Indoor air pesticide in dwellings of breastfeeding mothers of the Valencian Region (Spain): Levels, exposure and risk assessment

This study assessed the inhalation risk associated with indoor pesticide concentrations in the dwellings of 41 lactating mothers living in the Valencian Region, Spain, who were participants in the BETTERMILK project. Twenty-eight substances were investigated, including pyrethroid (PYRs), organophosphate (OPPs), and organochlorine (OCPs) pesticides. Bifenthrin, cypermethrin, lambda-cyhalothrin, malathion, permethrin and pyrimethanil were detected with frequencies ranging from 2% (malathion) to 80% (cypermethrin), and with an arithmetic mean concentration ranging from 4.1 ng m(-3) (bifenthrin) to 12.1 ng m-(3) (cypermethrin). The indoor air analysis was combined with several surveys to assess…

Congener profile, occurrence and estimated dietary intake of dioxins and dioxin-like PCBs in foods marketed in the Region of Valencia (Spain).

During 2006-2008, a monitoring program was conducted on 29 target compounds, including PCDD/Fs and dl-PCBs, comprising 150 randomly collected individual food samples marketed in the Region of Valencia, Spain, grouped into 8 categories (vegetables, cereals, fats and oils, eggs, milk and dairy products, fish products, meat and meat products and fish oil). For PCDD/Fs, the highest frequency of detection corresponds to 1,2,3,4,6,7,8-HpCDD, OCDD, 2,3,4,7,8-PeCDF; and PCBs 118, 105 and 156 were the more frequent dl-PCBs. The food groups presenting higher contamination, expressed as toxic equivalents (WHO-TEQs), were fish oil (6.38 pg WHO-TEQ g(-1)fat), fish (1.21 pg WHO-TEQ g(-1)w.w.) and milk an…

Biomonitoring of non-persistent pesticides in urine from lactating mothers: Exposure and risk assessment

Abstract The aim of the present study was to assess the exposure to pesticides in urine from Spanish lactating mothers (n = 116). Six nonspecific (dialkyl phosphates) and 20 specific metabolites of organophosphate pesticides (OPs), herbicides and pyrethroids were analyzed. The most frequently detected biomarkers were diethyl phosphate, p-nitrophenol, 3,5,6-trichloro-2-pyridinol and 3-phenoxybenzoic acid, whose geometric means were 1.9 ng·mL−1, 0.8 ng·mL−1, 1.5 ng·mL−1 and 1.4 ng·mL−1, respectively. Herbicide metabolites were the least frequently detected biomarkers with detection frequencies between 0% (2,4,5-Trichlorophenoxyacetic acid) and 22% (2,4-Dichlorophenoxyacetic acid). Multiple re…

Target analysis and retrospective screening of veterinary drugs, ergot alkaloids, plant toxins and other undesirable substances in feed using liquid chromatography-high resolution mass spectrometry.

A comprehensive strategy combining a quantitative method for 77 banned veterinary drugs, mycotoxins, ergot alkaloids and plant toxins, and a post-target screening for 425 substances including pesticides and environmental contaminants in feed were developed using a QuEChERS-based extraction and an ultra-high performance liquid chromatography coupled to high-resolution mass spectrometry (UHPLC-HRMS). The quantitative method was validated after previous statistical optimisation of the main parameters governing ionisation, and presented recoveries ranging, in general, from 80 to 120%, with a precision in terms of Relative Standard Deviation (RSD) lower than 20%. The full-scan accurate mass data…

Additional file 1: Table S1. of Distributions and determinants of urinary biomarkers of organophosphate pesticide exposure in a prospective Spanish birth cohort study

Intake of fruit and vegetables according to the maternal sociodemographic and life style characteristics. (DOC 49 kb)

Retrospective screening of pesticide metabolites in ambient air using liquid chromatography coupled to high-resolution mass spectrometry

A new methodology for the retrospective screening of pesticide metabolites in ambient air was developed, using liquid chromatography coupled to Orbitrap high-resolution mass spectrometry (UHPLC-HRMS), including two systematic workflows (i) post-run target screening (suspect screening) and (ii) non-target screening. An accurate-mass database was built and used for the post-run screening analysis. The database contained 240 pesticide metabolites found in different matrixes such as air, soil, water, plants, animals and humans. For non-target analysis, a "fragmentation-degradation" relationship strategy was selected. The proposed methodology was applied to 31 air samples (PM10) collected in the…

Determination of PAHs in airborne particles by accelerated solvent extraction and large-volume injection-gas chromatography-mass spectrometry.

Abstract A sensitive and automated method is presented for the determination of polycyclic aromatic hydrocarbons (PAHs) in airborne particulate matter. The procedure includes extraction of PM10-bound PAHs by accelerated solvent extraction (ASE) followed by gel permeation chromatography (GPC) clean-up, and large-volume programmable temperature vaporizer (PTV–LV) injection coupled to GC–MS. The limit of detection (LOD) of the whole method, based on a signal-to-noise ratio (S/N) of 3:1, ranged from 0.26 pg m−3 to 3 pg m−3 when air volumes of 760 m3 are collected. The hexane–acetone mixture (1:1, v/v) gave the best recoveries when ASE parameters were fixed at 125 °C, 1500 psi, and a total time …

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 extraction of 12 polycyclic aromatic hydrocarbons (PAHs) from mussel tissue. Several solvent systems and different operating conditions were investigated. The mixture dichloromethane-acetone (1:1, v/v) gave the best recoveries at 125 degrees C and 1500 psi, in a total time of 10 min. No yield difference was found between freeze-drying (Fd) or drying the wet mussel with diatomaceous earth (Ded) prior to extraction. The ASE method was validated using the standard reference material SRM 2977, a freeze-dried mussel tissue with naturally present organic contaminants. The performance…

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

Abstract 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 ha…

Health Risk Assessment of Exposure to 15 Essential and Toxic Elements in Spanish Women of Reproductive Age: A Case Study

This case study investigates the exposure of 119 Spanish women of reproductive age to 5 essential (Co, Cu, Mn, V, Zn) and 10 toxic (Ba, Be, Cs, Ni, Pb, Pt, Sb, Th, Al, U) elements and assesses their risk. The essential elements (Co, Cu, Mn, V, and Zn) showed average concentrations (GM: geometric mean) of 0.8, 35, 0.5, 0.2, and 347 μg/L, respectively. Five of the toxic elements (Ba, Cs, Ni, Al, U) exhibited detection frequencies of 100%. The GM concentrations of the novel toxic elements were 12 μg/L (Al), 0.01 μg/L (Pt), 0.02 μg/L (U), 0.12 μg/L (Th), 0.009 μg/L (Be) and 4 μg/L (Cs). The urine analysis was combined with a survey to assess any variations between subgroups…

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 …

Risk assessment and monitoring programme of nitrates through vegetables in the Region of Valencia (Spain)

This study was carried out to determine current levels of nitrate in vegetables marketed in the Region of Valencia (Spain) and to estimate the toxicological risk associated with their intake. A total of 533 samples of seven vegetable species were studied. Nitrate levels were derived from the Valencia Region monitoring programme carried out from 2009 to 2013 and food consumption levels were taken from the first Valencia Food Consumption Survey, conducted in 2010. The exposure was estimated using a probabilistic approach and two scenarios were assumed for left-censored data: the lower-bound scenario, in which unquantified results (below the limit of quantification) were set to zero and the up…

