F.J. Camino-Sánchez

Stir bar sorptive extraction: Recent applications, limitations and future trends

Stir bar sorptive extraction (SBSE) has generated growing interest due to its high effectiveness for the extraction of non-polar and medium-polarity compounds from liquid samples or liquid extracts. In particular, in recent years, a large amount of new analytical applications of SBSE has been proposed for the extraction of natural compounds, pollutants and other organic compounds in foods, biological samples, environmental matrices and pharmaceutical products. The present review summarizes and discusses the theory behind SBSE and the most recent developments concerning its effectiveness. In addition, the main results of recent analytical approaches and their applications, published in the last three years, are described. The advantages, limitations and disadvantages of SBSE are described and an overview of future trends and novel extraction sorbents and supports is given.

Validation of a GC–MS/MS method for simultaneous determination of 86 persistent organic pollutants in marine sediments by pressurized liquid extraction followed by stir bar sorptive extraction

A multiresidue method for the analysis of 86 persistent pollutants in marine sediments at ultra-trace level has been developed and validated using pressurized liquid extraction (PLE) and stir-bar sorptive extraction (SBSE) coupled with thermal desorption and gas chromatography-triple quadrupole mass spectrometry (TD-GC-MS/MS QqQ). The compounds analyzed belong to various families such as polychlorinated biphenyls, polycyclic aromatic hydrocarbons, polybrominated diphenylethers, organophosphorus and organochlorine pesticides and other pesticides such as urons, and triazines. The analytes have very different polarities and log K(ow) values, which is an important parameter in the optimization of a SBSE method. Due to PLE high efficiency and throughput rates, along with the proven ability for multiresidue analysis and excellent sensitivity of SBSE, we present an efficient method. The limits of quantification obtained ranged from 0.014 to 1.0 ng g(-1), with detection limits below pg g(-1) levels. In order to validate the proposed methodology, quality parameters such as recovery, linearity and reproducibility were studied. Recoveries ranged from 63% to 119%, reproducibility (in terms of Relative Standard Deviation for ten determinations) was lower than 35% in all cases, and determination coefficients higher than 0.990 for all analytes. The main factors that affect PLE, SBSE and GC-MS/MS procedures were optimized. The method was applied to the analysis of nine marine sediments obtained from the nine main submarine wastewater discharge points (emissaries) presents along the coast of Tenerife Island (Canary Islands, Spain).

Analysis of quinolone antibiotic derivatives in sewage sludge samples by liquid chromatography-tandem mass spectrometry: Comparison of the efficiency of three extraction techniques

This work presents a comparison of three extraction techniques -ultrasound-assisted extraction (USE), microwave-assisted extraction (MAE) and pressurized liquid extraction (PLE) - and evaluates their efficiency in the determination of quinolone antibiotics in sewage sludge samples. Extraction parameters for each technique were optimized using design of experiments, and the compounds were detected and quantified using liquid chromatography-tandem mass spectrometry (LC-MS/MS), operating in positive electrospray ionization (ESI) mode. The use of two selected reaction monitoring transitions for each compound allowed simultaneous quantification and identification in one run. Analytes were separated in less than 10 min. Marbofloxacin and cincophen were used as surrogates for amphoteric and acid quinolones, respectively. The limits of detection (LODs) were between 2 and 5 ng g(-1), and the limits of quantification (LOQs) were between 4 and 18 ng g(-1) for the various analytes. The inter- and intra-day variability was <7%. Due to the absence of certified reference materials (CRMs), the method was validated using matrix-matched calibration and a recovery assay with spiked samples. Recovery rates were between 97.9% and 104.8%. Statistical comparison demonstrated no significant differences between the three extraction techniques. The methods were successfully applied for the determination of quinolones in sewage sludge samples collected from different wastewater treatments plants (WWTPs) located in the province of Granada (Spain). The analytical methods developed here may be useful for the development of more in-depth studies on the occurrence and fate of these commonly used pharmaceuticals in WWTPs and in the environment.

Gas chromatography and ultra high performance liquid chromatography tandem mass spectrometry methods for the determination of selected endocrine disrupting chemicals in human breast milk after stir-bar sorptive extraction

In the present work, two specific, accurate and sensitive methods for the determination of endocrine disrupting chemicals (EDCs) in human breast milk are developed and validated. Bisphenol A and its main chlorinated derivatives, five benzophenone-UV filters and four parabens were selected as target analytes. The method involves a stir-bar sorptive extraction (SBSE) procedure followed by a solvent desorption prior to GC-MS/MS or UHPLC-MS/MS analysis. A derivatization step is also necessary when GC analysis is performed. The GC column used was a capillary HP-5MS with a run time of 26min. For UHPLC analysis, the stationary phase was a non-polar Acquity UPLC(®) BEH C18 column and the run time was 10min. In both cases, the analytes were detected and quantified using a triple quadrupole mass spectrometer (QqQ). Quality parameters such as linearity, accuracy (trueness and precision), sensitivity and selectivity were examined and yielded good results. The limits of quantification (LOQs) ranged from 0.3 to 5.0ngmL(-1) for GC and from 0.2 to 1.0ngmL(-1) for LC. The relative standard deviation (RSD) was lower than 15% and the recoveries ranged from 92 to 114% in all cases, being slightly unfavorable the results obtained with LC. The methods were satisfactorily applied for the determination of target compounds in human milk samples from 10 randomly selected women.

