Instrumental Techniques to Classify Olive Oils according to Their Quality.

This review includes an update of the publications on quality classification of olive oils into extra, virgin or lampante olive oil categories. Nowadays, the official method to carry out this classification is time-consuming and, sometimes, it is not systematic and/or objective. It is based on conventional physicochemical analysis and on a sensorial tasting of olive oils carried out by a panel of experts. The aim of this review was to explore and give value to the alternative techniques reported in the bibliography to complement the current official methods established for that classification of olive oils. Specifically considered were non-separation and separation analytical techniques which could contribute to correctly classify olive oils according to their physicochemical and/or sensorial characteristics. An in-depth description has been written on the methods used to differentiate these three types of olive oils and the main advantages and disadvantages of the proposed procedures. The techniques here reviewed could be a real and fast option to complement or even substitute some of the analysis included in the official method. Finally, general trends and detected difficulties found to address this issue have been discussed throughout the article.

Analytical methods for the determination of emerging contaminants in sewage sludge samples. A review.

Emerging contaminants are a heterogeneous group of chemicals that includes daily personal care products and pharmaceuticals (PPCPs), flame retardants, endocrine disrupting chemicals (EDCs) and nanoparticles (NPs). The present work is an overview focused in the research published in the scientific literature for the determination of this type of pollutants in sewage sludge samples in the last 5 years. Instrumental and sample preparation methods for the detection and quantification of the analytes of interest are reviewed, with an emphasis on the sample treatment techniques. Liquid chromatography (LC) and gas chromatography (GC) coupled to mass spectrometry are generally employed as the analytical technique of preference. Sample preparation techniques include conventional methods such as Soxhlet, solid-phase extraction (SPE), pressurized liquid extraction (PLE) or ultrasound-assisted extraction (UAE), but also other recent techniques, including novel microextraction techniques such as microextraction by packed sorbent (MEPS) or solid-phase microextraction (SPME).

Determination of Three Main Chlorogenic Acids in Water Extracts of Coffee Leaves by Liquid Chromatography Coupled to an Electrochemical Detector.

Coffee is a beverage widely consumed in the world. The coffee species most commercialized worldwide are Arabica (Coffea arabica) and Robusta (Coffea canephora). Roasted coffee beans are the most used, but coffee leaves are also consumed as infusion in several countries for traditional medicinal purposes. They contain several interesting phenolic antioxidant compounds mainly belonging to chlorogenic acids (CGAs). In the present work, a liquid chromatography-electrochemical detection (LC-EC) method was developed for the determination of three main chlorogenic acid isomers, namely 3-, 4-, and 5-caffeoylquinic acids (CQA), in coffee leaves aqueous extracts. Samples from eight coffee species, namely; Coffea arabica, Coffea canephora, Coffea liberica, Coffea humilis, Coffea mannii, Coffea charrieriana, Coffea anthonyi, and Coffea liberica var. liberica, were grown and collected in tropical greenhouses. Linearity of the calibration graphs was observed in the range from the limit of quantification to 1.0 × 10-5 M, with R² equal to 99.9% in all cases. High sensitivity was achieved with a limit of detection of 1.0 × 10-8 M for 3-CQA and 5-CQA (i.e., 3.5 µg/L) and 2.0 × 10-8 M for 4-CQA (i.e., 7.1 µg/L). The chromatographic profile of the samples harvested for each Coffea species was studied comparatively. Obtained raw data were pretreated for baseline variations and shifts in retention times between the chromatographic profiles. Principal Component Analysis (PCA) was applied to the pretreated data. According to the results, three clusters of Coffea species were found. In the water sample extracts, 5-CQA appeared to be the major isomer, and some species contained a very low amount of CQAs. Fluctuations were observed depending on the Coffea species and harvesting period. Significant differences between January and July were noticed regarding CQAs content. The species with the best CQAs/caffeine ratio was identified. The LC-EC data were validated by liquid chromatography-high resolution mass spectrometry (LC-HRMS).

Determination of quinolone residues in raw cow milk. Application of polar stir-bars and ultra-high performance liquid chromatography-tandem mass spectrometry.