Indoor Air Quality including Respiratory Viruses

The detection of SARS-CoV-2 in indoor environments is a cause of increasing concern. In this study, three sampling methodologies have been used in order to collect SARS-CoV-2 and 17 other respiratory viruses in indoor air, combined with a new analytical process to analyze respiratory viruses. Different areas of an ophthalmological hospital were investigated for the presence of these airborne viruses. Moreover, indoor air quality (IAQ) parameters (carbon dioxide, CO2; carbon monoxide, CO; nitrogen dioxide, NO2; volatile organic compounds, VOCs; formaldehyde, HCHO; and particulate matter, PM) have been examined to study the relationship between IAQ and airborne viruses. All indoor air and sur…

Determination of 40 currently used pesticides in airborne particulate matter (PM 10) by microwave-assisted extraction and gas chromatography coupled to triple quadrupole mass spectrometry

A confirmatory and sensitive procedure has been developed for the determination of 40 currently used pesticides (Cups) in airborne particulate matter (PM 10) at trace level. The proposed method includes extraction of PM 10-bound pesticides by microwave-assisted extraction (MAE) followed by a gel permeation chromatography (GPC) clean-up and determination by GC-MS/MS. The injection mode and the main parameters in MS/MS were optimized. The matrix effect was also evaluated. Recoveries ranged from 70 to 120% except for pyrimethanil and pirimicarb. The limit of quantification (LOQ) ranged from 1.32 to 39.47 pg m(-3), when air volumes of 760 m(3) were collected. The method was applied to 38 sample…

Biomonitoring exposure assessment to contemporary pesticides in a school children population of Spain

The exposure to pesticides amongst school-aged children (6-11 years old) was assessed in this study. One hundred twenty-five volunteer children were selected from two public schools located in an agricultural and in an urban area of Valencia Region, Spain. Twenty pesticide metabolites were analyzed in children's urine as biomarkers of exposure to organophosphate (OP) insecticides, synthetic pyrethroid insecticides, and herbicides. These data were combined with a survey to evaluate the main predictors of pesticide exposure in the children's population. A total of 15 metabolites were present in the urine samples with detection frequencies (DF) ranging from 5% to 86%. The most frequently detec…

Dynamic reaction cell inductively couple plasma-mass spectrometry optimization for seawater analysis

Abstract A direct method for dynamic reaction cell inductively coupled plasma- mass spectrometry (DRC-ICP-MS) trace mineral elements determination in seawater was optimized by Experimental Statistical Design. Five instrumental parameters, such as radiofrequency, sample, nebulizer and reaction gas flows, rejection parameter q and axial field voltage were studied. A Plackett-Burman design was used for screening the most important parameters and the most significant ones were optimized with a Central composite design. Fifteen elements and different isotopes for some of these were considered through the study. The optimization was achieved by using three different reaction gases (NH3, CH4 and O…

Exposure and cumulative risk assessment to non-persistent pesticides in Spanish children using biomonitoring.

Abstract The main objective of the present research is to evaluate the exposure to pesticides in children (n = 568) from the Valencian Region (Spain). Six non-specific and 20 specific metabolites of organophosphate pesticides (OPs), herbicides (Herb), and pyrethroids (Pyr) were analyzed in urine samples. The biomarkers with the highest detection frequencies (>70%) were diethyl phosphate, p-nitrophenol, 3-phenoxybenzoic acid, and 3,5,6-trichloro-2-pyridinol, whose geometric mean concentrations (ng·ml-n1) were 1.53, 1.03, 1.51 and 1.19, respectively. Robust regression models showed that the province of residence and the recent consumption of vegetables, legumes and cereals were some of the mo…

Validation of a multi-residue UHPLC-HRMS method for antibiotics screening in milk, fresh cheese, and whey

Abstract The aim of this study was to develop a UHPLC–HRMS methodology as a suitable tool for the screening of antibiotics in milk, fresh cheese, and whey. Compounds were analysed using an Orbitrap Exactive™ analyser working at a resolving power of 50,000 FWHM in full scan, both in positive and negative electrospray ionization mode, and a high mass accuracy (

Comprehensive analytical strategy for biomonitoring of pesticides in urine by liquid chromatography–orbitrap high resolution mass spectrometry

In this study we propose an analytical strategy that combines a target approach for the quantitative analysis of contemporary pesticide metabolites with a comprehensive post-target screening for the identification of biomarkers of exposure to environmental contaminants in urine using liquid chromatography coupled to high-resolution mass spectrometry (LC–HRMS). The quantitative method for the target analysis of 29 urinary metabolites of organophosphate (OP) insecticides, synthetic pyrethroids, herbicides and fungicides was validated after a previous statistical optimization of the main factors governing the ion source ionization and a fragmentation study using the high energy collision disso…

Analysis of four parabens and bisphenols A, F, S in urine, using dilute and shoot and liquid chromatography coupled to mass spectrometry

Abstract A new strategy for the analysis of 4 parabens (methylparaben, ethyl paraben, propyl paraben and butyl paraben) and 3 bisphenols (A, F and S) in human urine has been developed. Dilute and shoot and liquid chromatography coupled to mass spectrometry (LC-MS/MS) determination was employed. Procedural matched calibration, certified materials and spiked samples were used for validation. The obtained recoveries varied between 85 and 104% with a precision lower than 20% for all analytes. The LOQ was 0.20 ng mL for all analytes. Negative atmospheric pressure chemical ionization in the selected reaction monitoring mode was used for MS detection. The proposed method was successfully applied f…

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 reso…

Biomonitoring of bisphenols A, F, S in human milk and probabilistic risk assessment for breastfed infants

The present study addresses the presence of bisphenols A (BPA) and its analogs bisphenol F (BPF) and S (BPS) in milk of 120 mothers living in Valencia (Spain) and participating in the BETTERMILK project (year 2015). We also studied the factors that could influence the BPA levels and estimated the exposure and the risk for breast fed infants. The frequency of detection of total (conjugated + unconjugated) and unconjugated-BPA were 83% and 77%. with a geometric mean of 0.29 ng/mL and 0.15 ng/mL, respectively. The frequency of detection was much lower for total-BPF (22%) and total-BPS (1.1%). The place of residence of the mother and the use of personal care products showed significant associat…

Pesticide Inhalation Exposure of Applicators and Bystanders Using Conventional and Innovative Cropping Systems in the Valencian Region, Spain

This paper provides scientific results from a European LIFE project carried out in the Valencian region of Spain during the 2017 to 2018 time frame. In 2018, more than 60,000 tons of pesticides were commercialized in Spain, with approximately 15% destined for Valencian crops. In order to improve the air quality in the agricultural areas of this region, an innovative cropping system based on irrigation was developed and compared to conventional treatments based on hand-spray and turbo application. After applying conventional treatments to five types of crops (citrus, persimmon, nectarine, watermelon, and other stone fruits), a total of 13 active substances were detected in the air. The same …

Risk assessment of exposure to phthalates in breastfeeding women using human biomonitoring

In this study, we assessed the presence of 14 phthalate metabolites in the urine of 104 lactating mothers from Valencia (Spain) who took part in the human biomonitoring project BETTERMILK. Nine of the metabolites studied showed detection frequencies >80%, whereas the rest of the metabolites presented low detection frequencies (<5%). The concentrations ranged from <LoQ to 1291 ng/mL with monoethyl phthalate showing the highest concentration, with a geometric mean of 34.90 ng/mL. In general, the phthalate metabolite levels quantified in the present study were lower than the urinary levels found in previous studies that involved lactating mothers. The consumption of packaged juices and the fre…

