Christophoros Christophoridis

Vortex‐assisted liquid–liquid microextraction combined with gas chromatography‐mass spectrometry for the determination of organophosphate pesticides in environmental water samples and wines

A simple vortex-assisted liquid-liquid microextraction protocol followed by GC-MS is proposed for the determination of 12 organophosphate pesticides residues in environmental water samples and wines. The sample pretreatment employs the usage of low-density organic solvent. The parameters affecting the extraction efficiency (type and volume of organic extraction solvent, sample pH, ionic strength, extraction time, and centrifugation speed) were carefully examined. A mild emulsification process was involved by the addition of 40 μL toluene into 10 mL sample followed by sequential vortex-based agitation and manual shaking for 3 min. Following the extraction, the pesticide-rich organic solvent was recovered by centrifugation at 4000 rpm for 5 min. A fraction of the floated toluene was then collected and analyzed by GC-MS in SIM mode. Under the optimized conditions, the enrichment factor ranged between 65 and 389. Satisfactory linearity was observed for all pesticides tested with correlation coefficients higher than 0.9945 while the LODs were in the range of 2-11 ng L(-1) . The main advantages of the proposed method are the simplicity of operation, rapidity, low cost, and high sensitivity.

Fenton and Fenton-like oxidation of pesticide acetamiprid in water samples: Kinetic study of the degradation and optimization using response surface methodology

The aims of this study were (a) to evaluate the degradation of acetamiprid with the use of Fenton reaction, (b) to investigate the effect of different concentrations of H2O2 and Fe(2+), initial pH and various iron salts, on the degradation of acetamiprid and (c) to apply response surface methodology for the evaluation of degradation kinetics. The kinetic study revealed a two-stage process, described by pseudo- first and second order kinetics. Different H2O2:Fe(2+) molar ratios were examined for their effect on acetamiprid degradation kinetics. The ratio of 3 mg L(-1) Fe(2+): 40 mg L(-1) H2O2 was found to completely remove acetamiprid at less than 10 min. Degradation rate was faster at lower pH, with the optimal value at pH 2.9, while Mohr salt appeared to degrade acetamiprid faster. A central composite design was selected in order to observe the effects of Fe(2+) and H2O2 initial concentration on acetamiprid degradation kinetics. A quadratic model fitted the experimental data, with satisfactory regression and fit. The most significant effect on the degradation of acetamiprid, was induced by ferrous iron concentration followed by H2O2. Optimization, aiming to minimize the applied ferrous concentration and the process time, proposed a ratio of 7.76 mg L(-1) Fe(II): 19.78 mg L(-1) H2O2. DOC is reduced much more slowly and requires more than 6h of processing for 50% degradation. The use to zero valent iron, demonstrated fast kinetic rates with acetamiprid degradation occurring in 10 min and effective DOC removal.

Part II: temporal and spatial distribution of multiclass pesticide residues in lake sediments of northern Greece: application of an optimized MAE-LC-MS/MS pretreatment and analytical method.

The development and application of an analytical methodology for the pretreatment and determination of 253 multiclass pesticides, in lake sediment samples, using liquid chromatography coupled with mass spectrometry (LC-MS/MS) are described in this work. Sediments of lakes Volvi, Doirani, and Kerkini, located in northern Greece, were collected in two-time periods (fall/winter 2010 and spring/summer 2011) and analyzed, applying the developed analytical methodology. Microwave-assisted extraction (MAE) was applied to extract the pesticide residues from lake sediment samples. Analytical results were stored, categorized, and visualized using geographical information systems, in order to assess and observe spatial and temporal variations of the pollution. Main pesticides that were detected included the following: amitrole, tebuconazole, phoxim, diniconazole, sethoxydim, temephos, tetrachlorvinphos, pendimethalin, boscalid, disulfoton sulfone, lenacil, propiconazole, cycloxydim, pyridaben, and terbuthylazine. Amitrole, diniconazole, and tebuconazole were found to be common in all three lakes. Lakes Kerkini and Doirani exhibited increased concentrations during the first sampling period (winter 2010) with predominant pesticide classes, triazines/triazoles and organophosphates. Pollution is mainly located near the populated villages of the lakes and the nearby cultivations. During the second sampling period, pesticide concentrations appear lower and located in sediments near the center of the lake. Lake Volvi exhibits increased pesticide concentrations during the second sampling period, temporal and spatial variations and different pesticide profile pattern. Increased pollution occurs near the center of the lake during the first sampling period, mainly comprised by triazines/triazoles and organophosphates. During the second sampling period, the majority of the sediment samples demonstrated a different pesticide profile dominated by unclassified pesticides and triazines/triazoles. Mineralogical analysis of the samples demonstrates that sediments are mainly composed of clay, mud, and sand particles, and they present spatial variations. Near the center of the lakes, sediments appear to be more fine-grained with higher clay content and are more likely to adsorb pesticides.

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.