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This paper describes the synthesis of a silica based MSU-1 mesoporous solid and its application as sorbent in solid-phase extraction to pre-concentrate thirteen pesticides of low-high polarity (methomyl, cymoxanil, carbofuran, monolinuron, isoproturon, methidathion, methiocarb, malathion, phosalone, diazinon, penconazole, neburon and chlorotoluron) in ground and river water. The synthesis was based in an H-bonding interaction assembling (I 0 N 0 ) between two non-ionic components (the inorganic silica surface, I 0 and the polyethylene oxide template, N 0 ) by adding tetraethoxysilane to the non-ionic surfactant Brij®100, the latter previously dissolved in HCl 1 M. 50 mL water samples adjusted at pH= 3.5 were passed, at a flow rate of 5 mL/min, through a home-made cartridge containing 50 mg of MSU-1 sorbent, pre-conditioned with 5 mL of ultrapure water; then, the cartridge was washed with 5 mL of ultrapure water. Following elution with 5 mL of acetonitrile, the pesticides were determined by ultra performance liquid chromatography coupled to triple quadrupole-mass spectrometry. Two selected reaction monitoring transitions were monitored per compound, the most intense one being used for quantification and the second one for confirmation. Three points were used for identification, as established in the Directive 96/23/EC for LC-MS/MS analysis, which deals with confirmatory methods for organic residues and contaminants listed in the Group B (veterinary drugs and contaminants). Medium matrix effect (|20%||50%|). Therefore, the standard addition methodology was applied by adding an adequate amount of the pesticide standard mixture to the final sample extract. All pesticides were quantified using this approach for practical reasons, thus avoiding two different calibrations. The method quantification limit (MQL) of pesticides was 0.01 μg/L for all of them, except for diazinon (0.1 μg/L). Recoveries of the target pesticides at MQL and 0.25 µg/L concentration levels in blank river water were in the range 70.1-113.5% and 86.7-107.3%, respectively, with RSDs lower than 16.3% and 15.7%, respectively. Four ground water samples and three river water samples, taken from Almería (Spain), were analyzed by the proposed method and only phosalone at a concentration level of 0.05 µg/L was found in one river water sample., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The aim of this analytical study is to develop an improved multi-residue methodology of high sensitivity and expanded scope for pesticide residue analysis in honeybee wax combs. The method was validated for 160 pesticide residues (including acaricides, insecticides, fungicides and herbicides) gas chromatography amenable and covering a wide variety of polarity and chemical structure. This method of analysis applied gas chromatography coupled to a triple quadrupole mass spectrometer for the quantitative analysis of pesticide residues. The extraction procedure applied was based QuEChERs method allowing acceptable recoveries for most of the pesticides (98%), within the range 60-120% with an associated precision (RSD) <20%, at concentration levels of MQL of 10µgkg -1 for all pesticides with the exception of 3,5-dichloroaniline and chlordane (20µgkg -1 ). The expanded uncertainty of the results was ±35% on average (coverage factor k=2 for a confidence level of 95%). The chromatographic multi-residue method was applied to determine levels of pesticide residues in 50 honeybee wax comb samples randomly collected from different apiaries in Spain. A total of 32 pesticide residues (14 insecticides/acaricides, 10 insecticides, 6 fungicides and 2 herbicides) were detected in the samples. The highest pesticide concentrations were found for those with insecticide-acaricide activity like acrinathrin, chlorfenvinphos, coumaphos and fluvalinate-tau, some of them are mainly applied in apiculture for controlling the honeybee parasite Varroa destructor. The total load of pesticide residues ranged from 69 to 1000µgkg -1 for 40% of the analysed samples, 22% contained pesticide residues in the ranges of 1000-2000µgkg -1 , 24% between 2000 and 5000µgkg -1 and 14% of the samples contained residues between 5000 and 9557µgkg -1 ., (Copyright © 2016 Elsevier B.V. All rights reserved.)