New screening approach for risk assessment of pesticides in ambient air

We present a novel screening approach for inhalation risk assessment of currently used pesticides (CUPs) in ambient air, based on the measurements of pesticide levels in the inhalable fraction of the particulate matter (PM10). Total concentrations in ambient air (gas + particle phases) were estimated using a theoretical model of distribution of semi-volatile organic compounds between the gas and the particulate phase based on the octanol-air partition (K-oa) of each pesticide. The proposed approach was used in a pilot study conducted in a rural station in Valencia (Spain) from April through to October 2010. Twenty out of 82 analysed pesticides were detected in average concentrations ranging…

Dietary exposure to trace elements and health risk assessment in the Region of Valencia (Spain). A Total Diet Study

ABSTRACTDietary exposure of the Valencian region population to lead, cadmium, inorganic arsenic (iAs), chromium, copper, tin and methylmercury (meHg) was assessed in a total diet study carried out in the region of Valencia in 2010–11. A total of 8100 food samples were collected and analysed. Occurrence data were combined with consumption data to estimate dietary exposure in adults (> 15 years of age) and young children (6–15 years of age). The estimated intake was calculated by a probabilistic approach. Average intake levels (optimistic scenario) for lead, iAs, chromium and tin were 0.21, 0.08, 1.79 and 1.87 µg kg−1 bw day−1 respectively; for Cd and meHg average intake levels were 0.77 and …

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. …

Monitoring programme on cadmium, lead and mercury in fish and seafood from Valencia, Spain: levels and estimated weekly intake.

The study was carried out to determine the current levels of mercury, cadmium, and lead in fish and seafood from the market of Comunitat Valenciana, Spain. Levels of total mercury ranged from 0.02 to 3.15 mg kg⁻¹ w.w. (average = 0.073 mg kg⁻¹ w.w.). Cadmium concentrations ranged from 0.003 to 0.66 mg kg⁻¹ w.w. (average = 0.27 mg kg⁻¹ w.w.) for seafood, and between 0.003 and 0.71 mg kg⁻¹ w.w. (average = 0.01 mg kg⁻¹ w.w.) for marine fish. Concerning lead, concentrations from 0.02 to 0.36 mg kg⁻¹ w.w (average = 0.04 mg kg⁻¹ w.w.) were found in fish, and from 0.02 to 1.02 mg kg⁻¹ w.w. in seafood (average = 0.147 mg kg⁻¹ w.w.). The levels found were, in general, lower than maximum levels propos…

Quick determination of Glyphosate and AMPA at sub µg/L in drinking water by direct injection into LC-MS/MS

Abstract A sensitive, simple and quick method for the determination of glyphosate (Gly) and its degradation product, Aminomethyl phosphonic acid (AMPA), in water through ion chromatography coupled to quadrupole-linear ion trap mass spectrometry has been developed. Sample treatment was based on direct injection and acquisition was implemented in both MS2 and MS3 modes. The LoQs of the method were 0.03 µ/L for both Gly-and AMPA. The recoveries were between 91 and 118% and RSD was lower than 15%. The developed methodology was applied on 436 water samples.

Occurrence of biomarkers of pesticide exposure in non-invasive human specimens.

Biomonitoring has been used in many types of investigations, including national programmes and epidemiological studies, to explore the occurrence of biomarkers of pesticide exposure in the general population or relevant groups. This review discusses recent studies that measure levels of biomarkers of pesticide exposure in non-invasive human specimens such as urine, breast milk, meconium and hair. Specific and non-specific metabolites of organophosphate and pyrethroid insecticides have been widely investigated in urine, where some of the suitable biomarkers present rates of detection higher than 80%, which stand for an ongoing chronic exposure to traces of these chemicals. Hair is a promisin…

Biomonitoring of parabens in human milk and estimated daily intake for breastfed infants

In this study, we assessed the presence of four parabens in human milk of 120 mothers from Valencia (Spain) which took part in a human biomonitoring project (BETTERMILK). The detection frequency ranges of parabens were 41-60% and 61-89% for unconjugated- and total (unconjugated + conjugated)-parabens, respectively. The concentrations ranged from <LoQ to 31 ng/mL and from <LoQ to 49 ng/mL for unconjugated- and total-parabens, respectively. The frequency of use of some cosmetic products and human milk protein levels were the main predictors of parabens in milk. The study evidences the presence of both conjugated and unconjugated paraben forms in human milk. The newborns estimated daily intake…

Exposure and Risk Assessment of Hg, Cd, As, Tl, Se, and Mo in Women of Reproductive Age Using Urinary Biomonitoring

The present study analyzed the exposure and risk assessment of 4 toxic (Hg, Cd, As, Tl) and 2 essential (Se, Mo) elements in 119 Spanish women of reproductive age. The focus was on the elements for which risk-based benchmark, biomonitoring equivalents, or health-related human biomonitoring values have already been established. All elements presented frequencies of detection of 100% (greater than the limit of detection), except for Cd (99%). The 95th percentile concentrations were, for the toxic metals, 358.37 µg/L (total As), 1.10 µg/L (Cd), 0.41 µg/L (Tl), and 3.03 µg/L (total Hg) and, for the essential elements, 68.95 µg/L (total Se) and 154.67 (Mo). We examined sociodemographic factors a…

Determination of 60 Migrant Substances in Plastic Food Contact Materials by Vortex-Assisted Liquid-Liquid Extraction and GC-Q-Orbitrap HRMS

A GC-HRMS analytical method for the determination of 60 migrant substances, including aldehydes, ketones, phthalates and other plasticizers, phenol derivatives, acrylates, and methacrylates, in plastic food contact materials (FCM) has been developed and validated. The proposed method includes migration tests, according to Commission Regulation (EU) 10/2011, using four food simulants (A, B, C, and D1), followed by vortex-assisted liquid&ndash;liquid extraction (VA-LLE) and GC-Q-Orbitrap HRMS analysis in selected ion monitoring (SIM) mode, with a resolving power of 30,000 FWHM and a mass accuracy &le;5 ppm. The method was validated, showing satisfactory linearity (R2 &ge; 0.98 from 40 to 400 …

Biomonitoring of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in human milk: Exposure and risk assessment for lactating mothers and breastfed children from Spain

Abstract The main objective of the present research was to evaluate the levels of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (dl-PCBs) in the human milk of Spanish lactating women who participated in the BETTERMILK project so that exposure and risk could be assessed for these mothers and their breastfed children. The total ∑PCDD/Fs + dl-PCBs TEQ2005 concentrations in the upper-bound (UB) ranged from 1.29 to 13.48 pg TEQ2005 g−1 lipid. The estimated geometric mean level for the sum of PCDD/F and dl-PCBs was 4.10 and 4.42 pg TEQ2005 g−1 lipid, lower-bound (LB) and UB respectively and were below the reference leve…

Determination of bisphenol diglycidyl ether residues in canned foods by pressurized liquid extraction and liquid chromatography–tandem mass spectrometry