Seventeen quinolone antibiotics were determined in cows' milk. A method of high sensitivity, selectivity and accuracy was developed. Accuracy (trueness and precision), linearity, sensitivity, selectivity, decision limit and detection capability were established following the recommendations of the Commission Decision 2002/657/EC and the Food and Drug Administration (FDA) guideline. The use of polar stir-bar sorptive extraction (SBSE) prior to UHPLC-MS/MS analysis is proposed. The variables that affect SBSE were optimised using multivariate optimisation strategies. The ionic strength, the extraction time and the sample volume were studied. pH and stir-bar coating (polydimethylsiloxane, PDMS, and polyethyleneglycol modified silicone, PEG) were studied. PEG showed the best extraction yield at pH 6. For validation, a matrix-matched calibration and a recovery assay were carried out. Limits of quantification from 0.5 µg kg-1 for nalidixic acid, flumequine and piromidic acid, to 4.0 µg kg-1 for sarafloxacin were calculated. The precision (%, RSD) was lower than 15% for all antibiotics. Recoveries in fortified samples were between 88 and 114%.

Electrochemical Detectors in Liquid Chromatography: Recent Trends in Pharmaceutical and Biomedical Analysis.

Liquid chromatography (LC) coupled to an electrochemical (EC) detector is a complementary analytical tool compared to LC coupled with optical or mass spectrometry detectors (LC-MS). LC-EC can be applied to the determination of molecules difficult to be analyzed by other commercially available detectors. New EC detector design and new working electrode material have extended the scope of application in the field of pharmaceutical compounds analysis. Combining EC with LC-MS offers additional advantages compared to optical detectors in terms of drug stability and drug metabolism mimicry studies. Selected literature devoted to pharmacologically active compounds in their dosage forms, herbal drugs in natural products, drug residues in feed and/or in biological samples are reported in this review.

Polar stir bars for isolation and preconcentration of perfluoroalkyl substances from human milk samples prior to UHPLC-MS/MS analysis.

BACKGROUND: A new method for the determination of four perfluoroalkyl carboxylic acids (from C5 to C8) and perfluorooctane sulfonate in human milk samples using stir-bar sorptive extraction-ultra-HPLC-MS/MS has been accurately optimized and validated. METHODOLOGY: Polydimethylsiloxane and polyethyleneglycol modified silicone materials were evaluated. DISCUSSION: Overall, polyethyleneglycol led to a better sensitivity. After optimizing experimental variables, the method was validated reaching detection limits in the range of 0.05-0.20 ng ml(-1); recovery rates from 81 to 105% and relative standard deviations fewer than 13% in all cases. The method was applied to milk samples from five randomly selected women. All samples were positive for at least one of the target compounds with concentrations ranging between 0.8 and 6.6 ng ml(-1), being the most abundant perfluorooctane sulfonate.

Stir-membrane solid-liquid-liquid microextraction for the determination of parabens in human breast milk samples by ultra high performance liquid chromatography-tandem mass spectrometry.

In this article, stir-membrane solid-liquid-liquid microextraction (SM-SLLME) is tailored for the analysis of solid matrices and it has been evaluated for the determination of parabens in l breast milk samples. A three-phase microextraction mode was used for the extraction of the target compounds taking advantage of their acid-base properties. The unit allows the simultaneous extraction of the target compounds from the solid sample to an organic media and the subsequent transference of the analytes to an aqueous acceptor phase. The method includes the identification and quantification of the analytes by ultra high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). All the variables involved in the extraction procedure have been accurately studied and optimized. The analytes were detected and quantified using a triple quadrupole mass spectrometer (QqQ). The selection of two specific fragmentation transitions for each compound allowed simultaneous quantification and identification. The method has been analytically characterized on the basis of its linearity, sensitivity and precision. Limits of detection ranged from 0.1 to 0.2ngmL(-1) with precision better than 8%, (expressed as relative standard deviation). Relative recoveries were in the range from 91 to 106% which demonstrated the applicability of the stir-membrane solid-liquid-liquid microextraction for the proposed analytical problem. Moreover, the method has been satisfactorily applied for the determination of parabens in lyophilized breast milk samples from 10 randomly selected individuals.