Novel combination of non-aqueous capillary electrophoresis and multivariate curve resolution-alternating least squares to determine phenolic acids in virgin olive oil

This paper presents the development of a non-aqueous capillary electrophoresis method coupled to UV detection combined with multivariate curve resolution-alternating least-squares (MCR-ALS) to carry out the resolution and quantitation of a mixture of six phenolic acids in virgin olive oil samples. p-Coumaric, caffeic, ferulic, 3,4-dihydroxyphenylacetic, vanillic and 4-hydroxyphenilacetic acids have been the analytes under study. All of them present different absorption spectra and overlapped time profiles with the olive oil matrix interferences and between them. The modeling strategy involves the building of a single MCR-ALS model composed of matrices augmented in the temporal mode, namely spectra remain invariant while time profiles may change from sample to sample. So MCR-ALS was used to cope with the coeluting interferences, on accounting the second order advantage inherent to this algorithm which, in addition, is able to handle data sets deviating from trilinearity, like the data herein analyzed. The method was firstly applied to resolve standard mixtures of the analytes randomly prepared in 1-propanol and, secondly, in real virgin olive oil samples, getting recovery values near to 100% in all cases. The importance and novelty of this methodology relies on the combination of non-aqueous capillary electrophoresis second-order data and MCR-ALS algorithm which allows performing the resolution of these compounds simplifying the previous sample pretreatment stages.     

Simultaneous derivatization and air-assisted liquid–liquid microextraction of some aliphatic amines in different aqueous samples followed by gas chromatography-flame ionization detection

The paper presents a new method based on simultaneous derivatization and air-assisted liquid–liquid microextraction (AALLME) for the extraction and preconcentration of some aliphatic amines prior to gas chromatography-flame ionization detection (GC-FID). Primary aliphatic amines are derivatized and extracted simultaneously by a fast reaction with butylchloroformate (derivatization agent/extraction solvent) under mild conditions. The mixture of butylchloroformate and aqueous sample solution is rapidly sucked into a 10-mL glass syringe and then is injected into a test tube with conical bottom and the procedure is repeated seven times. After centrifuging the resulted cloudy solution, the derivatized analytes in the sedimented phase are determined by GC-FID. The influence of main factors on the efficiency of derivatization/extraction procedure is studied. Under the optimal conditions, the enrichment factors (EFs) for aliphatic amines are obtained in the range of 248–360 and limits of detection (LODs) are between 0.30 and 2.6 μg L⁻¹. The obtained extraction recoveries ranged from 50 to 72% and the relative standard deviation (RSD) was less than 4.8% for intra-day (n = 6) and inter-days (n = 4) precision. The method is successfully applied to determine some aliphatic amines in environmental water samples.     

An overview of analytical methodologies for the determination of antibiotics in environmental waters

The widespread occurrence of antibiotics as contaminants in the aquatic environment has increased attention in the last years. The concern over the release of antibiotics into the environment is related primarily to the potential for the development of antimicrobial resistance among microorganisms. This article presents an overview of analytical methodologies for the determination of quinolone (Qs) and fluoroquinolone (FQs), macrolide (MLs), tetracycline (TCs), sulfonamide (SAs) antibiotics and trimethoprim (TMP) in different environmental waters. The analysis of these antibiotics has usually been carried out by high-performance liquid chromatography (HPLC) coupled to mass spectrometry (MS) or tandem mass spectrometry (MS/MS) and to a lesser extent by ultraviolet (UV) or fluorescence detection (FD). A very important step before LC analysis is sample preparation and extraction leading to elimination of interferences and prevention of matrix effect and preconcentration of target analytes.     

Generation of anti-azoxystrobin monoclonal antibodies from regioisomeric haptens functionalized at selected sites and development of indirect competitive immunoassays

Azoxystrobin is a modern strobilurin fungicide used around the world to combat prime diseases affecting highly valuable crops. Accordingly, residues of this chemical are frequently found in food, even though mostly under maximum tolerated levels. We herein describe the development of an indirect competitive immunoassay for the determination of azoxystrobin residues. A panel of monoclonal antibodies displaying subnanomolar affinity to azoxystrobin was generated using, as immunizing haptens in mice, four functionalized derivatives carrying the same spacer arm located at different rationally chosen positions. This collection of antibodies was thoroughly characterized with homologous and heterologous antigens, and the immunoassay consisting of monoclonal antibody AZo6#49 and the coating conjugate OVA–AZb6, which displayed an IC₅₀ value of 0.102 μg L⁻¹ and a LOD of 0.017 μg L⁻¹, was eventually optimized. The response to different pH and ionic strength conditions of the specific assay was studied using a biparametric approach. In addition, the influence of Tween 20 and organic solvents over the assay parameters was also evaluated. After optimization, the developed immunochemical assay was applied to the analysis of azoxystrobin in spiked juices of relevant fruits and vegetables, showing excellent recoveries between 2 and 500 μg L⁻¹.     

Liquid chromatography/tandem mass spectrometric method for the simultaneous determination of tobacco-specific nitrosamine NNK and its five metabolites

A sensitive and robust high-performance liquid chromatography-electrospray ionization tandem mass spectrometry method to analyze 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) and its five metabolites in one passage was developed and validated. The method achieved excellent reproducibility and accuracy. Linearity was observed for all six compounds (R² = 0.999) with detection limits (S/N ≥ 3) ranging from 0.2 to 2.4 pg on column and 0.01-0.12 ng ml⁻¹ in samples injected. Average intra-day and inter-day variations (% R.S.D.) were 1.2 and 3.5%, respectively. A sample preparation method involving C8 and C18 solid phase extraction provided satisfactory recovery of the analytes in mouse urine. Each NNK metabolite was identified by its chromatographic retention time and specific fragmentation pattern. Since the carcinogenicity of NNK is related to its metabolism, the method described in this report should facilitate toxicological investigations into the carcinogenesis due to NNK exposure in the environment.     