Abstract A new confirmatory method for simultaneous determination of bisphenol diglycidyl ether residues (BADGE, BADGE·H2O, BADGE·2H2O, BADGE·H2O·HCl, BADGE·HCl, BADGE·2HCl, BFDGE and BFDGE·2HCl) from canned food has been developed. The proposed method includes extraction by pressurized liquid extraction (PLE) followed by liquid–liquid partition and purification by solid phase extraction (SPE). Several solvent systems and different operating conditions (time, temperature) have been investigated for PLE optimization. A reversed-phase high-performance liquid chromatography (RP-HPLC) coupled to atmospheric pressure chemical ionisation tandem mass spectrometry (APCI-MS–MS) method was developed …

Additional file 1: Table S1. of Distributions and determinants of urinary biomarkers of organophosphate pesticide exposure in a prospective Spanish birth cohort study

Intake of fruit and vegetables according to the maternal sociodemographic and life style characteristics. (DOC 49 kb)

Using semi-permeable membrane devices as passive samplers

Abstract We discuss the present state of, and future developments in, using semi-permeable membrane devices (SPMDs) for environmental monitoring of organic pollutants. SPMDs allow the determination of time-weighted average concentrations of bioavailable pollutants in the sampled media, reducing significantly the costs of analysis compared with active samplers. We summarize developments in SPMDs, including simplified devices and devices modified by incorporating solvents other than triolein, and applications. We review contaminants (e.g., organotin compounds, polycyclic musk, triclosan, petroleum biomarkers, nitrated PAHs, polychlorinated naphthalenes and a wide range of pesticides sampled i…

Biomonitoring of mercury in hair of children living in the Valencian Region (Spain). Exposure and risk assessment.

Abstract In this study, we assessed total mercury levels in hair specimens of 661 children, aged 6 to 11, participating in the BIOVAL programme, a human biomonitoring study carried out by the Health Department of the Regional Government of Valencia (Spain). The reference value (95th percentile) determined for this population, within this programme, was 3.25 μg g−1. Hg concentrations ranged between 0.03 μg g−1 and 8.71 μg g−1, with a geometric mean of 0.79 (CI 95%: 0.73–0.85) μg g−1. This mean value was five times higher than the average levels found in children of 17 other European countries (0.145 μg g−1). About 13% of children had hair mercury levels above the FAO/WHO JECFA guideline of 2…

Distributions and determinants of urinary biomarkers of organophosphate pesticide exposure in a prospective Spanish birth cohort study

Background: Prenatal exposure to organophosphate pesticides (OPs) has been associated with impaired child development. Pesticide exposure determinants need to be studied in order to identify sources and pathways of pesticide exposure. The aim of this paper is to describe prenatal exposure to OPs and evaluate the associated factors in pregnant women. Methods: The study population consisted of pregnant women ( n = 573) who participated in the INMA birth cohort study in Valencia (Spain, 2003 – 2006). OP metabolites were analyzed in maternal urine at the 32nd week of gestation using a liquid chromatography-high resolution mass spectrometry method. The analysis included non-specific (diethyl pho…

Combined target and post-run target strategy for a comprehensive analysis of pesticides in ambient air using liquid chromatography-Orbitrap high resolution mass spectrometry

Abstract A comprehensive strategy for the analysis of current airborne pesticides has been developed using liquid chromatography coupled to high resolution mass spectrometry. The methodology includes both quantitative target analysis and post-run target screening analysis. The quantitative method was validated after a previous statistical optimisation of the main factors governing the ion source ionization and a study of the single-stage Orbitrap fragmentation through the HCD cell. The quantitative method presented recoveries ranging from 73 to 116%, with precision (RSD) lower than 20%, for the 35 substances in the scope of the target method. The full-scan accurate mass data were acquired w…

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

Abstract 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 r…

Particle size distributions of currently used pesticides in ambient air of an agricultural Mediterranean area

This work presents first data on the particle size distribution of 16 pesticides currently used in Mediterranean agriculture in the atmosphere. Particulate matter air samples were collected using a cascade impactor distributed into four size fractions in a rural site of Valencia Region, during July to September in 2012 and from May to. July in 2013. A total of 16 pesticides were detected, including six fungicides, seven insecticides and three herbicides. The total concentrations in the particulate phase (TSP: Total Suspended Particulate) ranged from 3.5 to 383.1 pg m(-3). Most of the pesticides (such as carbendazim, tebuconazole, chlorpyrifos-ethyl and chlorpyrifos-methyl) were accumulated …

Biomonitoring of Phthalates, Bisphenols and Parabens in Children: Exposure, Predictors and Risk Assessment

Exposure to emerging contaminants, such as phthalates, bisphenols and parabens in children has been associated with possible neurodevelopment and endocrine alterations. In the present study, the biomonitoring of biomarkers in children (5–12 years old) from the Valencia Region (Spain) have been implemented using urines from the BIOVAL program. More than 75% of the children studied (n = 562) were internally exposed (&gt

Utilization of long duration high-volume sampling coupled to SPME-GC-MS/MS for the assessment of airborne pesticides variability in an urban area (Strasbourg, France) during agricultural application

Atmospheric samples have been collected between 14 March and 12 September 2012 on a 2-week basis (15 days of sampling and exchange of traps each 7 days) in Strasbourg (east of France) for the analysis of 43 pesticides. Samples (particle and gas phases) were separately extracted using Accelerated Solvent Extraction (ASE) and pre-concentrated by Solid Phase Micro-Extraction (SPME) before analysis by gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). Four SPME consecutive injections at distinct temperatures were made in order to increase the sensitivity of detection for the all monitored pesticides. Currently used detected pesticides can be grouped in four classes; those used i…

Development of a pressurised liquid extraction and liquid chromatography with electrospray ionization-tandem mass spectrometry method for the determination of domoic acid in shellfish.

Amnesic shellfish poisoning (ASP) is a potentially lethal human toxic syndrome which is caused by domoic acid (DA) that originates in marine phytoplankton belonging to the Pseudonitzschia genus. A confirmatory and sensitive procedure has been developed and validated for the determination of DA in shellfish. The proposed method includes pressurised liquid extraction (PLE) with methanol/acetone (9:1), florisil ® cleanup purification inside the PLE extraction cell and detection by liquid chromatography (LC) coupled to electrospray ionization in positive mode tandem mass spectrometry (ESI-MS–MS). Comparison of ionization sources (ESI, atmospheric pressure ionization (APCI) atmospheric pressure …

Wide-range screening of banned veterinary drugs in urine by ultra high liquid chromatography coupled to high-resolution mass spectrometry

In this work, an ultra high performance liquid chromatography-high resolution mass spectrometry (UHPLC-HRMS) methodology is proposed for the multi-class multi-residue screening of banned and unauthorized veterinary drugs in bovine urine, using an Orbitrap Exactive™ analyzer working at a resolving power of 50,000 FWHM in full scan, both in positive and negative mode. The method currently covers 87 analytes belonging to different families such as steroid hormones, β-agonists, resorcylic acid lactones (RAL), stilbens, tranquillizers, nitroimidazoles, corticosteroids, NSAIDs, amphenicoles, thyreostatics and other substances such as dapsone. A database including the elemental composition, the po…

Assessment of metal levels in foodstuffs from the Region of Valencia (Spain).