This paper reports the first application of the silica based mesoporous material MCM-41 as a sorbent in solid phase extraction, to pre-concentrate pharmaceuticals of very different polarity (atenolol, nadolol, pindolol, timolol, bisoprolol, metoprolol, betaxolol, ketoprofen, naproxen, ibuprofen, diclofenac, tolfenamic acid, flufenamic acid and meclofenamic acid) in surface waters. The analytes were extracted from 100mL water samples at pH 2.0 (containing 10(-3) mol/L of sodium chloride) by passing the solution through a cartridge filled with 100 mg of MCM-41. Following elution, the pharmaceuticals were determined by micro-liquid chromatography and triple quadrupole-mass spectrometry. Two selected reaction monitoring transitions were monitored per compound, the most intense one being used for quantification and the second one for confirmation. Matrix effect was found in real waters for most analytes and was overcome using the standard addition method, which compared favorably with the matrix matched calibration method. The detection limits in solvent (acetonitrile:water 10:90, v/v) ranged from 0.01 to 1.48 μg/L and in real water extracts from 0.10 to 3.85 μg/L (0.001-0.0385 μg/L in the water samples). The quantitation limits in solvent were in the range 0.02-4.93 μg/L, whereas in real water extracts were between 0.45 and 10.00 μg/L (0.0045 and 0.1000 μg/L in the water samples). When ultrapure water samples were spiked at two concentration levels of each pharmaceutical (0.1 and 0.2 μg/L) and quantified using solvent based calibration graphs, recoveries were near 100%. However, recoveries for most pharmaceuticals were comparable or better than de described above, when river water samples (spiked at the same concentration levels) were quantified by the standard addition method and slightly worse using the matrix matched calibration method. Five real samples (two rivers, one dam and two fountain water samples) were analyzed by the developed method, atenolol, timolol, betaxolol, nadolol and diclofenac being found in some of them, at levels higher than their quantitation limits., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A metabonomic study based on the application of multivariate curve resolution and alternating least squares (MCR-ALS) to three-way data sets obtained by liquid chromatography coupled to mass spectrometry detection (LC-MS) was carried out for Rambo and Raf tomato cultivars treated with carbofuran pesticide. Samples were picked up during a 21 days period after treatment and analyzed by LC-MS in scan mode, along with the corresponding blank samples. Then, MCR-ALS was applied to the three-way data sets using column wise augmented matrices, and the evolutionary profiles as a function of the time after treatment were estimated for the metabolites present in both cultivars, as well as their corresponding pure spectra estimations. A comparative study using those estimations showed that some of these metabolites followed different behavior for the different cultivars after treatment. Since all treated and untreated Rambo and Raf samples were picked up according to the same sampling protocol and in a similar state of maturation, any difference in the behavior between profiles can be interpreted as an effect due to the presence of pesticide and to the kind of cultivar. Based on this hypothesis, several PLS-DA approaches were tested to check if it would be possible to classify samples by using the metabolites MCR estimations. Results showed that PLS-DA models for classification of treated or non-treated (blank) samples were the best ones obtained (98.44% of correct classifications for the validation set), which supports the stress effects related to carbofuran treatment. In addition, excellent discrimination among the four groups could be attained (89.06% of correct classifications for the validation set)., (Copyright © 2011 Elsevier B.V. All rights reserved.)

This paper describes about an automated on-line enrichment method for the simultaneous determination of seven β-blockers in river water using a short liquid chromatography column for preconcentration coupled with LC-DAD. The method performs the preconcentration of 30 mL of river water samples (5% organic modifier) using a 50 mm×4.6 mm C18 column for enrichment and a 150 mm×4.6 mm C18 column for separation, allowing the determination of β-blockers at trace levels in river water. The analytical procedure was developed by optimizing the breakthrough parameters (flow rate, time of preconcentration and percentage of organic modifier added to the sample) in order to achieve the maximum sensitivity, and by optimizing the mobile phase (composition and flow rate) to get adequate separation of the components in a reasonable analysis time. Under the optimized conditions, the method was validated with respect to linearity, precision, limits of detection, limits of quantification and accuracy. Detection and quantitation limits ranged between 0.1 and 3.1 and between 1.0 and 5.0 ng mL(-1), respectively, whereas the RSD on inter-day precision was below 8%. To cope with the matrix effect in the determination of these drugs in river water samples, the standard addition methodology was successfully applied. Recoveries ranging from 81 to 115% proved the accuracy of the methodology proposed in this work., (Copyright © 2010 Elsevier B.V. All rights reserved.)

