Identification of ethoxyquin and its transformation products in salmon after controlled dietary exposure via fish feed.

Ethoxyquin (EQ) is an additive present in fish feed and its fate in fish should be carefully characterized due to food safety concerns regarding this compound. Therefore, the objective of this work was to identify the transformation products (TPs) of EQ in Atlantic salmon. Salmon in independent tanks were given feed containing ethoxyquin concentrations of 0.5 mg/kg, 119 mg/kg or 1173 mg/kg for 90 days. After the feeding trial, salmon fillets were extracted in acetonitrile and analyzed by liquid chromatography with traveling-wave ion mobility spectrometry coupled to high resolution mass spectrometry (UHPLC-TWIMS-QTOFMS). EQ was transferred from the feed to salmon fillets and 23 TPs were characterized, resulting from dimerization, oxygenation, cleavage, cleavage combined with oxygenation, cleavage combined with conjugation, and other uncategorized alterations. Moreover, EQ and some TPs were also detected in commercial salmon randomly sampled from different Norwegian fish farms. This study confirmed that the dimer 1,8'-EQDM was the main TP of EQ and, together with previous research, brought the overall number of characterized TPs to a total of 47.

Dietary exposure and neurotoxicity of the environmental free and bound toxin ß-N-methylamino-l-alanine.

The growing evidence supporting a link between exposure to the naturally occurring toxin ß-N-methylamino-l-alanine (BMAA) and progressive neurodegenerative diseases, has recently arisen the interest of the scientific community. Latest investigations suggest that dietary exposure to this algal toxin may have been largely underestimated. This paper reviews the state of the art regarding BMAA, with special attention paid to its neurotoxicity, its concentration levels in food, and human exposure. As for other environmental toxins, dietary intake is most likely the main route of exposure to BMAA for the general population. However, data concerning BMAA levels in foodstuffs are still scarce. It is concluded that further investigations on dietary intake and potential human health effects are clearly necessary to assess the risks to public health associated with BMAA exposure. Some critical remarks and recommendations on future research in this area are provided, which may help to identify approaches to reduce dietary BMAA exposure.

Comprehensive characterization of ethoxyquin transformation products in fish feed by traveling-wave ion mobility spectrometry coupled to quadrupole time-of-flight mass spectrometry.

Feed additives are typically used in intensive farming production over long periods, and hence, they can accumulate in farmed animal tissues. Concerns regarding the use of ethoxyquin as an antioxidant feed additive, have recently arisen due to its potential conversion into a series of transformation products (TPs). The aim of this work was to characterize the TPs of ethoxyquin in fish feed by a novel approach based on the use of traveling-wave ion mobility spectrometry (TWIMS) coupled to high-resolution quadrupole time-of-flight mass spectrometry (QTOFMS). First, ethoxyquin was oxidized under controlled conditions and the generated TPs were added to a comprehensive database. Atlantic salmon feeds were then screened for ethoxyquin TPs using both targeted and untargeted approaches. Twenty-seven TPs were tentatively identified during the oxidation experiments, fifteen of them also being present in the feed samples. In addition, ten other potential TPs were detected in fish feed following the untargeted approach. Thirty-one of these TPs have been reported for the first time in this work through the oxidation experiments and the feed samples. Therefore, this study provides valuable information on the oxidative fate of ethoxyquin in feed, which can be used for future evaluations of potential risk related to this additive.

Challenges in relating concentrations of aromas and tastes with flavor features of foods.

Flavor sensations in food are highly influenced by the aroma and taste compounds. Reviewing the extensive literature of recent years in this field has shown that the reconstitution of flavor based on aroma and taste compounds poses numerous problems. These are of different nature and include among others (a) chemical transformations among these compounds, (b) changes in the concentrations of the compounds responsible for the perceived flavor, (c) interactions among the chemical compounds that enhance or reduce a specific flavor sensation, and finally, (d) the complexity of the different food matrices and its influence in the flavor perception. Another difficulty that flavor scientists must face is how to properly model and visualize the complex relationships existing between the chemical composition of foods and the flavor perception. These problems have repercussions on the reconstitution of the flavor signature of food based on the natural concentrations of its key aroma and taste compounds. Therefore, the main aim of this review is to deal with all these issues to propose potential solutions for a robust transformation in a science-based quality approach.

Ion-Mobility-Derived Collision Cross Section as an Additional Identification Point for Multiresidue Screening of Pesticides in Fish Feed.

