Human Biomonitoring of food contaminants in Spanish children: Design, sampling and lessons learned

[EN] Human Biomonitoring (HBM) studies are highly useful for evaluating population exposure to environmental contaminants and are being carried out in increasing numbers all over the world. The use of HBM in the field of food safety, in a risk assessment context, presents a growing interest as more health-based guidance values (HBGV) in biological matrices are derived, and can be used in a complementary way to the external exposure approaches such as total diet studies or surveillance programmes. The aims of the present work are: i) to describe the methodological framework of the BIOVAL study, a cross-sectional HBM program carried out by the Health Department of the Regional Government of Valencia (Spain), that is linked to the food safety official control, and is focused on children from 6 to 11 years of age ii) to explain and discuss the pre-analytical results iii) to report and discuss on lessons learned from its design and implementation. The study population included 666 children from whom urine and hair were taken in order to analyse different biomarkers of exposure to food pollutants.Pérez-Torres, R.; Doménech Antich, EM.; Coscollà, C.; Yusà, V. (2017). Human Biomonitoring of food contaminants in Spanish children: Design, sampling and lessons learned. International Journal of Hygiene and Environmental Health. 220(8):1242-1251. doi:10.1016/j.ijheh.2017.07.006S12421251220

Qualitative screening of 116 veterinary drugs in feed by liquid chromatography-high resolution mass spectrometry. Potential application to quantitative analysis

Veterinarian and human pharmaceuticals may be intentionally added to animal feed to enhance animal production. Monitoring these substances is necessary for protecting the consumers. In this work, a screening method covering 116 human and veterinary drugs has been developed and validated in five types of animal feed at 0.02 and 0.2 mg kg−1. After a simple extraction and dilution, the samples were analysed by ultra-high performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UHPLC-QTOF MS). Nearly all compounds tested were detected at 0.02 mg kg−1, based on the presence of the accurate-mass (de)protonated molecule. However, the identification using a second accurate-mass ion was more problematic at this level. Finally, the procedure was applied to 22 feed samples, where trimethoprim, robenidine, or α- and β-nandrolone were detected and identified. The potential applicability of the method to quantitative analysis of the compounds detected in the samples was also evaluated

Influence of diet in urinary levels of metals in a biomonitoring study of a child population of the Valencian region (Spain)

[EN] Pollution by trace elements and its possible effect on organisms has become a worldwide concern due to the increasing presence of trace elements in the environment and especially in the food chain. Exposure to chemicals has traditionally been measured using environmental samples, however, human biomonitoring brings a different perspective, in which all sources and exposure pathways are integrated. The objective of this paper is to discern the possible relationship between children's diet and the metals found in children urine. With this aim in mind, a total of 120 voluntaries participated in a diet survey carried out in a school-aged population (age 6-11) from the Valencian region. In addition, twenty trace elements were analysed in children urine (arsenic, antimony, barium, beryllium, caesium, cadmium, cobalt, copper, lead, manganese, mercury, molybdenum, nickel, platinum, selenium, thallium, thorium, uranium, vanadium and zinc). Results permitted to compare metal levels in urine with metal levels of other biomonitoring studies to conclude that values, including ours, were similar in most studies. On the other hand, children who ate more vegetables had the highest values in cadmium, copper, molybdenum, antimony, thallium, vanadium, and zinc, while those who ate more fish reached higher values in mercury. Finally, children who ate more cereals and baked products had higher values in total arsenic. (c) 2017 Elsevier B.V. All rights reserved.This study was part of the research project CIPAV supported by the Conselleria de Educacion, Generalitat Valenciana (GV/2011/007).Pérez-Torres, R.; Doménech Antich, EM.; Conchado Peiró, A.; Sanchez, A.; Coscollà, C.; Yusà, V. (2018). Influence of diet in urinary levels of metals in a biomonitoring study of a child population of the Valencian region (Spain). The Science of The Total Environment. 618:1647-1657. https://doi.org/10.1016/j.scitotenv.2017.10.011S1647165761

Application of accelerated solvent extraction followed by gel performance chromatography and high-performance liquid chromatography for the determination of polycyclic aromatic hydrocarbons in mussel tissue

Accelerated solvent extraction (ASE) has been evaluated as a fast alternative to methanolic saponification for the extractionof 12 polycyclic aromatic hydrocarbons (PAHs) from mussel tissue. Several solvent systems and different operatingconditions were investigated. The mixture dichloromethane-acetone (1:1, v/v) gave the best recoveries at 125ºC and1500 psi, in a total time of 10 min. No yield difference was found between freeze-drying (Fd) or drying the wet musselwith diatomaceous earth (Ded) prior to extraction. The ASE method was validated using the standard reference materialSRM 2977, a freeze-dried mussel tissue with naturally present organic contaminants. The performance characteristicsof the ASE method (trueness: 70–110%; precision: 4–14% and limit of quantification (LOQ): 0.1–0.25mg/kg) meetthe criteria established by the European Union for quantitative methods of analysis for official control of organicresidues and contaminants. ASE provides a 24 times faster extraction than MSE and reduces 12 times the volume of solventrequired