UNE-EN ISO/IEC 17025:2005-accredited method for the determination of pesticide residues in fruit and vegetable samples by LC-MS/MS

A rapid, simple and sensitive multi-residue method was developed and validated for the simultaneous quantification and confirmation of 69 pesticides in fruit and vegetables using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The samples were extracted following the quick, easy, cheap, effective, rugged and safe method known as QuEChERS. Mass spectrometric conditions were individually optimised for each analyte in order to achieve maximum sensitivity in multiple reaction monitoring (MRM) mode. Using the developed chromatographic conditions, 69 pesticides can be separated in less than 17 min. Two selected reaction monitoring (SRM) assays were used for each pesticide to obtain simultaneous quantification and identification in one run. With this method in SRM mode, more than 150 pesticides can be analysed and quantified, but their confirmation is not possible in all cases according to the European regulations on pesticide residues. Nine common representative matrices (zucchini, melon, cucumber, watermelon, tomato, garlic, eggplant, lettuce and pepper) were selected to investigate the effect of different matrices on recovery and precision. Mean recoveries ranged from 70% to 120%, with relative standard deviations (RSDs) lower than 20% for all the pesticides. The proposed method was applied to the analysis of more than 2000 vegetable samples from the extensive greenhouse cultivation in the province of Almería, Spain, during one year. The methodology combines the advantages of both QuEChERS and LC-MS/MS producing a very rapid, sensitive, accurate and reliable procedure that can be applied in routine analytical laboratories. The method was validated and accredited according to UNE-EN-ISO/IEC 17025:2005 international standard (accreditation number 278/LE1027).

Validation of a method for the analysis of 77 priority persistent organic pollutants in river water by stir bar sorptive extraction in compliance with the European Water Framework Directive.

A multi-residue method for the analysis of semi-volatile organic pollutants in inland groundwater (river water) at ultra-trace levels in compliance with the European Water Framework Directive (WFD) has been developed and validated by stir bar sorptive extraction (SBSE) and thermal desorption coupled with gas chromatography-triple quadrupole mass spectrometry (SBSE-TD-GC-MS/MS(QqQ)). The method includes various families of compounds included in the WFD and other compounds listed as persistent organic pollutants that are banned in the Stockholm Convention of Persistent Organic Pollutants, such as polychlorinated biphenyls, polycyclic aromatics hydrocarbons, and other pesticides not included in the WFD. The method also can be applied for compliance with regional environmental laws. Extraction conditions were optimised in order to analyse simultaneously analytes with very different polarities and octanol-water partition coefficients, which is an important parameter in the optimisation of a SBSE method. The quantification limits (LOQs) obtained ranged from 0.14 to 10 ng L(-1), lower that others presented in previous publications, and complies with the requirement for analytical methods to be used in the analysis of the compounds included in the WFD. Several quality parameters as linearity, trueness and precision were studied with good results, and also uncertainty was estimated. The WFD requires that the level of uncertainty must be lower than 50%, and this requirement was met for all compounds. Precision (in terms of RSD) was lower than 30%, recoveries ranged between 74 and 111%, and determination coefficients were higher than 0.990 for all analytes. Different factors that affect the SBSE procedure were optimised. GC-MS/MS parameters have also been revised. The accuracy of the method was tested participating in a proficiency testing scheme for each group of analytes.

Validation of a method for the determination of tributyltin in seawater by stir bar sorptive extraction-liquid chromatography tandem mass spectrometry.