Graphical abstract

Biomonitoring of 20 elements in urine of children. Levels and predictors of exposure

The levels of 20 elements in the urine of one hundred twenty children (Ages 6-11) from an agricultural and an urban area of Valencia Region, Spain, were assessed. The seven essential elements analysed (Co, Cu, Mn, Mo, Se, V, Zn) presented average concentrations (geometric mean) ranging from 0.22 µg L(-1) to 63 µg L(-1) (except Zn with 525 µg L(-1)). Eight out of the 13 toxic elements determined (As, Ba, Cd, Cs, Ni, Pb, Tl, Hg) had frequencies of detection of 100%, with geometric mean concentrations from 0.17 µg L(-1) (Cd) to 33.6 µg L(-1) (As). About 18% of children revealed urinary levels of total As higher than the normal range of 100 µg L(-1) accepted by the ATSDR. The urine analysis was…

Optimization of Resolving Power, Fragmentation, and Mass Calibration in an Orbitrap Spectrometer for Analysis of 24 Pesticide Metabolites in Urine

Mass spectrometer parameters such as Resolving Power, type of fragmentation, and mass calibration mode were optimized in the analysis of 24 pesticide metabolites in human urine using Ultra-High Pressure Liquid Chromatography coupled to Orbitrap High-Resolution Mass Spectrometer (UHPLC-HRMS). The best results were achieved with a Resolving Power of 25,000 FWHM and by applying Collision Induced Dissociation fragmentation mode (40 eV).

Evaluation of sampling adsorbents and validation of a LC-HRMS method for determination of 28 airborne pesticides

A new strategy for sampling, using a low-volume sampler, and determination of airborne pesticides by liquid chromatography coupled to high-resolution mass spectrometry (UHPLC-HRMS) has been developed. The trapping efficiency of three adsorbents (sandwich PUF-XAD2-PUF; XAD-2 and XAD-4) was tested for 33 currently used pesticides and the first adsorbent (PUF-XAD2-PUF) was selected because it presented the highest retention capacity without breakthrough. Selected PUF-XAD2-PUF had the following design: 5 g of Amberlite XAD-2 sandwiched between two cylinders of PUF (6.87 cm(3), height: 1.4 cm, diameter: 2.5 cm). A validation of the analytical methodology that includes microwave extraction with e…

Multi-residue analysis of 30 currently used pesticides in fine airborne particulate matter (PM 2.5) by microwave-assisted extraction and liquid chromatography–tandem mass spectrometry

A confirmatory and rapid procedure has been developed for the determination of 30 currently used pesticides (CUP) in fine airborne particulate matter (PM 2.5) at trace level. The proposed method includes extraction of PM 2.5-bound pesticides by microwave-assisted extraction (MAE) followed by a direct injection into LC-MS/MS. The main parameters affecting the MAE extraction (time, temperature and volume of solvent) were optimised using statistical design of experiments (DoE). The matrix effect was also evaluated. Recoveries ranged from 72 to 109% and the limit of quantification (LoQ) was 32.5 pg m(-3) for chlorpyrifos, 13.5 pg m(-3) for fenhexamid, imazalil and prochloraz, and 6.5 pg m(-3) f…

Protein Biomarkers of Bovine Defective Meats at a Glance: Gel-Free Hybrid Quadrupole-Orbitrap Analysis for Rapid Screening

An understanding of biological mechanisms that could be involved in the stress response of animal cattle prior to slaughter is critical to create effective strategies aiming at the production of high-quality meat. The sarcoplasmic proteome of directly extracted samples from normal and high ultimate pH (pHu) meat groups was studied through a straightforward gel-free strategy supported by liquid chromatography hybrid quadrupole-Orbitrap high-resolution mass spectrometry (LC-HRMS) analysis. A stepped proteomic pipeline combining rapid biomarker hunting supported by qualitative protein Mascot scores followed by targeted label-free peptide quantification revealed 26 descriptors that characterize…

Probabilistic risk assessment of the exposure to polybrominated diphenyl ethers via fish and seafood consumption in the Region of Valencia (Spain)

The study was carried out to estimate the dietary intake of polybrominated diphenyl ethers (PBDEs) in the Region of Valencia (Spain) in order to evaluate the resultant risk. The PBDE levels in fish and seafood (a total of 206 samples) were determined. Dietary intake was estimated using results of PBDE analyses in fish and seafood marketed in the Region of Valencia over the period 2007-2012 and data of the first Valencian Food Consumption Survey, conducted in 2010. Two scenarios were assumed for left-censored results: the lower-bound (LB) scenario, in which unquantified results (below the limit of quantification (LOQ)) were set to zero and the upper-bound (UB) scenario, in which unquantified…

Biomonitoring of bisphenols A, F, S and parabens in urine of breastfeeding mothers: Exposure and risk assessment

In the present study we used human biomonitoring to assess the internal exposure and the risk to four parabens and three bisphenols in 103 Spanish breastfeeding mothers participating in the BETTERMIILK project. Urinary methylparaben (MP), ethylparaben (EP), propylparaben (PP) and butylparaben (BP) presented detection frequencies ranging from 12% (BP) to 92% (MP), while bisphenol A (BPA), bisphenol F (BPF) and bisphenol S (BPS) were detected in 76% (BPA) and 20% (BPF, BPS) of the mothers. Average paraben concentrations (geometric mean) ranged from 0.021 ng mL(-1) (BP) to 17.7 ng mL(-1) (MP), whereas bisphenols had geometric means concentrations from 0.042 ng mL(-1) (BPF) to 0.927 ng mL(-1) (…

New perspectives in the use of semipermeable membrane devices as passive samplers.

This review shows the state of the art, from 2000 to nowadays, of the use of semipermeable membrane devices (SPMDs) for monitoring persistent organic pollutants in both, air and aquatic environments. Since their first use in 1990, SPMDs have been employed for many environmental purposes, like air and water pollution monitoring. We have focussed the study in three subjects: (i) novel compounds accumulated by SPMDs, (ii) modifications of SPMDs to improve their specific uptake properties and (iii) alternatives in sample pre-treatment for the determination of pollutants accumulated in SPMDs.

GC–MS characterization of contemporary pesticides in PM10 of Valencia Region, Spain

Pesticides in the inhalable fraction of particulate matter (PM10) should be well tracked in order to contribute information to future exposure assessment in individuals of the general public. A total of 40 current-used pesticides and metabolites were searched for in ambient air samples collected from January through December 2010. The samples were taken from one remote, one urban and three rural sites in Valencia Region (Spain) and analyzed using liquid chromatography coupled to mass spectrometry in tandem (LC-MS/MS). In the PM10 fraction 17 pesticides and metabolites were detected overall, two of them currently banned (carbofuran and omethoate, although the latter is a metabolite of the pe…

Particle size distributions of currently used pesticides in a rural atmosphere of France

This work presents first data on the particle size distributions of current-used pesticides in the atmosphere. Ambient air samples were collected using a cascade impactor distributed into four size fractions in a rural site of Centre Region (France). Most pesticides were accumulated in the fine (0.1-1 mu m) particle size fraction such as cyprodinil, pendimethalin, fenpropidin, fenpropimorph and spiroxamine. Other pesticides such as acetochlor and metolachlor presented a bimodal distribution with maximum concentrations in the ultrafine (0.03-0.1 mu m) coarse (1-10 mu m) and in the ultrafine fine size ranges, respectively. No pesticides were detected in the size fraction >10 mu m. (C) 2013 El…

Biomonitoring of mercury in hair of breastfeeding mothers living in the Valencian Region (Spain). Levels and predictors of exposure

This study focused on the evaluation of the levels of total mercury in hair among 120 breastfeeding mothers aged 20 to 45-. The concentrations of Hg ranged from 0.07 to 6.87 mu g/g with a geometric mean (GM) of 1.22 mu g/g. This GM is six times higher than the average internal exposure of mothers from other 17 European countries (0.225 mu g/g). Near 70% of mothers presented levels of Hg above the USA EPA internal exposure guideline of 1 mu g/g, and 27% exceeded the EFSA health-based guidance value of 1.9 mu g/g. The multivariate regression analysis revealed that age, smoking and fish consumption (sword fish, small fat fish, small lean fish) were the major predictors of mercury in hair. (C) …

Determination of 21 perfluoroalkyl substances and organophosphorus compounds in breast milk by liquid chromatography coupled to orbitrap high-resolution mass spectrometry.