This overview covers the different chemometric strategies linked to chromatographic methodologies that have been used and presented in the recent literature to cope with problems related to incomplete separation, the presence of unexpected components in the sample, matrix effect and changes in the analytical signal due to pre-treatment of sample. Among the different chemometric strategies it focuses on pre-treatment of data to correct background and time shift of chromatographic peaks and the use of second-order algorithms to cope with overlapping peaks from analytes or from analytes and interferences in liquid chromatography coupled to diode array, fast-scanning fluorescence spectroscopy and mass spectrometry detectors. Finally the review presents the strategies used to deal with changes in the analytical response as result of matrix effect in liquid and gas chromatography, as well as the use of standardization strategies to correct modifications in the analytical signal as a consequence of sample pre-treatment in liquid chromatography., (Copyright © 2010 Elsevier B.V. All rights reserved.)

Multivariate science based calibration (SBC) has been applied to the resolution of overlapped peaks in liquid chromatography with diode array detection (LC-DAD). Complex river water samples spiked with 11 pharmaceutical substances resulted in poorly resolved chromatograms containing additional peaks from interfering matrix compounds and a change in the background absorbance due to the mobile phase gradient. Applying the present multivariate approach it was possible to resolve all 11 analytes from overlapping peaks, obtaining linear calibration lines (R(2)>0.96). Recovery percentages on spiked samples ranged between 74.6 and 113.5%, which are quite satisfactory taking into account the low concentration ranges considered to 1-7 μg L(-1)., (Copyright © 2010 Elsevier B.V. All rights reserved.)

This study reports the first analytical application of luminol chemiluminescence reaction for the sensitive detection of two benzoylurea insecticides (diflubenzuron and triflumuron). Off-line experiments demonstrated that previously irradiated traces of these benzoylurea insecticides largely enhanced the chemiluminescence emission yielded from the oxidation of luminol in methanol:water mixtures, by potassium permanganate in alkaline medium, the enhancement being proportional to the concentration of both pesticides. The two benzoylureas were determined in tomato samples by coupling liquid chromatography with post-column photoderivatization and detection based on this chemiluminescence reaction. Tomato samples were extracted using the QuEChERS method based on extraction with acetonitrile and dispersive solid-phase clean-up using primary and secondary amine (PSA). Interferences due to matrix effect were overcome by using matrix-matched standards. The optimised method was validated with respect to linearity, limits of detection and quantification, precision and accuracy. Under the optimised conditions, calibrations graphs were linear between 0.05 and 0.50 microg mL(-1) for diflubenzuron and between 0.10 and 1.00 microg mL(-1) for triflumuron. Method detection limits were 0.0025 and 0.0131 microg mL(-1) (equivalent to 0.0005 and 0.0026 mg kg(-1)) and quantification limits were 0.05 and 0.10 microg mL(-1) (equivalent to 0.01 and 0.02 mg kg(-1)) for diflubenzuron and triflumuron, respectively. In both cases, quantification limits were lower than the maximum residue levels (MRLs) established by the European legislation. The relative standard deviation of intra-day precision was below 10% and recoveries were between 79.7% and 94.2% for both pesticides.

A new sensitive method for the determination of three tetracyclines in surface water samples (tetracycline, chlortetracycline and oxytetracycline) using highly collinear data corresponding to photochemical-induced fluorescence excitation emission matrices, modelled with three-way data arrays chemometric tools has been developed. The method involves irradiation of aqueous basic solution of antibiotics with UV light and fluorescence determination of the generated photoproducts after solid phase preconcentration (SPE) with Oasis hydrophilic lipophilic balance (HLB) cartridges. The chemometric models were built by using an eight samples calibration set and samples corresponding to both a validation set and a test set. The latter set containing unsuspected interferents. Considering this latter samples, recoveries of 101.5, 97.9 and 102.2 were obtained for the three analytes. Evaluation of constant and proportional bias and precision were made by using the elliptical joint confidence region (EJCR) test for the estimated intercept and slope.

Multi-wavelength detectors offer improved detection capabilities for liquid chromatographic methods, but require multivariate approaches to utilise all the available information. The photodiode-array detector in high-performance liquid chromatography (HPLC) generates a three-dimensional data matrix, which is conventionally presented as an isometric projection or a contour plot. In this work, a new graphical technique is described for improving the quantitative results obtained from HPLC, using the available spectrochromatographic information in both the time and wavelength domains. The technique consists of performing cross-sections through the data matrix to obtain the maximum analytical information for each of the analytes. Hence, the resolution of overlapping peaks and the sensitivity in the determination are optimised. In order to demonstrate the validity and simplicity of the approach, the method has been applied to the resolution of synthetic mixtures of iprodione, procymidone and chlorothalonil. Also, the method has been satisfactorily applied to the simultaneous determination of the pesticides in environmental groundwater samples.