The main objective of this work is to develop an accurate, sensitive, simple and cost-effective method for the determination of tributyltin species (as cationic form) in seawater at ultra-trace levels. The method is based on the use of stir bar sorptive extraction (SBSE) followed by solvent desorption and liquid chromatography tandem mass spectrometry (SD-LC-MS/MS (QqQ)) analysis, operating in positive electrospray ionisation (ESI) and in the selected reaction monitoring (SRM) mode. Extraction and LC-MS/MS parameters were accurately optimised to achieve the highest recoveries and to enhance the analytical characteristics of the method. The different parameters that affect the extraction procedure, the chromatographic and spectrometric conditions, and the surrogate selection were evaluated. In contrast with previously proposed methods, the proposed method involves a simplified sample treatment. Quality parameters such as linearity, accuracy in terms of trueness and precision, uncertainty and specificity were examined with good results. The evaluation of two surrogates (tri-n-propyltin chloride and tripentyltin chloride) was also carried out. The limit of detection (LOD) and limit of quantification (LOQ) obtained were 0.8 and 2.5 ngL(-1), respectively. Precision, expressed as relative standard deviation (%RSD), was lower than 16%, and the determination coefficient (R(2)) was higher than 0.990 with a residual deviation for each calibration point lower than ±25%. Mean recoveries were between 92% and 102%. The accuracy of the method was also studied by participating in an external proficiency testing scheme. After validation, the method was applied to the analysis of all tributyltin species found in natural seawater samples. The method meets the requirements of the United States Environmental Protection Agency (US-EPA).

New method for the determination of parabens and bisphenol A in human milk samples using ultrasound-assisted extraction and clean-up with dispersive sorbents prior to UHPLC-MS/MS analysis.

A sensitive and accurate analytical method for the determination of methyl-, ethyl-, propyl- and butylparaben and bisphenol A in human milk samples has been developed and validated. The combination of ultrasound-assisted extraction (UAE) and a simplified and rapid clean-up technique that uses sorbent materials has been successfully applied for the preparation of samples prior to ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) analysis. The analytes were extracted from freeze-dried human milk samples using acetonitrile and ultrasonic radiation (three 15-min cycles at 70% amplitude), and further cleaned-up with C18 sorbents. The most influential parameters affecting the UAE method and the clean-up steps were optimized using design of experiments. Negative electrospray ionization (ESI) in the selected reaction monitoring (SRM) mode was used for MS detection. The use of two reactions for each compound allowed simultaneous quantification and identification in one run. The analytes were separated in less than 10min. Deuterium-labeled ethylparaben-d5 (EPB-d5) and deuterium-labeled bisphenol A-d16 (BPA-d16) were used as surrogates. The limits of quantification ranged from 0.4 to 0.7ngmL(-1), while inter- and intra-day variability was under 11.1% in all cases. In the absence of certified reference materials, recovery assays with spiked samples using matrix-matched calibration were used to validate the method. Recovery rates ranged from 93.8% to 112.2%. The proposed method was satisfactorily applied for the determination of four selected parabens and bisphenol A in human milk samples obtained from nursing mothers living in the province of Granada (Spain).

Evaluation of the presence of major anionic surfactants in marine sediments.

The contamination of aquatic environments has become the focus of increasing regulation and public concern due to their potential and unknown negative effects on the ecosystems. The present work develops a monitoring and statistical study, based on the analysis of variance test (ANOVA) and the multivariable analysis, both for insoluble soap and LAS in order to compare the behavior of different anionic surfactants in this environmental compartment. First, a novel and successfully validated methodology to analyze insoluble soap in these samples is developed. The matrix effect and the comparison of different extraction techniques were also performed. The optimized analytical methodologies were applied to 48 representative samples collected from the Almeria Coast (Spain) and then a statistical analysis to correlate anionic surfactant concentration and several variables associated with marine sediment samples was also developed. The results obtained showed relevant conclusions related to the environmental behavior of anionic surfactants in marine sediments.

Screening and Quantification of 65 Organic Pollutants in Drinking Water by Stir Bar Sorptive Extraction-Gas Chromatography-Triple Quadrupole Mass Spectrometry

A muti-class method for the analysis of semi-volatile organic pollutants in drinking water in compliance with the European legislation regarding the quality of the waters destined to human consumption and bottled water has been validated. The proposed method analyses and quantifies simultaneously all semi-volatile organic compounds, as all polycyclic aromatic hydrocarbons and organochlorinated pesticides included in the European Directive 98/83/EC, diverse organic contaminants listed by the US-EPA, polychlorinated biphenyls and diverse organophosphorous and organonitrogenated pesticides. The method has been validated according to ISO/IEC 17025:2005 requirements, following IUPAC and ISO guidelines for the evaluation of the trueness, precision, linearity, specificity, range and uncertainty. The accuracy of the method was tested participating in a proficiency testing scheme for each group of analytes. The method meets all quality requirements established by the directive; the mean recovery ranged between 85xa0% and 115xa0%, and the precision, expressed as relative standard deviation, was between 3xa0% and 23xa0%. Due to the high sensitivity obtained with the combination of SBSE and triple quadrupole mass spectrometry, a screening method has been proposed that allows the analysis of up to five samples simultaneously, which in combination with the simultaneous analysis of diverse families of analytes, enhances the productivity of the methodology and reduces the costs.