In this study, a stainless steel wire/ionic liquid-solid phase microextraction technique was developed for the direct extraction of APs from water samples. Some parameters were optimised, such as selection of the substrate and ILs, extraction time, extraction temperature, stirring rate and sample pH, etc. The experimental data demonstrated that the etched stainless steel wire was a suitable substrate for IL-coated SPME. The coating was prepared by directly depositing the ILs onto the surface of the etched stainless steel wire, which exhibited a porous structure and a high surface area. The [C8MIM][PF6] IL exhibited maximum efficiency with an extraction time of 30 min, and the aqueous sample was maintained at 40 1C and adjusted to pH 2 under stirring conditions. The enrichment factor of the IL coating for the four APs ranged from 1382 to 4779, the detection limits (LOD, S/N¼3) of the four APs ranged from 0.01 to 0.04 ng mL1 and the RSD values for purified water spiked with APs ranged from 4.0 to 11.8% (n¼3). The calibration graphs were linear in the concentration range from 0.5 to 200 ng mL1 (R240.9569). The optimised method was successfully applied for the analysis of real water samples, and the method was suitable for the extraction of APs from water samples.

Persistent organic pollutants (POPs) encompass many organic contaminant classes that show high persistence, susceptibility for long-range transport (LRT), and potential for biomagnification in food chains (1,2). Air is an efficient medium for the global dissemination of persistent organic pollutants (POPs). Epidemiological studies investigating the health risks related to air pollution suggest that ambient air pollution (including polycyclic aromatic hydrocarbons, PAHs) may be responsible for increased rates of diseases like lung cancer (3, 4). Air pollution is an important environmental problem that can result from both human and natural actions. To reduce pollution levels and minimize harmful effects on human health, it is necessary to improve air monitoring and provide useful information to the communities. Recently, biomonitoring methods using passive plant samplers may offer a practicable low cost alternative, especially in terms of high spatial resolution and time-averaged data series (5, 6). In this study, seasonal distribution characteristics of PAHs in Salix matsudana leaves covering its annual life cycle were carried out in order to evaluate plant leaf response sensitivity on air pollution. Salix matsudana leaves were collected throughout different development phases of plant leaf inclusive of bud break to fallen leaves, covering from spring (May) to autumn (November). Simultaneously, particle and gas samples were collected using a high volume air sampler. Seven different PAHs were determined from three types of samples. The leaf area and lipid content changed from season to season: both parameters increased rapidly during the spring season, maintained a stable state in summer season, while lipid content dramatically decreased in autumn season. Except spring season, total PAHs showed similar seasonal trends between plant leaves and air samples, with correlation coefficients equal to 0.74 and 0.56 in summer and autumn season, respectively. In this work, it has been demonstrated that climate changes, such as rainfall and air mass movement, influence the daily concentrations of PAHs in leaf. Furthermore, PAH composition profile in leaves and air phase have been correlated by principal component analysis.

tIn this work, two different extraction procedures for the analysis of different polycyclic aromatic hydro-carbons (PAHs) in water by microextraction by packed sorbent (MEPS) have been compared in terms ofsensitivity, reliability and time of analysis. The first method, called “draw-eject”, consists of a sequenceof cycles of aspirations and injections in the same vial; the second one, called “extract-discard”, consistsof a similar cycle sequence, but the aspired sample in this case is discarded into waste. The relevant par-tition equilibriums and extraction rates have been calculated by multivariate regression from the dataobtained after MEPS gas chromatography–mass spectrometry (MEPS-GC–MS) analysis of 16 PAHs fromwater samples. Partitioning parameters for a priori prediction of solute sorption equilibrium, recover-ies and preconcentration effects in aqueous and solvent systems have been calculated and comparedfor the two extraction procedures. Finally, real samples from sea, agricultural irrigation wells, streamsand tap water were analyzed. Detection (S/N ≥ 3) and quantification (S/N ≥ 10) limits were calculated forthe extraction processes. Under the experimental conditions used for the “draw-eject” procedure, thesevalues were in the range 0.5–2 ng L−1and 1.6–6.2 ng L−1, while for the “extract-discard” procedure theyranged from 0.2 to 0.8 ng L−1and from 0.8 to 2.0 ng L−1, respectively.