A validated solid-liquid extraction method for the HPLC determination of polyphenols in apple tissues Comparison with pressurised liquid extraction

A solid-liquid extraction procedure followed by reversed-phase high-performance liquid chromatography (RP-HPLC) coupled with a photodiode array detector (DAD) for the determination of polyphenols in freeze-dried apple peel and pulp is reported. The extraction step consists in sonicating 0.5 g of freeze-dried apple tissue with 30 mL of methanol-water-acetic acid (30:69:1, v/v/v) containing 2 g of ascorbic acid/L, for 10 min in an ultrasonic bath. The whole method was validated, concluding that it is a robust method that presents high extraction efficiencies (peel: >91%, pulp: >95%) and appropriate precisions (within day: R.S.D. (n = 5) <5%, and between days: R.S.D. (n = 5) <7%) at the different concentration levels of polyphenols that can be found in apple samples. The method was compared with one previously published, consisting in a pressurized liquid extraction (PLE) followed by RP-HPLC-DAD determination. The advantages and disadvantages of both methods are discussed.     

Pesticides in water and the performance of the liquid-phase microextraction based techniques. A review

The control of pesticides in surface, drinking and groundwater is nowadays a real necessity. In the European Community, their concentration must comply with the established parametric and environmental quality standards (EQSs). Regarding the new legislation, this article updates the information concerning the monitoring of pesticides and the technical specifications for their measurement in water samples where ultra-sensitive analytical methods are required. For some compounds, like pesticides, there is still a need to improve the performance of the existing methods. High sensitive techniques like gas chromatography tandem mass spectrometry (GC–MS/MS) and liquid chromatography coupled with mass spectrometry (LC–MS) have been developed. However, for most of the substances present at trace and ultra-trace levels the extraction and preconcentration steps are so far essential for their detection. Advances at a micro scale have been made and different types of microextractions are being developed. Liquid-phase microextraction (LPME) is an example. The study of this technique has increased in the last years and some innovations have been recently reported for pesticides water analysis. This article reviews the new developed LPME-based techniques and compares its performance with the analytical specifications established for pesticides water monitoring. The results show that LPME-based techniques can be a promising tool to improve the nowadays performance of methods used in pesticides water control.     

A simple ion chromatography method for inorganic anion analysis in edible seaweeds

A new, simple, fast and sensitive ion chromatography (IC) method, for the simultaneous analysis of fluoride, chloride, nitrite, bromide, nitrate, phosphate and sulphate in edible seaweeds was developed and reported for the first time. The validation of the analytical method was studied in terms of linearity, sensitivity, precision and accuracy. All standard calibration curves showed very good correlation between anion peak area and concentration (r > 0.999). Limits of detection and quantitation ranged between 0.002-0.05 mg/L and 0.01-0.1 mg/L, respectively and indicated the high sensitivity of the method. Relative standard deviation values of repeatability and inter-day precision for standard anions with the same sample were less than 2%. Anion recoveries ranged from 97 to 113% for chloride and from 87 to 105% for sulphate, respectively and showed the fairly good accuracy of the method. The method was applied to the analysis of inorganic anions in brown and red edible seaweeds. Brown seaweeds were characterized by higher chloride content up to 33.7-36.9%, while red seaweeds were characterized by higher sulphate content (45-57%). Sulphate content in seaweeds is related to the presence of sulphated polysaccharides of biological importance. The method developed was well applicable to mineral anion analysis in edible seaweeds and shows suitability and reliability of use in other food samples of nutritional importance.     

An overview of sample preparation and extraction of synthetic pyrethroids from water,sediment and soil

The latest developments in sample preparation and extraction of synthetic pyrethroids from environmental matrices viz., water, sediment and soil were reviewed. Though the synthetic pyrethroids were launched in 1970s, to the best of authors’ knowledge there was no review on this subject until date. The present status and recent advances made during the last 10 years in sample preparation including conservation and extraction techniques used in determination of synthetic pyrethroids in water, sediment and soil were discussed. Pre- and post-extraction treatments, sample stability during extraction and its influence upon the whole process of analytical determination were covered. Relative merits and demerits including the green aspects of extraction were evaluated. The current trends and future prospects were also addressed.     

Determining the lowest sulfur detection limit in diesel fuel by ultraviolet fluorescence

Abstract

This technical review article focuses on determining a robust and precise lower-level sulfur detection procedure. When measuring under 0.1?ppm and approaching zero values, the limits of the instrument are pushed to separate real signal response from noise. One of the performance parameters in method validation studies is to determine these near-zero value samples reliably when the instrument works near the noise signal level. The study examined the early stages of the method development process, regarding the determination of the validation parameters limit of blank, limit of detection (LOD), and limit of quantification (LOQ). The sulfur content in diesel fuel was determined with guidance from the standard ISO 20846:2011. The average sulfur readings of a diesel test sample and blank (99% iso-octane) were measured as 3.9 and 0.0196?ppm, respectively. For a 1.5% diluted diesel test sample the mean sulfur value was measured as 0.0613?ppm and this value was verified as the LOD. For a 3% diluted diesel test sample the mean sulfur value was measured as 0.1158?ppm and this result was verified as the LOQ. The LOD and LOQ were tested for conformity. The accuracy of these tested values was checked according to EUROCHEM guidelines.