Ion mobility spectrometry allows for the measurement of the collision cross section (CCS), which provides information about the shape of an ionic molecule in the gas phase. Although the hyphenation of traveling-wave ion mobility spectrometry (TWIMS) with high-resolution quadrupole time-of-flight mass spectrometry (QTOFMS) has been mainly used for structural elucidation purposes, its potential for fast screening of small molecules in complex samples has not yet been thoroughly evaluated. The current work explores the capabilities of ultrahigh-performance liquid chromatography (UHPLC) coupled to a new design TWIMS-QTOFMS for the screening and identification of a large set of pesticides in complex salmon feed matrices. A database containing TWIMS-derived CCS values for more than 200 pesticides is hereby presented. CCS measurements showed high intra- and interday repeatability (RSD < 1%), and they were not affected by the complexity of the investigated matrices (ΔCCS ≤ 1.8%). The use of TWIMS in combination with QTOFMS was demonstrated to provide an extra-dimension, which resulted in increased peak capacity and selectivity in real samples. Thus, many false-positive detections could be straightforwardly discarded just by applying a maximum ΔCCS tolerance of ±2%. CCS was proposed as a valuable additional identification point in the pesticides screening workflow. Several commercial fish feed samples were finally analyzed to demonstrate the applicability of the proposed approach. Ethoxyquin and pirimiphos-methyl were identified in most of the analyzed samples, whereas tebuconazole and piperonil butoxide were identified for the first time in fish feed samples.

Optimization of a Differential Ion Mobility Spectrometry-Tandem Mass Spectrometry Method for High-Throughput Analysis of Nicotine and Related Compounds: Application to Electronic Cigarette Refill Liquids.

Fast market penetration of electronic cigarettes is leading to an exponentially growing number of electronic refill liquids with different nicotine contents and an endless list of flavors. Therefore, rapid and simple methods allowing a fast screening of these products are necessary to detect harmful substances which can negatively impact the health of consumers. In this regard, the present work explores the capabilities of differential ion mobility spectrometry coupled to tandem mass spectrometry for high-throughput analysis of nicotine and 11 related compounds in commercial refill liquids for electronic cigarettes. The influence of main factors affecting the ion mobility separation, such as modifier types and concentration, separation voltage, and temperature, was systematically investigated. Despite small molecular weight differences among the studied compounds, a good separation was achieved in the ion mobility cell under the optimized conditions, which involved the use of ethanol as a polar gas-phase chemical modifier. Indeed, differential ion mobility was able to resolve (resolution >4) nicotine from its structural isomer anabasine without the use of any chromatographic separation. The quantitative performance of the proposed method was then evaluated, showing satisfactory precision (RSD ≤ 16%) and recoveries ranging from 85 to 100% for nicotine, and from 84 to 126% for the rest of the target analytes. Several commercial electronic cigarette refill liquids were analyzed to demonstrate the applicability of the method. In some cases, significant differences were found between labeled and measured levels of nicotine. Anatabine, cotinine, myosmine, and nornicotine were also found in some of the analyzed samples.

Gonyaulax taylorii, a new yessotoxins-producer dinoflagellate species from Chilean waters.

In summer 2009, during a survey in Bahía Mejillones, a dense bloom of a dinoflagellate from the genus Gonyaulax was detected, as well as the presence of yessotoxin. Phytoplankton samples were analyzed in detail by light and scanning electron microscopy (SEM), revealing the presence of Gonyaulax taylorii. Morphological examination showed that the cells in the bloom fit in Gonyaulax jollifei Murray et Whitting sensu Dodge, subsequently classified as Gonyaulax taylorii by Carbonell-Moore. In this context, some inconsistencies have been found in regard to the holotype; the plate 1"' appears as two plates, 1‴ and 2‴, showing a suture that does not exist in Dodge's figure of G. jollifei, from where the holotype was drawn, nor within the samples collected. Therefore, this plate has been originally described erroneously as two plates named 1"' and 2"' instead of only one named 1‴. After this correction, this species has five instead of six postcingular plates. For this reason, the description of this species must be emended. Phytoplankton net samples were found to contain yessotoxin and homoyessotoxin, with concentrations below 1pgcell-1. The present study identifies, therefore, the dinoflagellate G. taylorii as a new source of yessotoxins.