Abstract The human exposure to perfluoroalkyl (PFASs) and organophosphorus (OPs) compounds is a cause of concern and its determination in biological matrices, including human milk, is an emergent approach for evaluate their exposure. A comprehensive strategy for the quantitative determination of 21 PFASs and OPs compounds in breast milk was developed. The proposed method includes an extraction and clean-up procedure based on the QuEChERs methodology followed by an ultra-high performance liquid chromatography coupled to high-resolution mass spectrometry (UHPLC-HRMS) determination. The full-scan mass data were acquired with a resolution of 50000 FWHM and a mass accuracy better than 5 ppm. Met…

Retrospective analysis of pesticide metabolites in urine using liquid chromatography coupled to high-resolution mass spectrometry

Abstract A comprehensive retrospective analysis of pesticide metabolites in urine was developed, using liquid chromatography coupled to Orbitrap high-resolution mass spectrometry (UHPLC-HRMS) that includes both post-run target (suspect screening) and non-target screening. An accurate-mass database comprising 263 pesticide metabolites was built and used for the post-run screening analysis. For non-target analysis, a “fragmentation-degradation” relationship strategy was selected. The proposed methodology was applied to 49 real urine samples from pregnant women. In the post-target analysis 26 pesticide metabolites were tentatively identified, 8 of which (2-diethylamino-6-methyl-pyrimidinol; 3-…

Microwave-assisted extraction of polybrominated diphenyl ethers and polychlorinated naphthalenes concentrated on semipermeable membrane devices

Abstract Microwave-assisted extraction (MAE) has been evaluated as an alternative to dialysis for the extraction of polybrominated diphenyl ethers (PBDEs) and polychlorinated naphthalenes (PCNs) sampled by semipermeable membrane devices (SPMDs), using gas chromatography coupled to tandem mass spectrometry (GC–MS–MS). For MAE optimization a two level full factorial design 2 3 , plus a centre point, which involves 11 randomized runs was used. The results showed that the temperature had a significant influence on the extraction of the nine PBDEs and four PCNs tested. Also, the solvent volume had a positive influence on the extraction of PBDEs and PCNs, but only in latter compounds, it achieves…

Dietary exposure and risk assessment of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and dioxin-like polychlorinated biphenyls of the population in the Region of Valencia (Spain)

Dietary exposure of the Valencia Region population to polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and PCBs was assessed in the Region of Valencia in 2010–2011. A total of 7700 food samples were collected. Occurrence data were combined with consumption data to estimate dietary exposure in adults (&gt;15 years of age) and young people (6–15 years of age). The estimated intake was calculated by a probabilistic approach. Average intake levels (upper-bound scenario) were 1.58 and 2.76 pg toxic equivalent (TEQ) kg−1 body weight (bw) day−1 for adults and young people, respectively. These average intakes are within range of the tolerable daily intake of 1–4 pg W…

Microwave-assisted extraction of OCPs, PCBs and PAHs concentrated by semi-permeable membrane devices (SPMDs)

Abstract Microwave-assisted extraction (MAE) has been evaluated as an alternative to dialysis for extraction of some water-borne hydrophobic contaminants sampled by semi-permeable membrane devices (SPMDs). Seven organochlorine pesticides (OCPs), 11 polychlorinated biphenyls (PCBs) and 13 polycyclic aromatic hydrocarbons (PAHs) were accumulated in SPMDs at nanogram levels and extracted with three 3-min irradiation cycles with 33 mL of a solvent mixture hexane–water (10:1,v/v) in each cycle. The developed MAE method gave for all analytes investigated statistically comparable extraction yields with those found by dialysis carried out with a total volume of 250 mL hexane for 48 h at room temper…

Analysis of currently used pesticides in fine airborne particulate matter (PM 2.5) by pressurized liquid extraction and liquid chromatography-tandem mass spectrometry.

During and after the application of currently used pesticides (CUPs) a significant fraction of applied pesticides can be lost to the air. A confirmatory and rapid procedure has been developed for the determination of four fungicides (carbendazim, thiabendazol, imazalil and bitertanol), three insecticides (imidacloprid, methidathion and pyriproxyfen), one helicide (methiocarb) and one acaricide (hexythiazox) in fine airborne particulate matter (PM 2.5) at trace level. The proposed method includes extraction of PM 2.5-bound pesticides by pressurized liquid extraction (PLE) followed by a direct injection into LC-MS/MS. The main parameters affecting the performance of the electrospray ionizatio…

Children’s exposure to polycyclic aromatic hydrocarbons in the Valencian Region (Spain): Urinary levels, predictors of exposure and risk assessment

Polycyclic aromatic hydrocarbons (PAHs) are pollutants that are released into the environment during incomplete combustion of organic matter and which can have a negative effect on human health. PAHs enter the human body mostly through ingestion of food or inhalation of tobacco smoke. The purpose of the present study is to evaluate the internal levels of PAHs that children living in the Valencian Region (Spain) are exposed to. In total, we measured eleven biomarkers of exposure to naphthalene, fluorene, phenanthrene, pyrene, and benzo(a)pyrene in the urine of 566 children aged 5-12. The analytical method was based on a liquid-liquid extraction of the PAH metabolites from the urine samples, …

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

Abstract 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 …

Design of experiment approach for the optimization of polybrominated diphenyl ethers determination in fine airborne particulate matter by microwave-assisted extraction and gas chromatography coupled to tandem mass spectrometry.

Abstract A sensitive and selective procedure for the determination of 12 polybrominated diphenyl ethers (BDE-28, BDE-49, BDE-47, BDE-66, BDE-100, BDE-119, BDE-99, BDE-155, BDE-154, BDE-153, BDE-139 and BDE-183) in airbone particulate matter (PM2.5) at trace level has been developed. The proposed method includes extraction PM2.5-bound PBDEs by microwave-assisted extraction (MAE) followed by gel permeation chromatography (GPC) clean-up and determination by GC-MS/MS using a programmed temperature vaporizer (PTV) in large volume injection (LVI) mode to introduce the sample to the chromatographic system. A design of experiment (DoE) approach was used for the optimization of large volume injectio…

Polybrominated diphenyl ethers in foods from the Region of Valencia: Dietary exposure and risk assessment

Abstract Dietary exposure to polybrominated diphenyl ethers (PBDEs) of the population in the Region of Valencia, Spain, was assessed. A group of 320 composite samples of different fatty foods was collected and analyzed, including the following: vegetable oils, and foods of animal origin such as (a) fish and seafood, (b) eggs, (c) milk and dairy products, and (d) meat and meat products. Two scenarios were assumed for left-censored results: lower-bound (LB) and upper-bound (UB). Vegetable oils, and fish and seafood presented the highest content of PBDEs [mean values of 503 and 464 pg g−1 wet weight (ww) for total PBDEs, respectively, in the UB]. The dominating congeners were BDE47 in the food…

Human risk assessment and regulatory framework for minerals in food

Analytical methods for human biomonitoring of pesticides. A review.

