Development of a greener and sustainable method to determine acrylamide in corn products by LC-MS/MS: Evaluation of levels in corn-based products.

Acrylamide (AA) is produced through the reaction between sugars and amino acids present in starchy foods cooked at high temperature. It is classified as probably carcinogenic to humans. In 2019, the European Commission reported a list of foods for monitoring the presence of AA, which includes cereal snacks. This study presents the development and validation of an analytical approach for detecting AA in popcorn and corn-based snacks. It includes solid-liquid extraction and clean-up with dispersive solid phase extraction followed by analysis through liquid chromatography coupled with tandem mass spectrometry. The proposed method was characterized in terms of recoveries (84-105%), and precision (< 16.1%). Limits of quantification were 17 and 60 µg kg-1 for corn and popcorn, respectively. Sustainability of the methodology was evaluated using AGREEprep and BAGI, providing values of 0.43 and 65.0, respectively. Twenty-four corn-based products were analyzed, with AA levels from 219 to 418 µg kg-1.

Analysis of drugs including illicit and new psychoactive substances in oral fluids by gas chromatography-drift tube ion mobility spectrometry.

In this study, a gas chromatograph (GC) has been coupled to a drift tube ion mobility spectrometer (IMS) in order to develop an analytical procedure for the determination of psychoactive substances in oral fluids. Working parameters, including the GC-IMS interface ones, were adjusted in order to obtain sensitive and robust signals. A volume of 500 µL of oral fluid was extracted with 250 µL chloroform and, after centrifugation, were injected into the GC-IMS system. Amphetamine, methylone, α-PVP, ketamine, lidocaine, MPHP, cocaine, THJ-2201, and 5F-ADB were employed as model compounds, providing limits of detection from 6 to 15 µg L-1 and recoveries from 70 to 115% for field oral fluids spiked with target analytes at 250, 500, and 600 µg L-1. Moreover, two oral fluid certified reference materials were analysed by the proposed GC-IMS based methodology with obtained relative percentage errors lower than 8.4%, being the proposed GC-IMS procedure a reliable, selective, and sensitive technique for the determination of psychoactive substances in oral fluids.

Dual mixed-mode poly (vinylpyridine-co-methacrylic acid-co-ethylene glycol dimethacrylate)-based sorbent for acidic and basic drug extraction from oral fluid samples.

In this study, a dual mixed-mode polymer sorbent was prepared via one-step thermally initiated polymerization of 4-vinylpyridine (VP), methacrylic acid (MAA) and ethylene glycol dimethacrylate (EGDMA) for the solid-phase extraction (SPE) of basic and acidic drugs. The use of VP and MAA as ionizable functional monomers allowed the tailoring of ion-exchange and hydrophobic features of the polymer. The obtained polymer was characterized by Fourier-transform infrared spectroscopy and scanning electron microscopy. Next, the retention behavior of dual mixed-mode polymer towards basic and acidic drugs was investigated. Moreover, the practical capability of this novel material was tested for the extraction of relevant drugs such as cocaine, 3-methylmethcathinone, and diazepam in oral fluid samples. Recovery values (at different spiked levels in blank oral fluid samples), ranging from 69 to 99%, and limits of detection (LODs), between 0.10 and 0.25 µg L-1, were obtained.

Skin Permeation of Hazardous Compounds of Tobacco Smoke in Presence of Antipollution Cosmetics.

Negative health effects of active and passive smokers have been widely described, but the effect of tobacco smoke on the skin has been less explored. In this study, an analytical methodology has been developed to evaluate the dermal permeation of hazardous compounds present in tobacco smoke, using an exposition chamber to simulate finite and infinite smoking conditions, in vitro vertical Franz diffusion cells, and Strat-M® membranes as human skin simulants. Moreover, the antipollution effect of three cosmetics has been evaluated, showing a significant efficacy to reduce dermal permeation of hazardous tobacco-smoke compounds such as of nicotine and aromatic hydrocarbons.

Direct and fast determination of polychlorinated biphenyls in contaminated soils and sediments by thermal desorption-gas chromatography-tandem mass spectrometry.

A direct procedure based on thermal desorption-gas chromatography-tandem mass spectrometry (TD-GC-MS-MS) was developed for the fast extraction of seven polychlorinated biphenyls (PCBs) from sediments and soils. PCBs were directly extracted, from 20 to 75 mg of sample, without any chemical pre-treatment or use of organic solvents, after the addition of 10 µL internal standard (PCB 195) in acetone. Sample treatment was totally automated. PCBs were extracted at 250 °C for 20 min, using a helium flow and the PCBs were trapped in a cryogenic Tenax trap at -10 °C. After that, analytes were directly desorbed at 270 °C and introduced to the GC-MS-MS system. Recoveries were established using spiked soil and sediment from 2.5 to 50 ng g-1, obtaining values from 74 to 127%. The limits of quantification were from 1.0 to 1.7 ng g-1 for soil and from 0.3 to 0.4 ng g-1 for sediments, respectively. Precision, assessed as the relative standard deviation (RSD), was lower than 8 and 11% for sediment and soil analysis, respectively, except for PCB-28 in soil samples which provided a RSD of 18%. Certified reference material and field samples were analysed by the proposed TD-GC-MS-MS method. Results were compared by a paired samples Student's t-test with those obtained by a reference extraction procedure based on pressurized solvent extraction, followed by stir bar sorptive extraction, being statistically comparable (α = 0.05). A comprehensive greenmetric evaluation of the proposed method was carried out, having the TD extraction a negligible environmental impact as compared to conventional extraction procedures.