Reactivity of vinca alkaloids during water chlorination processes: Identification of their disinfection by-products by high-resolution quadrupole-Orbitrap mass spectrometry.

Concerns about the presence of anticancer drugs in the environment are rapidly increasing mainly due to their growing use in the developed countries and their known cytotoxic effects. Vinca alkaloids are widely used in cancer therapy; however, very scarce information is available on their occurrence, environmental fate and toxicological effects on aquatic organisms. Even less attention has been paid to their potential transformation products, which can exert higher toxicity than the parent compounds. Thus, in the present work, the reactivity of vincristine, vinblastine, vinorelbine and its metabolite 4-O-deacetyl vinorelbine during water chlorination processes has been investigated for the first time. Under the studied chlorination conditions, vincristine was fairly stable whereas vinblastine, vinorelbine and 4-O-deacetyl vinorelbine were quickly degraded. A total of sixty-five disinfection by-products were tentatively identified by ultra-high performance liquid chromatography coupled to high-resolution hybrid quadrupole-Orbitrap tandem mass spectrometry. Among them, twenty by-products corresponded to mono-chlorinated compounds, eight to di-chlorinated compounds and two to tri-chlorinated compounds, which may be of major environmental concern. Other disinfection by-products involved hydroxylation and oxidation reactions. Although the structures of these by-products could not be positively confirmed due to lack of commercial standards, their chemical formulas and product ions can be added to databases, which will allow their screening in future monitoring studies.

Determination of bisphenols in beverages by mixed-mode solid-phase extraction and liquid chromatography coupled to tandem mass spectrometry.

Facing growing restrictions on the use of bisphenol A in food contact materials, several bisphenol analogs are arising as major alternatives to replace this chemical in most of its applications. This work reports a simple and robust method based on mixed-mode solid-phase extraction and stable-isotope dilution liquid chromatography-tandem mass spectrometry for the analysis of bisphenol A and its main analogs - bisphenol S, 4,4'-sulfonylbis(2-methylphenol), bisphenol F, bisphenol E, bisphenol B, bisphenol Z, bisphenol AF, bisphenol AP, tetrabromobisphenol A and bisphenol P - in alcoholic and non-alcoholic beverages. Mixed-mode solid-phase extraction, combining cationic exchange and reversed-phase mechanisms, was optimized to provide a selective extraction and purification of the target analytes. Derivatization of bisphenols with pyridine-3-sulfonyl chloride allowed increasing their ionization efficiency by electrospray ionization. Validation of the proposed method was performed in terms of selectivity, matrix effects, linearity, precision, measurement uncertainty, trueness and limits of detection. Satisfactory repeatability and intermediate precision were obtained; the related relative standard deviations were ≤9% and ≤12%, respectively. The relative expanded uncertainty (k=2) was below 20% for all bisphenol analogs and the trueness of the method was demonstrated by recovery experiments. Limits of detection (LOD) ranged from 1.6ngL(-1) to 27.9ngL(-1) for all compounds. Finally, several canned and non-canned beverages were analyzed to demonstrate the applicability of the method. Only bisphenol A and three bisphenol F isomers were detected in any of the samples. Bisphenol A concentration ranged from

Development and validation of a stable-isotope dilution liquid chromatography-tandem mass spectrometry method for the determination of bisphenols in ready-made meals.

Due to their growing consumption, ready-made meals are a major dietary component for many people in today's society, representing an important potential route of human exposure to several food contaminants. The recent restrictions in the use of bisphenol A have led the plastic industry to look for alternative chemicals, most of them belonging to the same family of p,p'-bisphenols. The aim of the current work was to develop and validate a method based on stable-isotope dilution liquid chromatography-tandem mass spectrometry for the analysis of bisphenol A and its main analogs - bisphenol S, 4,4'-sulfonylbis(2-methylphenol), bisphenol F, bisphenol E, bisphenol B, bisphenol Z, bisphenol AF, bisphenol AP, tetrabromobisphenol A and bisphenol P - in solid foodstuffs, and particularly in ready-made meals. Extraction was carried out by ultrasound-assisted extraction after sample disruption with sand. A selective solid-phase extraction procedure was then applied to reduce potential matrix interferences. Derivatization of bisphenols with pyridine-3-sulfonyl chloride increased their ionization efficiency by electrospray ionization. Validation of the proposed method was performed in terms of selectivity, matrix effects, linearity, precision, measurement uncertainty, trueness and limits of detection. Satisfactory repeatability and intermediate precision were obtained; the related relative standard deviations were ≤7.8% and ≤10%, respectively. The relative expanded uncertainty (k=2) was below 17% for all bisphenol analogs and the trueness of the method was demonstrated by spike recovery experiments. Low limits of detection, in the range from 0.025µgkg(-1) to 0.140µgkg(-1), were obtained for all compounds. To demonstrate the applicability of the proposed method, it was eventually applied to several ready-made meals purchased from different supermarkets in Belgium.

