Development of a solid-phase microextraction gas chromatography with microelectron-capture detection method for a multiresidue analysis of pesticides in bovine milk

A simple and rapid method based on solid-phase microextraction (SPME) technique followed by gas chromatography with microelectron-capture detection (GC-microECD) was developed for the simultaneous determination of more than 30 pesticides (pyrethroids and organochlorinated among others) in milk. To our knowledge, this is the first application of SPME for the determination of pyrethroid pesticides in milk. Negative matrix effects due to the complexity and lipophility of the studied matrix were reduced by diluting the sample with distilled water. A 2(5-1) fractional factorial design was performed to assess the influence of several factors (type of fiber coating, sampling mode, stirring, extraction temperature, and addition of sodium chloride) on the SPME procedure and to determine the optimal extraction conditions. After optimization of all the significant variables and interactions, the recommended procedure was established as follows: DSPME (using a polydimethylsiloxane (PDMS)/divinylbenzene (DVB) coating) of 1 mL of milk sample diluted with Milli-Q water (1:10 dilution ratio), at 100 degrees C, under stirring for 30 min. The proposed method showed good linearity and high sensitivity, with limits of detection (LOD) at the sub-ng mL(-1) level. Within a day and among days precisions were also evaluated (R.S.D.<15%). One of the most important attainments of this work was the use of external calibration with milk-matched standards to quantify the levels of the target analytes. The method was tested with liquid and powdered milk samples with different fat contents covering the whole commercial range. The efficiency of the extraction process was studied at several analyte concentration levels obtaining high recoveries (>80% in most cases) for different types of full-fat milks. The optimized procedure was validated with powdered milk certified reference material, which was quantified using external calibration and standard addition protocols. Finally, the DSPME-GC-microECD methodology was applied to the analysis of milk samples collected in farms of dairy cattle from NW Spain.     

Analysis of industrial contaminants in indoor air. Part 2. Emergent contaminants and pesticides

This article reviews recent literature on the analysis of several contaminants related to the industrial development in indoor air in the framework of the REACH project. In this second part, the attention is focused on emergent contaminants and biocides. Among these chemicals, phthalates, polybrominated and phosphate flame retardants, fragrances, pesticides, as well as other emerging pollutants, are increasing their environmental and health concern and are extensively found in indoor air. Some of them are suspected to behave as priority organic pollutants (POPs) and/or endocrine disrupting compounds (EDC), and can be found both in air and associated to the suspended particulate matter (PM) and settled dust. Main literature considered for this review is from the last ten years, reporting analytical developments and applications regarding the considered contaminants in the indoor environment. Sample collection and pretreatment, analyte extraction or desorption, clean-up procedures, determination techniques, and performance results are summarized and discussed.     

Development of a matrix solid-phase dispersion method for the simultaneous determination of pyrethroid and organochlorinated pesticides in cattle feed

A matrix solid-phase dispersion (MSPD) method was developed for the simultaneous extraction of 36 common pesticides and breakdown products (mostly pyrethroids and organochlorines) in cattle feed. Different parameters affecting the extraction efficiency (such as dispersing phase, clean-up adsorbent and elution volume) were investigated. The experimental procedure was optimized using a multivariate statistical approach and the final analyses were carried out by GC-muECD. Several protocols for extract purification were also studied. As far as we know, this is the first application of MSPD for the extraction of most of the target pesticides from animal feed. Using the optimized extraction conditions, the method was validated in terms of accuracy, and precision (within-a-day and among-days), using a certified reference material (CRM 115) as well as spiked cattle feedingstuffs at different concentration levels. A matrix effect study was also carried out using various real samples. The recoveries were satisfactory (>75% in most cases) and the quantification limits, at the sub-ngg(-1) or low-ngg(-1) level, complied with the regulated maximum residue levels (MRLs) in animal feed and in main crops used in the preparation of cattle feeding materials. Finally, the MSPD-GC-muECD methodology was applied to the analysis of real cattle feed samples collected in farms of dairy cattle from NW Spain.     