The practice of adding adulterating substances (water, starch, sodium citrate, urea, sucrose, melamine, etc) in milk products in order to raise profits is worldwide employed. In addition, higher priced milk, coming from minor dairy species, such as goat and buffalo showing high nutritional and economical value, is often illegally integrated with the lower priced cow milk. The presence of species-specific proteins, different from those declared in label, may be a serious problem for people with allergies. The development of proper analytical methods is therefore essential to protect consumer benefits and product authenticity, as well as to detect economic frauds. Several analytical techniques, including capillary electrophoresis1, polymerase chain reaction2,

Phthalate esters (PAEs) are commonly used as nonreactive plasticisers in vinyl plastics to increase the flexibility of plastic polymers. Numerous studies have indicated that the PAEs as a class of endocrine-disrupting chemicals. In addition, the studies have also shown that a major source of human exposure to phthalates is the diet. To date, the largest problem in PAEs analysis is the high blank value because PAEs are widely used in various applications and products. To overcome this shortcoming, gas purge microsyringe extraction (GP-MSE) was applied, which established a new and low-blank-value analytical method for PAE analysis to analyse PAEs in foodstuffs. In this study, GP-MSE was used as a clean-up method, and the overall recoveries ranged from 85.7 to 102.6%, and the RSD was less than 10%. More importantly, this method can overcome the problem of the high blank value in PAE analysis. This method was applied for measuring PAEs in 78 foodstuffs. The results showed that a wide variety of PAE concentrations were found in the different groups, and the content of PAEs (varies from 658 to 1610 ng g−1 fresh weight) is greatest in seafood. The concentrations were in the following order: DEHP > DBP > DEP ≈ DMP > BBP ≈ DNOP. Finally, the daily intake of PAEs was estimated for adults based on the levels of PAEs in foodstuffs. The total EDIdiet values of 3.2 and 12.9 μg kg−1 bw d−1 were calculated for DEHP based on the mean and highest concentrations in foodstuffs, respectively.

Phytohormones play a vital role in plant growth and metabolic processes1. As a minor component of the metabolome, phytohormones are of particular significance due to their role in the regulation of germination, growth, reproduction, and the protective responses of plants against stress. In fact, they control the balanced response of plants to adverse environmental conditions or biological threats. Thus, the simultaneous quantitative profiling of different classes of phytohormones provides a useful basis for defining additive, synergistic or antagonistic hormonal activities in biofertilizers or natural compounds. Phytohormones are typically present at trace levels in biological matrices, and the coexistence of a wide variety of interferents make their analysis rather challenging2. In this work, an integrated sample pre-treatment and derivatization method based on a new coated carbon fiber microextraction that allows a rapid extraction, separation, and highly sensitive phytohormone detection has been realized and characterized. Carbon fibers, chosen as substrate for their excellent high thermal and chemical stabilities, high porosity, and low cost, were chemically modified to obtain new surface characteristics in terms of polarity and adsorbing capacities. Three phytohormones (jasmonic acid, indole-3-acetic acid and abscisic acid) were simultaneously extracted, in-situ derivatized with N,O-bis(trimethylsilyl)trifluroacetamide and directly subjected to analysis by gas chromatography‒mass spectrometry. The developed method allowed in few step and short time low detection limits (0.62 – 3.72 ng mL‒1), good linearity (in the range 3.0 – 5000 ng mL‒1) and recoveries (81.6 to 105.8%). Furthermore, enrichment response factors (calculated as the ratio of peak areas obtained by SPME thermal desorption and direct injection) up to 3200, high derivatization rates (≥ 90%) and good reproducibility (RSD ≤ 20% at 50 ng mL-1) were obtained. The developed method was applied for the evaluation of phytohormone concentration in blended tomato samples.