Transformation of tamoxifen and its major metabolites during water chlorination: Identification and in silico toxicity assessment of their disinfection byproducts.

The selective estrogen receptor modulator tamoxifen is the most commonly used drug for the treatment and prevention of breast cancer. Tamoxifen is considered as a pro-drug since it is known to exert its pharmacological effect through its major active metabolites, 4-hydroxy-tamoxifen and 4-hydroxy-N-desmethyl-tamoxifen, which are mainly excreted in the urine in the days following administration. In the present work, the reactivity of tamoxifen and its major active metabolites in free chlorine-containing water was investigated for the first time. Under the studied chlorination conditions, tamoxifen was fairly stable whereas its metabolites were quickly degraded. A total of thirteen chlorinated byproducts were tentatively identified by ultra-high performance liquid chromatography coupled to high-resolution hybrid quadrupole-Orbitrap tandem mass spectrometry. Time-course profiles of the identified byproducts were followed in real wastewater samples under conditions that simulate wastewater disinfection. A preliminary assessment of their acute aquatic toxicity at two trophic levels by means of quantitative structure-activity relationship models showed that the identified byproducts were up to 110-fold more toxic than the parent compounds.

Degradation of the anticancer drug erlotinib during water chlorination: Non-targeted approach for the identification of transformation products.

Erlotinib is a highly potent tyrosine kinase inhibitor used in the treatment of the most common type of lung cancer. Due to its recent introduction, very scarce information is available on its occurrence, environmental fate and toxicological effects on aquatic organisms. During chlorination processes normally carried out in wastewater treatment plants and in the pretreatment of hospital effluents, chlorinated transformation products can be formed with an enhanced toxicity relative to the parent compound. Thus, the reactivity of the cytostatic drug erlotinib in free chlorine-containing water was investigated for the first time in the present work. A non-targeted screening approach based on the use of differential profiling tools was applied in order to reveal its potential transformation products. Structural elucidation of the detected transformation products was performed by ultra-performance liquid chromatography coupled to high-resolution hybrid quadrupole-Orbitrap tandem mass spectrometry. The proposed approach allowed detecting a total of nineteen transformation products, being eighteen of them described for the first time in this work, which demonstrates its potential in environmental analysis. Among them, six compounds presented chlorine atoms in their structures, which may be of major concern. Other transformation products involved hydroxylation and oxidation reactions. Time-course profiles of erlotinib and its transformation products were followed in real wastewater samples under conditions that simulate wastewater disinfection. Although the structures of these transformation products could not be positively confirmed due to lack of standards, their chemical formulas and product ions can be added to databases, which will allow their screening in future monitoring studies.

Derivatization of bisphenol A and its analogues with pyridine-3-sulfonyl chloride: multivariate optimization and fragmentation patterns by liquid chromatography/Orbitrap mass spectrometry.

RATIONALE: Due to the growing restrictions on the use of bisphenol A (BPA), several other bisphenols are gaining importance as substitutes for BPA in a variety of applications. There is, therefore, a real need for selective and sensitive methods based on mass spectrometry which will allow the human exposure to these new bisphenols to be assessed. METHODS: Derivatization of BPA and its substitutes with pyridine-3-sulfonyl chloride is used to enhance the detection capability of bisphenols by electrospray ionization mass spectrometry. A multivariate experimental design, Box-Behnken response surface, was used to evaluate the influence of the main variables potentially affecting the derivatization yield. Fragmentation patterns for all the derivatized bisphenols were acquired by high-resolution/accurate-mass Orbitrap mass spectrometry. RESULTS: Temperature and pH were identified as the most important factors affecting the derivatization yield of bisphenols. Fragmentation of the protonated molecules produced abundant analyte-specific product ions. Most of the derivatized bisphenols showed significant improvements in their signal-to-noise ratios compared with the underivatized forms. The stability of these derivatives was demonstrated through several freeze/thaw cycles, short-term room temperature and long-term cold storage. CONCLUSIONS: Derivatization of BPA and its structural analogues with pyridine-3-sulfonyl chloride is proposed as a specific, sensitive, high-throughput approach to their analysis by liquid chromatography coupled to electrospray ionization mass spectrometry.