Biomonitoring of polycyclic aromatic hydrocarbons in urine of lactating mothers: Urinanry levels, association with lifestyle factors, and risk assessment

Polycyclic aromatic hydrocarbons (PAHs) are pollutants produced during incomplete combustion of organic matter and several industrial processes. Humans can be exposed to PAHs through ingestion of food, inhalation of tobacco smoke or polluted air, and dermal contact, causing immunologic, developmental, and reproductive problems. In the present research, eleven metabolites of PAHs were analyzed in the urine of 110 lactating women living in Spain (2015). PAH metabolites were extracted from the urine samples by liquid-liquid extraction and their determination was performed by liquid chromatography coupled to tandem mass spectrometry. In addition, information on lifestyle and dietary habits of the participants was collected using a questionnaire. All the PAH metabolites were detected in more than 70% of the samples, except for 3-hydroxybenzo(a)pyrene which was detected in less than 1% of the samples. The highest urinary levels were found for naphthalene metabolites, with geometric means of 0.8 (1-hydroxynaphthalene) and 7.1 ng ml-1 (2-hydroxynaphthalene). The statistical analysis showed that smoking status, as well as the ingestion of certain food groups (vegetables, cereals, oils and fats, smoked fish and coffee), were the main influencing factors of exposure to PAHs. The estimated daily intake (EDI) was calculated for naphthalene, fluorene, phenanthrene, and pyrene, ranging from 6 to 1522 ng kg-1·day-1. The non-cancer risk associated to PAH exposure was estimated, showing hazard quotients (HQs) and hazard indexes (HIs) below 1. Therefore, it did not reveal a significant health risk for Spanish women due to PAH exposure

Determination of per- and polyfluorinated substances in airborne particulate matter by microwave-assisted extraction and liquid chromatography-tandem mass spectrometry

A sensitive and confirmatory analytical method has been developed for the determination of 12 ionic perand polyfluorinated alkyl substances (PFAS) in fine airborne particulate matter (PM2.5) at trace levels. The proposed method includes extraction of PM2.5-bound PFAS by microwave-assisted extraction (MAE) followed by centrifugation and injection into the liquid chromatograph coupled to a triple quadrupole tandem mass spectrometry system (LC-MS/MS). The main parameters affecting the performance of MAE were optimised using statistical design of experiments (DoE). Recoveries ranged from 83 to 120% and the method quantification limit (MQL) was 1.4 pg m−3, when air volumes of 720 m3 were sampled. This method was successfully applied to 41 samples collected from five stations of the monitoring network of the Valencian Regional Government (Spain) during April-July 2010. Eight out of 12 PFCs investigated were quantified in at least one sample (PFBA, PFPeA, PFHxS, 6:2 FTS, PFOA, PFNA, PFOS and PFDA). The measured concentrations ranged from 1.4 to 34.3 pg m−3

Determination of 3-MCPD by GC-MS/MS with PTV-LV injector used for a survey of Spanish foodstuffs

3-Monochloropropane-1,2-diol (3-MCPD) is the most common chemical contaminant of the group of chloropropanols. It can occur in foods and food ingredients at low levels as a result of processing, migration from packaging materials during storage and domestic cooking. A sensitive method for determination of 3-MCPD in foodstuffs using programmable temperature vaporization (PTV) with large-volume injection (LVI) gas chromatography (GC) with tandem mass spectrometry detection (MS/MS) has been developed and optimized. The optimization of the injection and detection parameters was carried out using statistical experimental design. A Plackett-Burman design was used to estimate the influence of resonance excitation voltage (REV), isolation time (IT), excitation time (ET), ion source temperature (IST), and electron energy (EE) on the analytical response in the ion trap mass spectrometer (ITMS). Only REV was found to have a statically significant effect. On the other hand, a central composite design was used to optimize the settings of injection temperature (T(inlet)), vaporization temperature (T(vap)), vaporization time (t(vap)) and flow (Flow). The optimized method has an instrumental limit of detection (signal-to-noise ratio 3:1) of 0.044 ng mL(-1). From Valencian, Spain, supermarkets 94 samples of foods were surveyed for 3-MCPD. Using the optimized method levels higher than the limit established for soy sauce by the European Union were found in some samples. The estimated daily intake of 3-MCPD throughout the investigated foodstuffs for adults and children was found about 0.005 and 0.01%, respectively, of the established provisional tolerable daily intake