In this work a new analytical method for a rapid and simultaneous determination of 28 organophosphorus pesticides (OPPs) residues in edible fungus using gas purge microsyringe extraction (GP-MSE), coupled with on-line gas chromatography–mass spectrometry (GP-MSE–GC–MS) has been developed and optimized. GP-MSE, a novel gas-flow liquid-phase microextraction technique, has been then fruitfully used as innovative and one-step extraction procedure, allowing a direct injection into the gas chromatograph coupled with mass spectrometry detector (GC–MS) system without any further cleaning step. Once optimized, the GP-MSE–GC–MS analysis procedure showed reproducibility values, resolutions, linear responses, detection and quantification limits that allowed to consider this method suitable for the analysis of the 28 OPPs in real samples. Furthermore, OPP recoveries and the relative standard deviations (RSDs) ranged from 85.26% to 100.21%, and from 1.6% to 6.9%, respectively. This procedure was then used for the analysis of real samples and the obtained results were compared with those of ultrasonic extraction-solid phase extraction. Among the 28 OPPs, 14 of them were found in Lentinus edodes and Enoki mushrooms fungus samples, with a total concentrations of 112.7 and 210.7 μg kg−1, respectively. This work demonstrated then that GP-MSE–GC–MS provided a highly efficient, solvent-saving, accurate and sensitive quantitative analysis method for a rapid determination of OPPs in edible fungus.

Over the years, two-dimensional Liquid Chromatography (2D-LC) has played a key role in the field of proteomics for the analysis and isolation of proteins from complex matrices, before their characterization by Mass Spectrometry1,2. In 2D-LC method development, a large number of experimental variables have to be extensively studied to take full advantage of the claimed features of the chromatographic separations3. In the last decade, significant improvements in LC column technology and instrumentation have been made and the introduction of superficially porous particles opened new possibilities in terms of speed and resolution. Here an automated method combining size exclusion with reverse phase chromatography and UV detection is proposed for protein separations in food samples. For the first dimension separation, a size-exclusion column, packed with 3 μm ultra-pure silica particles densely bonded with a proprietary hydrophilic surface chemistry, was used, ensuring high efficiency and resolution. A reversed phase widepore column was used for the second dimension separation, based on core-shell particle technology that provides striking increases in peak capacity and resolution at lower backpressures. Different collection trap systems were placed on a 10-port switching valve and tested to focus the proteins coming from the first dimension column, before their selective elution in the second dimension column. A protein standard mixture of bovine serum albumin, -lactoglobulin and glucose oxidase was used to optimize the gradient chromatographic separation conditions, after evaluating their retention behavior in each single column. Finally, the optimized 2D-LC method was applied to the protein analysis in eggs, infant milk powder and soy flour samples.

Sample preparation is an essential step in analysis, greatly influencing the reliability and accuracy of resulted the time and cost of analysis. It is widely accepted that this analytical step is the most labor-intensive and error-prone part of the analytical process. The recent advances in this field have been focused on the miniaturization and integration of sample preparation online with analytical instrumentation, in order to reduce laboratory workload and increase analytical performance. Solid-Phase Microextraction (SPME) is a very simple and efficient, solventless sample preparation method, invented by Pawliszyn in 1989) . SPME has been widely used in different fields of analytical chemistry since its first applications to environmental and food analysis and is ideally suited for coupling with mass spectrometry (MS). Micro extraction by packed sorbent (MEPS) has emerged in the last few years as a powerful sample preparation approach suitable to be easily automated with liquid and gas chromatographic systems applied in a variety of analytical areas (pharmaceutical, clinical, toxicological, environmental and food research). Both technique allow to integrate in a one-step procedure all steps of the conventional liquid– liquid extraction (LLE) such as extraction, concentration, (derivatization) and transfer to the chromatograph, considerably simplifying the sample preparation procedure. In this presentation, a critical comparison between the two procedures will be carried out, considering also the recent innovation in these fields.