Paralytic Shellfish Toxins in Mollusks from Galicia Analyzed by a Fast Refined AOAC 2005.06 Method: Toxicity, Toxin Profile, and Inter-Specific, Spatial, and Seasonal Variations.

Paralytic shellfish poisoning is an important concern for mollusk fisheries, aquaculture, and public health. In Galicia, NW Iberian Peninsula, such toxicity has been monitored for a long time using mouse bioassay. Therefore, little information exists about the precise toxin analogues and their possible transformations in diverse mollusk species and environments.

Paralytic Shellfish Poisoning (PSP) in Mussels from the Eastern Cantabrian Sea: Toxicity, Toxin Profile, and Co-Occurrence with Cyclic Imines.

In the late autumn of 2018 and 2019, some samples taken by the official monitoring systems of Cantabria and the Basque Country were found to be paralytic shellfish poisoning (PSP)-positive using a mouse bioassay. To confirm the presence of PSP toxins and to obtain their profile, these samples were analyzed using an optimized version of the Official Method AOAC 2005.06 and using LC-MS/MS (HILIC).

Multianalyte, high-throughput liquid chromatography tandem mass spectrometry method for the sensitive determination of fungicides and insecticides in wine.

Evidence of pesticide transfer from grapes to wine, added to differences in the national regulations regarding the number and the maximum concentration of these species in wine, demands analytical procedures suitable for their routine control in this foodstuff. In this research, solid-phase extraction (SPE) and ultra-performance liquid chromatography (UPLC), with tandem mass spectrometry (MS/MS) detection, are combined to obtain a sensitive and rapid procedure to determine 50 pesticides in red and white wines. Efficiency and selectivity of sample preparation are correlated with the type of sorbent, the elution solvent, and the physicochemical properties of pesticides.

Evaluation of the aqueous phototransformation routes of phenyl ethyl azolic fungicides by liquid chromatography accurate mass spectrometry.

Similarities and differences among the phototransformation routes of four azolic fungicides (diniconazole, DIN, imazalil, IMA; penconazole, PEN; and propiconazole, PRO) in surface water aliquots are investigated. Selected compounds share a common chemical structure consisting on dichlorophenyl and azolic rings connected through an ethylene bridge, which is substituted with different functionalities. Liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) was employed as analytical technique to follow the time-course of precursor fungicides and to detect and to identify their photo-transformation products (TPs).

Selective extraction and determination of neonicotinoid insecticides in wine by liquid chromatography-tandem mass spectrometry.

A simplified, high throughput procedure for the determination of five neonicotinoid insecticides in red and white wines, using liquid chromatography (LC)-tandem mass spectrometry (MS/MS), is presented. The effects of different experimental parameters (extraction sorbent, solvent elution and clean-up conditions) in the efficiency and the selectivity of the sample preparation process were assessed through calculation of the extraction yields and the matrix effects (MEs). Wines (10mL) were concentrated using OASIS HLB cartridges, on-line connected to Florisil clean-up cartridges, with acetonitrile serving as the elution solvent.

Evaluation of nitrate effects in the photodegradability of cyprodinil. Kinetics study and transformation products elucidation.

The effects of nitrate in the kinetics and the transformation routes of the fungicide cyprodinil (CYP) were investigated using aqueous solutions, ultrapure water and river water samples, spiked with the precursor compound and containing different levels of nitrate. Samples were exposed either to 254 nm radiation or to solar light, depending on the experiment. Time course of CYP and formation of transformation products (TPs) were simultaneously assessed by direct injection of different irradiation time aliquots in a liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) system.

Multiclass semi-volatile compounds determination in wine by gas chromatography accurate time-of-flight mass spectrometry.

The performance of gas chromatography (GC) with accurate, high resolution mass spectrometry (HRMS) for the determination of a group of 39 semi-volatile compounds related to wine quality (pesticide residues, phenolic off-flavours, phenolic pollutants and bioactive stilbenes) is investigated. Solid-phase extraction (SPE) was used as extraction technique, previously to acetylation (phenolic compounds) and dispersive liquid-liquid microextraction (DLLME) concentration. Compounds were determined by GC coupled to a quadrupole time-of-flight (QTOF) MS system through an electron ionization (EI) source.

Liquid chromatography quadrupole time-of-flight mass spectrometry selective determination of ochratoxin A in wine.

The performance of liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) for ochratoxin A (OTA) determination in wine is evaluated for the first time. Sample preparation was optimized to obtain quantitative recoveries at the same time that the efficiency of electrospray ionization (ESI) remained unaltered between sample extracts and calibration standards. Under final conditions, samples (20 mL) were concentrated using a reversed-phase solid-phase extraction (SPE) cartridge, followed by OTA elution with 1 mL of ethyl acetate.

Comprehensive evaluation of the photo-transformation routes of trans-resveratrol.