Biomonitoring of both currently-used and banned-persistent pesticides is a very useful tool for assessing human exposure to these chemicals. In this review, we present current approaches and recent advances in the analytical methods for determining the biomarkers of exposure to pesticides in the most commonly used specimens, such as blood, urine, and breast milk, and in emerging non-invasive matrices such as hair and meconium. We critically discuss the main applications for sample treatment, and the instrumental techniques currently used to determine the most relevant pesticide biomarkers. We finally look at the future trends in this field.

Occurrence of currently used pesticides in ambient air of Centre Region (France)

Ambient air samples were collected, from 2006 to 2008 at three rural and two urban sites in Centre Region (France) and analyzed for 56 currently used pesticides (CUPS), of which 41 were detected. The four CUPs most frequently detected were the herbicides trifluralin, acetochlor and pendimethalin and the fungicide chlorothalonil, which were found with frequencies ranging between 52 and 78%, and with average concentrations of 1.93, 1.32, 1.84 and 12.15 ng m(-3), respectively. Among the detected pesticides, concentrations of eight fungicides (spiroxamine, fenpropimorph, cyprodinil, tolyfluanid, epoxiconazole, vinchlozolin, fluazinam, fludioxinil), two insecticides (propargite, ethoprophos), an…

Exposure to non-persistent pesticides in the Spanish population using biomonitoring: A review

Abstract Although Spain does not have a regular national human biomonitoring program yet, different research groups are active in evaluating the exposure of children and adults to chemicals. In the last seven years, several studies in Spain have evaluated the internal exposure of the population to currently used pesticides. The present review analyzes the scope of these studies, the employed analytical methods and the main results of the exposure and risk, mainly for children and mothers. The frequency of exposure to biomarkers of exposure to organophosphate pesticides is high. Some non-specific dialkyl phosphate metabolites (DAPs), such as the diethyl phosphate (DEP), present Detection Fre…

Exposure assessment of Spanish lactating mothers to acrylamide via human biomonitoring.

Abstract 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 co…

Exposure and risk assessment to arsenic species in Spanish children using biomonitoring

We present a new approach to arsenic (As) risk assessment using biomonitoring. In this pilot study we determined the levels of total and speciated urinary arsenicin 109 Spanish school children aged between 6 and 11 years, and interpreted these concentrations in a risk assessment context. The geometric mean (GM) for total As (TAs) was 33.82 mu/L. The order of occurrence and average concentrations of the different species was arsenobetaine (AsB) (100%, 15 mu g/L), dimethylarsinic (DMA) (97%, 8.32 mu g/L), monomethylarsonic (MMA) (26%, 027 mu g/L) and inorganic As (iAs) (4%, 0.14 mu g/L). 18% of children presented exposures to inorganic arsenic (7.52 mu g/g creatinine) higher than guidance val…

Determination of acrylamide in coffee and chocolate by pressurised fluid extraction and liquid chromatography-tandem mass spectrometry.

A selective and sensitive procedure has been developed and validated for the determination of acrylamide in difficult matrices, such as coffee and chocolate. The proposed method includes pressurised fluid extraction (PFE) with acetonitrile, florisil clean-up purification inside the PFE extraction cell and detection by liquid chromatography (LC) coupled to atmospheric pressure ionisation in positive mode tandem mass spectrometry (APCI-MS-MS). Comparison of ionisation sources (atmospheric pressure chemical ionisation (APCI), atmospheric pressure photoionization (APPI) and the combined APCI/APPI) and clean-up procedures were carried out to improve the analytical signal. The main parameters aff…

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

Abstract 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…

Development of a novel methodology for determination of dialkyl phosphates in human urine using liquid chromatography-tandem mass spectrometry

Abstract In this study a fast and sensitive method was developed for the quantitative determination of six dialkyl phosphates (DAPs) in human urine using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The proposed methodology was based on liquid-liquid extraction (LLE) with diethyl ether and ethyl acetate using MgSO4 and NaCl, followed by liquid chromatography and mass spectrometry detection in the selected reaction mode (SRM) with negative electrospray ionization (ESI-). Detection settings were optimized by design of experiments (DoE). Dibutyl phosphate (DBP) was used as internal standard. Several criteria established in the SANTE/11813/2017 guidance document for pesticide resi…

Comprehensive analysis of photoinitiators and primary aromatic amines in food contact materials using liquid chromatography High-Resolution Mass Spectrometry

Abstract A comprehensive strategy for the analysis of UV-ink photoinitiators and primary aromatic amines (PAAS) in food-packaging materials such as, juice tetrabricks, pouches and bags has been developed using liquid chromatography coupled to Orbitrap High-Resolution Mass Spectrometry (LC-Orbitrap-HRMS). The methodology includes both quantitative target analysis and post-run target screening analysis. The quantitative method was validated after a previous optimisation of the single-stage Orbitrap fragmentation through the Higher-Energy Collisional Dissociation (HCD) Cell. Overall, the quantitative method presented recoveries ranging from 78% to 119%, with a precision (RSD) lower than 20%, f…

Analytical strategies for organic food packaging contaminants

In this review, we present current approaches in the analysis of food-packaging contaminants. Gas and liquid chromatography coupled to mass spectrometry detection have been widely used in the analysis of some relevant families of these compounds such as primary aromatic amines, bisphenol A, bisphenol A diglycidyl ether and related compounds, UV-ink photoinitiators, perfluorinated compounds, phthalates and non-intentionally added substances. Main applications for sample treatment and different types of food-contact material migration studies have been also discussed. Pressurized Liquid Extraction, Solid-Phase Microextraction, Focused Ultrasound Solid-Liquid Extraction and Quechers have been …

Liquid chromatography‐Orbitrap Tribrid high‐resolution mass spectrometry using data dependent‐tandem mass spectrometry with triple stage fragmentation as a screening tool to perform identification and risk assessment of unknown substances in food contact epoxy resin

A new, fast, and automatic approach has been applied for the tentative identification of unknown substances released by food contact epoxy resin after performing a migration test with food simulant. This approach combines intelligent data acquisition with AcquireX linked to liquid chromatography-Orbitrap Tribrid high-resolution mass spectrometry using data dependent-tandem mass spectrometry with triple stage fragmentation coupled to Compound Discoverer™ software for automated data processing and compound identification. The identification of the observed features was performed using a set of identification criteria, including exact mass, isotope pattern, tandem mass spectrometry spectra mat…

Evaluation of mycotoxins and their metabolites in human breast milk using liquid chromatography coupled to high resolution mass spectrometry

Humans can be exposed to mycotoxins through the food chain. Mycotoxins are mainly found as contaminants in food and could be subsequently excreted via biological fluids such as urine or human breast milk in native or metabolised form. Since breast milk is usually supposed as the only food for new-borns, the occurrence of mycotoxins in thirty-five human milk samples was evaluated by a newly developed method based on QuEChERS extraction and UHPLC-HRMS detection. The method described here allows the detection of target mycotoxins in order to determine the quality of this initial feeding. The method has been fully validated, with recoveries ranging from 64% to 93% and relative standard deviatio…

Sampling and analysis of pesticides in ambient air.