Depuration and anatomical distribution of domoic acid in the surf clam Mesodesma donacium.

In northern Chile, domoic acid (DA) has been detected in several bivalve species. In Mesodesma donacium, one of the most important commercial species for local fishermen, no information is available on depuration, or on the anatomical distribution of this toxin and its potential use as a palliative measure to minimize the consequences of ASP outbreaks. Deputation of DA is very fast in M. donacium, and can be adequately described by means of a two-compartment model. The estimated rates for the first and second compartments were 1.27 d(-1) and 0.24 d(-1), respectively, with a transfer rate between compartments of 0.75. Having high depuration rates protects this species from being affected by Pseudo-nitzschia blooms for an extended period of time. Taking this into account, the time in which the bivalves are unsafe for consumers is very short, and therefore the economic losses that could result by the DA outbreaks in local fisheries should be moderate. In relation to anatomical distribution, at least during the uptake phase, the toxin was evenly distributed within the soft tissues, with a total toxin burden corresponding to 27%, 32% and 41% for Digestive Gland (DG), Foot (FT) and Other Body Fractions (OBF), respectively. Since the contribution of each organ to the toxin concentration is a function of both weight contribution and toxin burden, the pattern of toxin distribution showed the following trend: "all other body fractions" (OBF) > Foot (FT) > Digestive Gland (DG). Thus, the highest concentration of DA, with a contribution close to 72%, corresponds to the edible tissues (OBF + FT), while the DG (non-edible tissue) only contributes the remaining 28%. Consequently, in view of the anatomical distribution of domoic acid in M. donacium, the elimination of the digestive gland does not substantially reduce the toxicity of the final product and therefore selective evisceration would not improve their quality for human consumption.

Carotenoid profile of tomato sauces: effect of cooking time and content of extra virgin olive oil.

The consumption of carotenoid-rich vegetables such as tomatoes and tomato sauces is associated with reduced risk of several chronic diseases. The predominant carotenoids in tomato products are in the (all-E) configuration, but (Z) isomers can be formed during thermal processing. The effect of cooking time (15, 30, 45 and 60 min) and the addition of extra virgin olive oil (5% and 10%) on the carotenoid extractability of tomato sauces was monitored using liquid chromatography-tandem mass spectrometry (LC-ESI-MS/MS) and LC-ultraviolet detection (LC-UV). The thermal treatment and the addition of extra virgin olive oil increased the levels of antioxidant activity, total carotenoids, Z-lycopene isomers, α-carotene and ß-carotene. These results are of particular nutritional benefit since higher lycopene intake has been associated with a reduced risk of lethal prostate and a reduction of prostate-specific antigen (PSA) levels. Moreover, ß-carotene has been reported to suppress the up-regulation of heme oxygenase-1 gene expression in a dose dependent manner and to suppress UVA-induced HO-1 gene expression in cultured FEK4.

Toxicity evaluation of new agricultural fungicides in primary cultured cortical neurons.

Fungicides are crucial for food protection as well as for the production of crops of suitable quality and quantity to provide a viable economic return. Like other pesticides, fungicides are widely sprayed on agricultural land, especially in wine-growing areas, from where they can move-off after application. Furthermore, residues of these agrochemicals can remain on crops after harvest and even after some food processing operations, being a major exposure pathway. Although a relatively low toxicity has been claimed for this kind of compounds, information about their neurotoxicity is still scarce. In the present study, nine fungicides recently approved for agricultural uses in the EU - ametoctradin, boscalid, cyazofamid, dimethomorph, fenhexamid, kresoxim-methyl, mepanipyrim, metrafenone and pyraclostrobin - have been evaluated for their toxicity in primary cultured mouse cortical neurons. Exposure to 0.1-100µM for 7 days in vitro resulted in a dose-dependent toxicity in the MTT cell viability assay. Strobilurin fungicides kresoxim-methyl (KR) and pyraclostrobin (PY) were the most neurotoxic compounds (lethal concentration 50 were in the low micromolar and nanomolar levels, respectively) causing a rapid raise in intracellular calcium [Ca(2+)]i and strong depolarization of mitochondrial membrane potential. KR- and PY-induced cell death was reversed by the calcium channels blockers MK-801 and verapamil, suggesting that calcium entry through NMDA receptors and voltage-operated calcium channels are involved in KR- and PY-induced neurotoxicity. These results highlight the need for further evaluation of their neurotoxic effects in vivo.