Liquid chromatography (LC) combined with accurate mass spectrometry (MS), based on the use of a hybrid quadrupole time-of-flight (TOF) MS system, is employed to systematically investigate the photo-transformation routes of trans-resveratrol. Experiments were performed in quartz tubes, containing ethanolic solutions (12% v/v) of the precursor compound, exposed to different ultraviolet (UV) sources and to solar light. Time-courses of trans-resveratrol and transformation products (TPs) were investigated by direct injection of different reaction times aliquots in the LC-QTOF-MS system.

Time-of-flight accurate mass spectrometry identification of quinoline alkaloids in honey.

Time-of-flight accurate mass spectrometry (TOF-MS), following a previous chromatographic (gas or liquid chromatography) separation step, is applied to the identification and structural elucidation of quinoline-like alkaloids in honey. Both electron ionization (EI) MS and positive electrospray (ESI+) MS spectra afforded the molecular ions (M(.+) and M+H(+), respectively) of target compounds with mass errors below 5 mDa.

Assessment of dispersive liquid-liquid microextraction conditions for gas chromatography time-of-flight mass spectrometry identification of organic compounds in honey.

The suitability of the dispersive liquid-liquid microextraction (DLLME) technique for gas chromatography (GC) characterization of minor organic compounds in honey samples is evaluated. Under optimized conditions, samples were pre-treated by liquid-liquid extraction with acetonitrile followed by DLLME using carbon tetrachloride (CCl4, 0.075 mL) as extractant.

Investigation of liquid chromatography quadrupole time-of-flight mass spectrometry performance for identification and determination of hydroxylated stilbene antioxidants in wine.

The performance of liquid chromatography (LC) followed by quadrupole time-of-flight (QTOF) mass spectrometry (MS) for the determination of hydroxylated stilbene compounds in red and white wine samples is assessed. When combined with a solid-phase extraction step, LC-QTOF-MS allowed the selective determination of five target compounds (trans- and cis-resveratrol, trans-piceatannol, trans-piceid and trans-pterostilbene) attaining limits of quantification between 3 and 20ngmL(-1) and providing linear responses up to 4000ngmL(-1). Recoveries, established against standards prepared in methanol, varied between 93% and 115%.

Assessment of silicone as support to investigate the transformation routes of organic chemicals under environmental conditions and UV exposure. Application to selected fungicides.

The suitability of bulk silicone as support to follow the degradation of chemical compounds under environmental conditions and UV radiation is illustrated selecting three fungicides (fenhexamid, FEN; triadimenol, TRI and difenoconazole, DIF) as model compounds. These precursor species were first absorbed in silicone supports (10 mm length × 2 mm i.d.

Liquid chromatography time-of-flight mass spectrometry evaluation of fungicides reactivity in free chlorine containing water samples.

Liquid chromatography (LC) combined with tandem mass spectrometry (MS/MS), based on the use of a hybrid quadrupole-time-of-flight mass analyzer, was used to investigate the reactivity of nine fungicides in free chlorine-containing water samples. Three of the selected compounds (fenhexamid, FEN; pyrimethanil, PYR; and cyprodinil, CYP) displayed a poor stability in presence of moderate chlorine levels; thus, the effects of different parameters on their half-lives (t(1/2)) were evaluated. Sample pH, bromide traces, and the water matrix affected their relative stabilities.

Dispersive liquid-liquid microextraction with non-halogenated extractants for trihalomethanes determination in tap and swimming pool water.

An effective, low solvent consumption, reduced cost and high throughput sample preparation method for the determination of four trihalomethanes (THMs) in tap and swimming pool water samples is presented. THMs extraction and concentration were performed by dispersive liquid-liquid microextraction (DLLME), based on the use of non-halogenated and low volatile solvents as extractants. Analytes were further determined by gas chromatography with micro-electron capture detection (GC-microECD).

Determination of hydroxylated stilbenes in wine by dispersive liquid-liquid microextraction followed by gas chromatography mass spectrometry.

Dispersive liquid-liquid microextraction (DLLME) has been proposed, for first time, to determine the concentrations of three hydroxylated stilbenes (trans-isomers of pterostilbene, resveratrol and piceatannol) in wine samples. DLLME was preceded by an acetylation step and followed by gas chromatography mass spectrometry (GC-MS) to achieve limits of quantification (LOQs) comprised between 0.6 and 5 ngmL(-1), linear responses up to 5000 ngmL(-1), excellent accuracy (overall recoveries ranged from 90 to 102% for samples spiked at different levels from 50 to 1000 ngmL(-1)) and standard deviations below 12%.

Dispersive liquid-liquid microextraction using non-chlorinated, lighter than water solvents for gas chromatography-mass spectrometry determination of fungicides in wine.

A novel and low solvent consumption method for the sensitive determination of fungicide residues in wine samples is proposed. Analytes were extracted by dispersive liquid-liquid microextraction (DLLME) and further determined by gas chromatography-mass spectrometry (GC-MS). Under optimized conditions, a binary mixture of acetone and 1-undecanol (0.