enhanced sensitivity, rendering it appropriate for routine wine screening purposes.