Determination of dimethyl fumarate and other potential allergens in desiccant and antimould sachets

A method for the determination of dimethyl fumarate (DMF), benzothiazole (BT) and tert-butylphenol (TBP) in desiccant and antimould agents employed for protecting consumer products from humidity and mould has been developed. The method is based on ultrasound-assisted extraction (UAE) followed by GC-MS analysis. Parameters that could affect the extraction of the compounds have been optimised using a multivariate approach. In the final conditions, the extraction is performed using only 0.5 or 1 mL ethyl acetate and applying ultrasound energy for 5 min. Simultaneous extractions could also be carried out in 5 min without losing efficiency. The method was validated showing good linearity (R ² >0.995). Both intra- and inter-day precisions were studied at several concentration levels, being satisfactory in all cases (RSD <10%). Recovery was evaluated in four real desiccant samples at different compound concentrations, ranging between 87% and 109%. Limits of detection and quantification were in the low nanogramme per gramme level, thus allowing the determination of DMF at concentrations well below the limit established by the recent EU Directive (0.1 μg/g). The proposed procedure was applied to the determination of the target compounds in several desiccant and antimould samples. Although most of them were simply labelled as “silica gel”, more than 70% of the tested samples contained high amounts of DMF, many of them at the high microgram per gramme level. Many samples also showed the presence of the other two potential allergens. These results demonstrate that the content of the “desiccant” sachets and tablets in consumer products does not usually belong with the label of the desiccant, and hence, the high risk of exposition to the powerful allergen DMF and other potentially harmful chemicals through consumer goods should be a matter of concern.     

Rapid and sensitive determination of pyrethroids indoors using active sampling followed by ultrasound-assisted solvent extraction and gas chromatography

A fast and simple method to analyze pyrethroids as well as other components of frequently used domestic insecticide preparations in indoor air is presented. The proposed method, based on sampling with an adsorbent followed by ultrasound-assisted solvent extraction, was developed with the aim to simplify the traditional extraction methodologies applied up to date to determine pesticides in air. The analytes were retained on a very small amount of adsorbent, which allowed using solely 1 mL of solvent for desorption. The quantification was performed by gas chromatography with microelectron-capture detection (GC-muECD) and gas chromatography coupled to mass spectrometry (GC-MS). The influence of main factors involved in the ultrasound-assisted solvent extraction step (type of adsorbent and type of solvent, solvent volume and extraction time) was studied using an experimental design approach to account for possible factor interactions. The sampling step was studied for two adsorbents (Tenax TA and Florisil), finding that 1 m(3) air could be sampled without losses of analytes. In this way, the analysis of pyrethroids in air by the proposed method could be carried out within a total time shorter than an hour, including sampling. Linearity was demonstrated in a wide concentration range. Efficiency of the total sampling-extraction process was studied at several concentration levels (2, 10, 100 and 1000 ng/m(3)), obtaining quantitative recoveries for all compounds, with good precision (RSD < 10%). Method detection limits were below 1 ng/m(3) in air when GC-muECD was employed, and about one order of magnitude higher for GC-MS. In addition, the proposed method was applied to real samples collected in contaminated closed rooms, in which some of the target compounds were determined.     

Application of solid-phase microextraction to the study of the photochemical behaviour of five priority pesticides: "on-fiber" and aqueous photodegradation

Solid-phase microextraction (SPME) is applied to study the photochemical degradation of five priority pesticides: atrazine, alachlor, aldrin, dieldrin, endrin. Analyses were carried out by gas chromatography-mass spectrometry. The possibility of studying the photochemical degradation of the target compounds in solid-phase microextraction fibers, "photo-SPME", is evaluated employing different SPME coatings. The target analytes were extracted from aqueous solutions using different commercial coatings and then, the fibers were exposed to UV light. Results indicated that on-fiber photodegradation takes place in a considerably major extent using PDMS coating for an irradiation time of 30min. On-fiber photodegradation kinetics of each analyte were determined by UV irradiation of the PDMS for different times. A large number of photoproducts were generated and they were tentatively identified by means of their mass spectra and with the aid of literature. In this way, main photodegradation mechanisms could be postulated. Aqueous photodegradation studies followed by SPME were performed and compared with photo-SPME. All the photoproducts detected in the aqueous experiments were previously found in the photo-SPME experiments. This study shows the potential of photo-SPME to evaluate the photo-transformation of organic pollutants.     