Developments in the sampling and determination of pesticides in ambient air have been discussed and data on the occurrence of pesticides in atmosphere have been presented. Developments in active sampling methods were reviewed and the different materials used for trapping pesticides from gas and particulate phases were discussed. Likewise, the use and developments of passive air samplers were reviewed. This article pays special attention to the analysis of pesticides trapped from ambient air, and recapitulate the procedures for extraction, clean-up and determination of these substances. Improvements in sampling procedures, analytical methods and monitoring activities are necessary to advance…

Biomonitoring of glyphosate and AMPA in the urine of Spanish lactating mothers

The objectives of this study were to evaluate the urinary levels of Glyphosate (Gly) and its metabolite aminomethylphosphonic acid (AMPA) in Spanish breastfeeding mothers (n = 97), to identify the main predictors of exposure and to perform a risk assessment. Urine samples were analyzed using a method based on solid phase extraction and liquid chromatography tandem mass spectrometry (LC-MS/MS) determination. The developed method showed limits of quantification of 0.1 μg/L for both analytes. The detection frequencies (DFs) were 54% for Gly and 60% for AMPA, with geometric means (GMs) of 0.12 μg/L and 0.14 μg/L, respectively. In the statistical analysis, no relationship was found between the u…

Determination of four parabens and bisphenols A, F and S in human breast milk using QuEChERS and liquid chromatography coupled to mass spectrometry

Abstract For the first time, a multiresidue, sensitive and high throughput method for determination of bisphenol A, F and S and 4 parabens (methyl paraben, ethyl paraben, propyl paraben and butyl paraben) in human breast milk was developed. The proposed method includes an extraction and clean-up procedure based on QuEChERS methodology followed by liquid chromatography coupled to triple quadrupole mass spectrometry determination. Negative atmospheric pressure chemical ionization in the selected reaction monitoring mode was used for mass detection. During the method validation the recoveries varied between 83 and 115% with a precision lower than 20% for all analytes using spiked levels from 0…

Selection of sampling adsorbents and optimisation and validation of a GC-MS/MS method for airborne pesticides

ABSTRACTA methodology for the sampling and determination of airborne pesticides has been developed. The trapping efficiency of three adsorbents, namely XAD-2,XAD-4 and a sandwich sorbent (PUF-XAD2-PUF), was tested for 34 pesticides and the latter was selected because it presented the highest retention capacity without breakthrough. Pesticides were determined by gas chromatography coupled to an ion trap mass spectrometer in tandem. The method showed recoveries ranging from 70% to 120% with limits of quantification in the range of 16.1–322.6 pg m−3 when 155 m3 were sampled. This analytical strategy was applied to 10 indoor air samples collected in dwellings from the Valencian Region. Six pest…

Methodological Aspects for the Implementation of the Air Pesticide Control and Surveillance Network (PESTNet) of the Valencian Region (Spain)

A large amount of pesticide, applied mainly during agricultural practice, is released into the atmosphere, decreasing air quality and potentially causing public health problems. The Valencian region, after Andalusia, is the Spanish region with the highest consumption of pesticides owing to its large areas of agricultural land and the existence of crops that require intensive use of pesticides. In this work, we describe the sampling and analytical tools developed in the last decade and their transference to the Regional Department for Environment, where the main objective of the research was the creation and implementation of an Air pesticide control and surveillance network (PESTNet) in the…

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…

Chronic cumulative risk assessment of the exposure to organophosphorus, carbamate and pyrethroid and pyrethrin pesticides through fruit and vegetables consumption in the region of Valencia (Spain).

In the present study, the chronic cumulative exposure to organophosphorus (OPs), carbamates (CBs) and pyrethroid and pyrethrin (PPs) pesticides in the region of Valencia through fruit and vegetables consumption is presented. A total of 752 samples and 84 pesticides were studied of which, 52 were OPs, 23 CBs and 9 PPs. Residue data were derived from the Valencia Region monitoring program 2007-2011 and food consumption levels from a questionnaire-based dietary survey conducted in 2010 in the same area. The relative potency factor (RPFs) approach was used to estimate chronic cumulative dietary exposure to OPs, CBs and PPs using acephate, oxamyl and deltamethrin as index compounds, respectively…

Human exposure and risk assessment to airborne pesticides in a rural French community

Abstract Outdoor air samples collected during the pesticide agricultural application period (spring and summer) from a rural community in the Centre Region (France) were analyzed to investigate temporal variation of atmospheric pesticide levels (2006–2013) and human inhalation exposure in adults, children and infants. The most frequently detected pesticides were herbicides (trifluralin, pendimethalin), fungicides (chlorothalonil) and insecticides (lindane and α-endosulfan). The three currently-used pesticides most frequently detected presented concentrations ranging from 0.18 to 1128.38 ng m − 3 ; 0.13 to 117.32 ng m − 3 and 0.16 to 25.80 ng m − 3 for chlorothalonil, pendimethalin and trifl…

Target analysis of primary aromatic amines combined with a comprehensive screening of migrating substances in kitchen utensils by liquid chromatography-high resolution mass spectrometry.

An analytical strategy including both the quantitative target analysis of 8 regulated primary aromatic amines (PAAs), as well as a comprehensive post-run target screening of 77 migrating substances, was developed for nylon utensils, using liquid chromatography-orbitrap-high resolution mass spectrometry (LC-HRMS) operating in full scan mode. The accurate mass data were acquired with a resolving power of 50,000 FWHM (scan speed, 2 Hz), and by alternating two acquisition events, ESI+ with and without fragmentation. The target method was validated after statistical optimization of the main ionization and fragmentation parameters. The quantitative method presented appropriate performance to be u…

Development of a method for the analysis of seven banned azo-dyes in chilli and hot chilli food samples by pressurised liquid extraction and liquid chromatography with electrospray ionization-tandem mass spectrometry

An automated, confirmatory and sensitive procedure has been developed and validated for the determination of Sudan (I-IV), Sudan Orange G, Sudan Red 7B and Para Red in hot chilli food samples. The proposed method includes pressurised liquid extraction (PLE) with acetone, gel permeation chromatography (GPC) clean-up and detection by liquid chromatography (LC) coupled to electrospray ionization in positive mode tandem mass spectrometry (ESI-MS-MS). The main parameters affecting the performance of the different ionization sources and PLE parameters were previously optimised using statistical design of experiments (DOE). The method was in-house validated on chilli powder and chilli meat. Linear…

Dietary exposure to trace elements and health risk assessment in the region of Valencia, Spain: a total diet study

Dietary exposure of the Valencian region population to lead, cadmium, inorganic arsenic (iAs), chromium, copper, tin and methylmercury (meHg) was assessed in a total diet study carried out in the region of Valencia in 2010–11. A total of 8100 food samples were collected and analysed. Occurrence data were combined with consumption data to estimate dietary exposure in adults (&gt; 15 years of age) and young children (6–15 years of age). The estimated intake was calculated by a probabilistic approach. Average intake levels (optimistic scenario) for lead, iAs, chromium and tin were 0.21, 0.08, 1.79 and 1.87 µg kg−1 bw day−1 respectively; for Cd and meHg average intake levels were 0.77 and 0.54 …