Pesticide residues in fruit samples: comparison of different QuEChERS methods using liquid chromatography-tandem mass spectrometry.

Acetate- and citrate-buffered quick, easy, cheap, effective, rugged, safe (QuEChERS) pretreatment methods were evaluated for the determination of various pesticides in peaches, grapes, apples, bananas, pears, and strawberries from various regions of Greece, using LC-MS/MS. The purposes of this study were (i) to evaluate which type of QuEChERS method was the most appropriate and effective for each matrix; (ii) to apply the selected QuEChERS method for each matrix, in order to detect and quantify pesticide residues in various fruit samples using UPLC-MS/MS; (iii) to examine the concentration distribution of pesticide classes among fruit originating from various areas; and (iv) to assess pesticide concentration distribution between peel and flesh of fruit in order to evaluate the penetration of pesticide residues in the fruit flesh. Acetate-buffered QuEChERS was found to be the most suitable technique for most of the fruit matrices. According to the recovery values at two different concentration levels, peaches should preferably be treated by the citrate-buffered type, whereas grapes, bananas, apples, pears, and strawberries are best treated by the acetate-buffered version, although the differences in efficiency were small. The addition of graphitized carbon black significantly decreases the recovery of specific pesticides in all matrices except for strawberries. The majority of values do not exceed the official maximum residue levels set by the European Commission. Organophosphates proved to be the most commonly detected category along with triazines-triazoles-conazoles group and by carbamates. Apples and pears seem to be the most contaminated fruit matrices among those tested. Distribution of pesticide classes shows variations between different regions, suggesting different pesticide application practices. In the case of peaches and pears, there is an equal distribution of detected pesticides between peel and flesh, indicating penetration of contaminants into the fruit flesh.

Photocatalytic degradation of molinate in aqueous solutions.

In this study, the degradation of molinate through heterogeneous photocatalysis, using two different types of the semiconductor TiO2 as photocatalyst, as well as through homogeneous treatment, applying the photo-Fenton reaction, has been investigated. As far as heterogeneous photocatalysis is concerned, the degradation of the pesticide follows apparent first-order kinetics, while the type of the catalyst and the pH value of the solution affect the degradation rate. The effect of the addition of electron scavengers (H2O2 and K2S2O8) was also studied. In the case of photo-Fenton-assisted system, the degradation also follows pseudo-first-order kinetics. Parameters such as iron's and electron scavenger's concentration and inorganic ions strongly affect the degradation rate. The extent of pesticide mineralization was investigated using dissolved organic carbon (DOC) measurements. The toxicity of the treated solution was evaluated using the Microtox test based on the luminescent bacteria Vibrio fischeri. The detoxification and mineralization efficiency was found to be dependent on the system studied, and although it did not follow the rate of pesticide disappearance, it took place in considerable extent. The study of the photodegradation treatment was completed by the determination of the intermediate by-products formed during the process, which was carried out using LC-MS/MS technique and led to similar compounds with both processes.

Photo-Fenton decomposition of ß-blockers atenolol and metoprolol; study and optimization of system parameters and identification of intermediates.

Active pharmaceutical compounds reach the wastewater treatment plants mainly through excretion and improper disposal, and, because of insufficient treating methods, they end up to surface water or even potable water in some cases. Atenolol and metoprolol are ß-blockers, members of cardiovascular pharmaceuticals group. They are generally used in the treatment of disorders such as hypertension, angina and arrhythmias. They have been in long-term use in Europe and North America, and they have also been detected in the aquatic environment. In this study the degradation of atenolol and metoprolol in aqueous solutions by means of the photo-Fenton reaction was investigated. The purpose of this study was: (i) to investigate the influence of the concentrations of iron and hydrogen peroxide, by means of central composite design, (ii) to study the degradation kinetics in aqueous solutions, (iii) to evaluate the mineralization and the toxicity evolution of the target compounds and (iv) to identify the degradation products. It has been found that increase of iron and hydrogen peroxide concentration accelerate the degradation of atenolol and metoprolol, while the kinetics of the process can be characterized as pseudo-first order. In general the photo-Fenton method has proved to be effective in decomposing and mineralizing the target compounds. The determination of the by-products formed during the degradation using LC-MS/MS equipment and the evaluation of the toxicity of the treated solution in different stages of the process would offer significant, innovative information regarding the treatment of water and wastewater containing active pharmaceutical compounds, especially of the ß-blocker group.

Heterogeneous photocatalytic degradation of prometryn in aqueous solutions under UV-Vis irradiation.

In this study, the heterogeneous photocatalytic degradation of prometryn using TiO(2) as photocatalyst was investigated. The main objectives of the study were: (I) to evaluate the kinetics of the pesticide disappearance, (II) to compare the photocatalytic efficiency of two different types of TiO(2), (III) to examine the influence of various parameters such as initial concentration of pesticide or catalyst and presence of oxidants (H(2)O(2) and K(2)S(2)O(8)), (IV) to evaluate the degree of mineralization and (V) to assess the detoxification efficiency of the studied processes. The experiments were carried out in a 500 ml pyrex UV reactor equipped with a 125 W high-pressure mercury lamp surrounded by a pyrex filter blocking wavelengths below 290 nm. Prometryn concentration was determined using HPLC. It was found that the degradation of the pesticide follows the first order kinetics according to the Langmuir-Hinshelwood model. Parameters like the type and concentration of the catalyst affect the degradation rate. A synergistic effect was observed when an oxidant was added in the TiO(2) suspensions increasing the reaction rate of photodegradation. In order to examine the extent of pesticide mineralization, DOC measurements were carried out. After 6h of illumination, mineralization was achieved up to almost 70%. The toxicity of the treated solution was evaluated using the Microtox test based on the luminescent bacteria Vibrio fisheri, in order to compare the acute toxicity of prometryn and its photoproducts. The detoxification efficiency was found to be dependent on the studied system and it did not follow the rate of pesticide disappearance.

Photocatalytic decolorization and degradation of dye solutions and wastewaters in the presence of titanium dioxide.

In this study, the photocatalytic degradation of two commercial azo dyes in the presence of TiO(2) suspensions as photocatalyst has been investigated. The degradation of the dyes follows a pseudo-first-order kinetics according to the Langmuir-Hinshelwood model. Under the certain experimental conditions, in the presence of TiO(2) P-25 decolorization is achieved within 100 min of illumination, while in the presence of TiO(2) Hombikat UV-100 complete color disappearance is accomplished in less than 50 min of light exposure. The influence of various parameters, such as the type and mass of the catalyst, the initial concentration of the dye, etc. on the degradation process was examined. The mineralization of organic carbon was also evaluated by measuring the dissolved organic carbon (DOC) of the dye solutions. Moreover, the toxic properties of the dye solutions treated by photocatalysis were examined by the use of a Microtox bioassay (Vibrio fischeri). Finally, experiments using real textile wastewater were also carried out, in order to examine the effectiveness of the method to a more complex substrate.