Optimization of a microwave-assisted extraction large-volume injection and gas chromatography–ion trap mass spectrometry procedure for the determination of polybrominated diphenyl ethers, polybrominated biphenyls and polychlorinated naphthalenes in sediments

A sensitive and rapid method for the determination of polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs) and polychlorinated naphthalenes (PCNs) in sediment samples is proposed. The method involving microwave-assisted extraction (MAE) and large-volume injection (LVI) gas chromatography (GC)–ion trap mass spectrometry (ITMS), and the experimental conditions were optimized using the statistical design of experiments (DOE). A Plackett–Burman (P–B) design was chosen to estimate the influence of five factors, such as resonance excitation voltage (EV), isolation time (IT), excitation time (ET), ion source temperature (IST) and electron energy (EE) on the analytical response in the ITMS determination. In order to increase the analytical response, 70 μL of the final extract were injected into the GC–tandem mass spectrometry (MS–MS) using a programmable temperature vaporizer (PTV). The factor settings involving injection temperature, vaporization temperature, vaporization time and flow during the evaporation step were previously optimized using a central composite design (CCD). The MAE was carried out using the hexane–acetone (1:1, v/v) mixture and the extraction conditions were optimized with a CCD. The highest response was obtained with a volume of 48 mL, a temperature of 152 °C and an extraction time of 24 min. The optimized method gives recoveries between 75 and 95% with relative standard deviations (R.S.D.) that ranged from 4 to 13%. The limit of detection (LOD) ranged between 4 and 20 pg g−1 dry weight (dw) when 5 g of sediment were analyzed. The MAE method was applied to the analyses of polyhalogenated compounds in sediments collected in the harbour of Valencia (Spain). The proposed method may serve as an alternative for GC–negative chemical ionization (NCI)–MS and can be used in government testing programmes

Exposure assessment of Spanish lactating mothers to acrylamide via human biomonitoring

Acrylamide (AA) is an organic compound classified as 'Probably carcinogenic to humans' (Group 2 A) that can be found principally in processed carbohydrate-rich foods and tobacco smoke. In humans, after exposure, AA is rapidly metabolized and excreted in urine, predominantly as N-acetyl-S-(2-carbamoylethyl)-l-cysteine (AAMA), N-acetyl-S-(2-carbamoyl-2-hydroxyethyl)-l-cysteine (GAMA3) and N-Acetyl-3-[(3-amino-3-oxopropyl)sulfinyl]-L-alanine (AAMA-Sul), which can be used as short-term biomarkers of exposure to AA. In this study, the presence of AA metabolites in urine samples of lactating mothers living in Spain (n = 114) was analyzed by 'dilute and shoot' and liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). All urinary metabolites were detected in 100% of the analyzed samples, with geometric means of 70, 33 and 15 ng ml−1, for AAMA, AAMA-Sul and GAMA3, respectively. The consumption of coffee, bread and precooked food products were found to be significant predictors of internal exposure to AA. An estimated daily intake (EDI) of AA based on its urinary metabolites was calculated, obtaining mean values between 1.2 and 1.9 μg AA·kg bw−1·day−1 in the target population. The risk assessment was evaluated using both reverse and forward dosimetry, showing an average margin of exposure (MOE) of 349 and a hazard quotient (HQ) of 5.5. Therefore, AA exposure should be considered a medium priority for risk assessment follow-up in the Spanish population, since a health concern with respect to non-neoplastic toxicity could not be discarded

Determination of acrylamide in foods by pressurized fluid extraction and liquid chromatography-tandem mass spectrometry used for a survey of Spanish cereal-based foods

An automated and rapid method for the determination of acrylamide in different food products is presented. The method involves pressurized fluid extraction (PFE) of foods with acetonitrile and precipitation with Carrez reagents. The final extract is analysed by liquid chromatography coupled to electrospray ionization tandem mass spectrometry (ESI-MS-MS). The main parameters affecting the performance of ESI-MS-MS and PFE were optimized using a design of experiments approach. The limit of quantification of the method was 5 microg kg(-1), and recoveries from incurred samples ranged between 93 and 101%. The accuracy was evaluated using the reference test materials FAPAS T3002, T3005 and T3011. Using the optimized method, 62 food samples of potato chips, snacks, biscuits, breakfast cereals and crisp bread sampled from Valencia, Spain, supermarkets were surveyed for acrylamide levels. The levels were similar to those reported in the European Union and USA