Development of immunosorbents for the analysis of forchlorfenuron in fruit juices by ion mobility spectrometry.

The advantages of using smart materials as immunosorbents in the analysis of complex matrices by ion mobility spectrometry (IMS) have been highlighted in this study. A novel analytical method has been proposed for the sensitive, selective, and fast determination of residues of the plant growth regulator forchlorfenuron in fruit juices. Three different monoclonal antibodies (s3#22, p2#21, and p6#41) were employed for the production of immunosorbents, based on Sepharose gel beads, which were characterized in terms of loading capacity, solvent resistance, and repeatability for its use in solid-phase extraction (SPE). Immunosorbents that were prepared with antibody p6#44 provided the best performance, with a loading capacity of 0.97 µg, a 10% (v/v) 2-propanol tolerance, and a reusability of at least eight uses. The SPE procedure involved the use of a column with 0.15 g Sepharose beads, containing 0.5 mg antibody, which was loaded to 20 mL of the sample, washed with 2 mL of water plus 2 mL of 10% (v/v) 2-propanol, and eluted with 2 mL of 2-propanol. The cleaned extract was directly analyzed by IMS, giving a limit of detection of 2 µg L-1 with a relative standard deviation of 7.6%. Trueness was assessed by the analysis of blank grape and kiwifruit juice samples spiked with forchlorfenuron concentrations from 10 to 400 µg L-1, with recoveries from 80 to 115%. The analytical performance of the proposed immunosorbent was compared with conventional extraction and cleanup methods, such as QuEChERS and C18-based SPE, giving the cleanest extracts for accurate determinations of forchlorfenuron by IMS. Graphical abstract ᅟ.

Comprehensive analysis of airborne pesticides using hard cap espresso extraction-liquid chromatography-high-resolution mass spectrometry.

A hard cap espresso extraction procedure has been developed to recover airborne pesticides in particulate matter trapped in filters. This extraction step was made for 20s at 72°C and 19bar using 50mL of 20% (v/v) acetonitrile in water. After that, based on NaCl salting out, extracts were concentrated 22 times and analysed by ultra-high performance liquid chromatography - high resolution mass spectrometry. 35 pesticides were evaluated, as a proof of concept, being validated the whole methodology and compared the extraction method with that based on microwave assisted extraction for 20min. In short, the method avoids cross-contamination of samples, it is relatively fast and consumes only 10mL acetonitrile and 8g NaCl per sample; thus, offering a low cost and green alternatively to available methods based on pressurized solvent extraction or microwave-assisted treatment.

Hard cap espresso extraction-stir bar preconcentration of polychlorinated biphenyls in soil and sediments.

A Nespresso© hard cap espresso machine has been employed for the quantitative extraction of polychlorinated biphenyls (PCBs) from sediments and soils. Sample extraction was performed from five grams of sample in less than 40 s, with 200 mL ethanol 40% (v/v) in water and PCBs were concentrated using stir bar sorptive extraction (SBSE) and determined by thermal desorption-gas chromatography-tandem mass spectrometry (TD-GC-MS-MS). Eleven PCB congeners (28, 52, 77, 80, 81, 101, 118, 138, 153,169, and 180) were determined in soils and sediments with limits of quantification in the 0.03-0.08 ng g-1 range. Extraction efficiency was established by the analysis of soil samples spiked with the studied PCBs at concentrations from 0.1 to 10.0 ng g-1, obtaining quantitative recoveries from 81 to 120% and an adequate precision with relative standard deviations lower than 20%. Certified reference materials and natural samples were analyzed by the proposed hard cap espresso extraction and results were compared with those provided by a reference procedure based on pressurized solvent extraction, obtaining statistically comparable results. Therefore, the use of a hard cap espresso machine in tandem with SBSE and TD-GC-MS-MS allowed a simple, sensitive and quantitative determination of PCBs.

Use of semipermeable membrane devices for monitoring pesticides in indoor air.

In this work, 40 pesticides from different categories were analyzed in the air of 20 indoor places that have an intensive use of pesticides. Passive sampling was carried out by using semipermeable membrane devices (SPMDs) deployed for 7 days. SPMDs were analyzed using microwave-assisted extraction and GC/MS. PCB-195 was used as an internal standard. Recoveries ranged between 81 and 108% for many compounds, with RSD values < 11%. Typical LOD values for 7 days of sampling were from 0.1 to 3.1 ng/m. Propamocarb, propoxur, carbosulfan, pirimicarb, metribuzin, metalaxyl, pendimethalin, oxadiazon, phenothrin, and permethrin were detected in 11 sampling sites, with air concentrations in the range from 1 to 921 ng/m. However, the pesticide levels found cannot be considered a serious health problem according to results from other pesticide monitoring studies.