Study of the photoinduced degradation of polycyclic musk compounds by solid-phase microextraction and gas chromatography/mass spectrometry

Polycyclic musks are widely used synthetic fragrances that have been identified during the last few years in biota samples and environmental matrices. Nevertheless, there is a lack of information concerning the photodegradation behavior of these compounds. In this work, the photoinduced degradation of six polycyclic musk compounds (Cashmeran, Celestolide, Phantolide, Galaxolide, Traseolide and Tonalide) was studied using a solid-phase microextraction (SPME) fiber as support. Musk fragrances were extracted from aqueous solutions using SPME fibers that were subsequently exposed to ultraviolet (UV) irradiation for different times. To study the degradation kinetics and to tentatively identify the photoproducts generated, gas chromatography coupled to ion trap mass spectrometry was used. Aqueous photodegradation studies were also performed. The on-fiber photodegradation approach avoids the need for further extraction processes and makes the identification of photoproducts easier, due to their higher concentration on the fibers. All musk compounds were easily photodegraded, suggesting that UV irradiation could work as a decontamination tool for these musks.     

Application of multivariate calibration to the simultaneous routine determination of ethanol, glycerol, fructose, glucose and total residual sugars in botrytized-grape sweet wines by means of near-infrared reflectance spectroscopy

The simultaneous determination of ethanol, glycerol, fructose, glucose and residual sugars in botrytized-grape sweet white wines was performed by means of near-infrared reflectance using 19 interference filters and a partial least squares (PLS) model in latent variables as a multivariate calibration technique. The results were compared with those obtained using other multivariate calibration techniques, such as MLR, SWR and PCR, by means of a validation set of samples with known compositions. Ethanol, fructose and residual sugars were well predicted by all the multivariate techniques. Glycerol and glucose showed the highest prediction residuals. The technique may be of practical interest in the routine analysis of these types of wines with low cost in terms of samples, time and personnel. Received: 12 June 1995 / Revised: 5 February 1996 / Accepted: 7 February 1996     

Recent Advances in Sample Preparation for Cosmetics and Personal Care Products Analysis

The use of cosmetics and personal care products is increasing worldwide. Their high matrix complexity, together with the wide range of products currently marketed under different forms imply a challenge for their analysis, most of them requiring a sample pre-treatment step before analysis. Classical sample preparation methodologies involve large amounts of organic solvents as well as multiple steps resulting in large time consumption. Therefore, in recent years, the trends have been moved towards the development of simple, sustainable, and environmentally friendly methodologies in two ways: (i) the miniaturization of conventional procedures allowing a reduction in the consumption of solvents and reagents; and (ii) the development and application of sorbent- and liquid-based microextraction technologies to obtain a high analyte enrichment, avoiding or significantly reducing the use of organic solvents. This review provides an overview of analytical methodology during the last ten years, placing special emphasis on sample preparation to analyse cosmetics and personal care products. The use of liquid–liquid and solid–liquid extraction (LLE, SLE), ultrasound-assisted extraction (UAE), solid-phase extraction (SPE), pressurized liquid extraction (PLE), matrix solid-phase extraction (MSPD), and liquid- and sorbent-based microextraction techniques will be reviewed. The most recent advances and future trends including the development of new materials and green solvents will be also addressed.     

Optimization of a sensitive method for the determination of nitro musk fragrances in waters by solid-phase microextraction and gas chromatography with micro electron capture detection using factorial experimental design

A solid-phase microextraction method (SPME) followed by gas chromatography with micro electron capture detection for determining trace levels of nitro musk fragrances in residual waters was optimized. Four nitro musks, musk xylene, musk moskene, musk tibetene and musk ketone, were selected for the optimization of the method. Factors affecting the extraction process were studied using a multivariate approach. Two extraction modes (direct SPME and headspace SPME) were tried at different extraction temperatures using two fiber coatings [Carboxen–polydimethylsiloxane (CAR/PDMS) and polydimethylsiloxane–divinylbenzene (PDMS/DVB)] selected among five commercial tested fibers. Sample agitation and the salting-out effect were also factors studied. The main effects and interactions between the factors were studied for all the target compounds. An extraction temperature of 100 °C and sampling the headspace over the sample, using either CAR/PDMS or PDMS/DVB as fiber coatings, were found to be the experimental conditions that led to a more effective extraction. High sensitivity, with detection limits in the low nanogram per liter range, and good linearity and repeatability were achieved for all nitro musks. Since the method proposed performed well for real samples, it was applied to different water samples, including wastewater and sewage, in which some of the target compounds (musk xylene and musk ketone) were detected and quantified. Figure Stardardized Pareto charts for the main effects and interactions