A review on the fermentation of foods and the residues of pesticides-biotransformation of pesticides and effects on fermentation and food quality.

Residues of pesticides in food are influenced by processing such as fermentation. Reviewing the extensive literature showed that in most cases, this step leads to large reductions in original residue levels in the fermented food, with the formation of new pesticide by-products. The behavior of residues in fermentation can be rationalized in terms of the physical-chemical properties of the pesticide and the nature of the process. In addition, the presence of pesticides decrease the growth rate of fermentative microbiota (yeasts and bacterias), which provokes stuck and sluggish fermentations. These changes have in consequence repercussions on several aspects of food sensory quality (physical-chemical properties, polyphenolic content, and aromatic profile) of fermented food. The main aim of this review is to deal with all these topics to propose challenging needs in science-based quality management of pesticides residues in food.

Home Cooking and Phenolics: Effect of Thermal Treatment and Addition of Extra Virgin Olive Oil on the Phenolic Profile of Tomato Sauces.

Tomato products are a key component of the Mediterranean diet, which is strongly related to a reduced risk of cardiovascular events. The effect of cooking time (15, 30, 45, and 60 min) and the addition of extra virgin olive oil (5 and 10%) on the phenolic content of tomato sauces was monitored using liquid chromatography coupled to tandem mass spectrometry. Concentration of phenolics in the tomato sauces decreased during the cooking process, with the exception of caffeic acid and tyrosol. The main degradation observed was the oxidation of quercetin, since the hydroxy-function at the C-ring of this flavonoid is not blocked by a sugar moiety, unlike rutin. Higher levels of virgin olive oil in tomato sauce seemed to enhance the extraction of phenolic compounds from the tomato, leading to higher phenolic contents in the sauces. Thus, the food matrix containing the phenolic compounds plays a crucial role in determining their accessibility.

A comprehensive study on the phenolic profile of widely used culinary herbs and spices: rosemary, thyme, oregano, cinnamon, cumin and bay.

Herbs and spices have long been used to improve the flavour of food without being considered as nutritionally significant ingredients. However, the bioactive phenolic content of these plant-based products is currently attracting interest. In the present work, liquid chromatography coupled to high-resolution/accurate mass measurement LTQ-Orbitrap mass spectrometry was applied for the comprehensive identification of phenolic constituents of six of the most widely used culinary herbs (rosemary, thyme, oregano and bay) and spices (cinnamon and cumin). In this way, up to 52 compounds were identified in these culinary ingredients, some of them, as far as we know, for the first time. In order to establish the phenolic profiles of the different herbs and spices, accurate quantification of the major phenolics was performed by multiple reaction monitoring in a triple quadrupole mass spectrometer. Multivariate statistical treatment of the results allowed the assessment of distinctive features among the studied herbs and spices.

Identification and quantification of grapefruit juice furanocoumarin metabolites in urine: an approach based on ultraperformance liquid chromatography coupled to linear ion trap-Orbitrap mass spectrometry and solid-phase extraction coupled to ultraperformance liquid chromatography coupled to triple quadrupole-tandem mass spectrometry.

Grapefruit is a rich source of flavonoids but also contains furanocoumarins, which are known to strongly interact with a variety of medications. Thus, characterization of grapefruit furanocoumarin metabolites may help in a better understanding of grapefruit-drug interactions. In the present work, identification of the main metabolites of grapefruit juice furanocoumarins in urine was performed by ultraperformance liquid chromatography (UPLC) coupled to linear ion trap-Orbitrap mass spectrometry (LTQ-Orbitrap). Glucuronides of 6',7'-dihydroxybergamottin and a hydroxybergamottin-like metabolite were identified for the first time as grapefruit juice metabolites. Afterward, a fast and sensitive method based on solid-phase extraction (SPE) and UPLC coupled to triple quadrupole-tandem mass spectrometry (QqQ-MS/MS) was developed for determination of the identified metabolites in urine. The proposed method was applied to urine samples of five volunteers after intakes of moderate doses of grapefruit, lemon, and orange juices. Furanocoumarin metabolites were only detected in urines after consumption of grapefruit juice.