Development of a versatile, easy and rapid atmospheric monitor for benzene, toluene, ethylbenzene and xylenes determination in air.

A new procedure for the passive sampling in air of benzene, toluene, ethylbenzene and xylene isomers (BTEX) is proposed. A low-density polyethylene layflat tube filled with a mixture of solid phases provided a high versatility tool for the sampling of volatile compounds from air. Several solid phases were assayed in order to increase the BTEX absorption in the sampler and a mixture of florisil and activated carbon provided the best results. Direct head-space-gas chromatography-mass spectrometry (HS-GC-MS) measurement of the whole deployed sampler was employed for a fast determination of BTEX. Absorption isotherms were used to develop simple mathematical models for the estimation of BTEX time-weighted average concentrations in air. The proposed samplers were used to determine BTEX in indoor air environments and results were compared with those found using two reference methodologies: triolein-containing semipermeable membrane devices (SPMDs) and diffusive Radiello samplers. In short, the developed sampling system and analytical strategy provides a versatile, easy and rapid atmospheric monitor (VERAM).

Evaluation of working air quality by using semipermeable membrane devices. Analysis of organophosphorus pesticides.

It has been evaluated the use of semipermeable membrane devices (SPMDs) as passive samplers of organophosphorus pesticides from air, in order to determine the contamination of working environments. Additionally, the use of SPMDs as portable samplers has been also considered. The analytical methodology for the determination of diazinon, chlorpyrifos-methyl, pirimiphos-methyl, chlorpyrifos and fenthion in SPMDs exposed to contaminated air was based on microwave-assisted extraction and gas chromatography with mass spectrometry determination. Limit of detection (LOD) values from 2 to 4ngSPMD(-1) and repeatability from 2 to 7% were obtained by using the aforementioned methodology. Theoretical calculated sampling rates were employed for the estimation of the pesticide concentration in air, by using the pesticide mass retained in the deployed SPMD. The obtained LOD values, for a sampling time of 7 days, were from 1 to 2ngm(-3). The evaluation of the air quality of a pesticide laboratory with an intensive use of diazinon and chlorpyrifos has been made in order to check the operation safety conditions.

Assessing air quality inside vehicles and at filling stations by monitoring benzene, toluene, ethylbenzene and xylenes with the use of semipermeable devices.

BTEX (benzene, toluene, ethylbenzene, and xylenes) were used as target molecules to evaluate the quality of air inside motor vehicles and near filling stations, using semipermeable membrane devices (SPMDs) as low-cost passive sampling devices. A direct, fast, simple methodology based on the use of headspace-gas chromatography-mass spectrometry detection (HS-GC-MS) was developed for BTEX determinations, without any sample pre-treatment. SPMDs (25.4 cm2 surface, filled with 100 microL triolein) were employed as static samplers. After the selected deployment time, the SPMDs were heated inside a HS vial at 150 degrees C for 20 min and BTEX compounds were determined by GC-MS in selected ion monitoring (SIM) mode in less than 12 min. The proposed method provides limits of detection of less than 1 ng SPMD(-1) for all compounds studied; which is equivalent to 0.3-8 ng m(-3) in air for a deployment time of 24 h, and to 9-200 microg m(-3) for 10 min time, as a function of the compound considered. Using sampling times of around 24 h, concentrations from 0.2 to 145 microg m(-3) were measured inside motor vehicles. For exposure times from 2 to 40 min, concentrations of BTEX ranging from 0.03 to 79 mg m(-3) were measured at filling stations, especially during refueling of vehicles with gasoline.

Comparison of different mass spectrometric detection techniques in the gas chromatographic analysis of pyrethroid insecticide residues in soil after microwave-assisted extraction.

A comparative study was carried out for the simultaneous determination of 11 pyrethroid insecticides in soil by gas chromatography (GC)--ion trap (IT)--mass spectrometry (MS), by means of two different ionization modes; electron impact and negative chemical ionization and three data acquisition procedures; full scan, selected ion monitoring and MS/MS. Pyrethroids investigated were tetramethrin, bifenthrin, phenothrin, lambda-cyhalothrin, permethrin, cyfluthrin, cypermethrin, flucythrinate, esfenvalerate, fluvalinate and deltamethrin. Soil samples were treated with toluene/water by microwave-assisted extraction for 9 min at 700 W and a cleaning up with florisil was performed. Clean soil samples were spiked with pyrethroids at a spiking level of 10, 25 and 50 ng/g. The method employed provides a concentration factor of 10. The ionization gas employed in the negative chemical ionization mode was methane. The use of MS/MS acquisition, in electron impact ionization, provided the best results, due to its high selectivity and sensitivity, giving very low limits of detection from 0.08 to 0.54 ng/g. In negative chemical ionization full scan and selected ion monitoring methods detection limits from 0.12 to 1.40 ng/g were found. The proposed methods were applied to several levels from 10 to 50 ng/g of spiked soils, being electron impact MS/MS method which minimizes matrix spectrum interferences and provided recovery average values from 84% to 120% with relative standard deviations which varied from 3.2 to 7.2%.