Determinants of exposure to acrylamide in European children and adults based on urinary biomarkers: results from the "European Human Biomonitoring Initiative" HBM4EU participating studies.

Little is known about exposure determinants of acrylamide (AA), a genotoxic food-processing contaminant, in Europe. We assessed determinants of AA exposure, measured by urinary mercapturic acids of AA (AAMA) and glycidamide (GAMA), its main metabolite, in 3157 children/adolescents and 1297 adults in the European Human Biomonitoring Initiative. Harmonized individual-level questionnaires data and quality assured measurements of AAMA and GAMA (urine collection: 2014-2021), the short-term validated biomarkers of AA exposure, were obtained from four studies (Italy, France, Germany, and Norway) in children/adolescents (age range: 3-18 years) and six studies (Portugal, Spain, France, Germany, Luxembourg, and Iceland) in adults (age range: 20-45 years). Multivariable-adjusted pooled quantile regressions were employed to assess median differences (ß coefficients) with 95% confidence intervals (95% CI) in AAMA and GAMA (µg/g creatinine) in relation to exposure determinants. Southern European studies had higher AAMA than Northern studies. In children/adolescents, we observed significant lower AA associated with high socioeconomic status (AAMA:ß = - 9.1 µg/g creatinine, 95% CI - 15.8, - 2.4; GAMA: ß = - 3.4 µg/g creatinine, 95% CI - 4.7, - 2.2), living in rural areas (AAMA:ß = - 4.7 µg/g creatinine, 95% CI - 8.6, - 0.8; GAMA:ß = - 1.1 µg/g creatinine, 95% CI - 1.9, - 0.4) and increasing age (AAMA:ß = - 1.9 µg/g creatinine, 95% CI - 2.4, - 1.4; GAMA:ß = - 0.7 µg/g creatinine, 95% CI - 0.8, - 0.6). In adults, higher AAMA was also associated with high consumption of fried potatoes whereas lower AAMA was associated with higher body-mass-index. Based on this large-scale study, several potential determinants of AA exposure were identified in children/adolescents and adults in European countries.

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.

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

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 Frequencies (DFs) in the range of 65-92% in various studies. Also, the specific biomarker of the chlorpyrifos (3,5,6-trichloro-2-pyridinol, TCPy), achieves Detection Frequencies between 74% and 100% in many studies. For pyrethroids, the metabolite 3-phenoxybenzoic acid (PBA) is present, in general, in more than the 65% of the studied samples. Highly polar herbicides were only assessed in one study and both glyphosate and its metabolite aminomethylphosphonic acid showed Detection Frequencies around 60%. However, putting the biomonitoring data in a risk assessment context, the mean Hazard Quotient (HQ), used as a metric for the individual risk, ranges from 0.0006 (glyphosate) to 0.93 in farm workers (parathion), which means that is unlike that the exposure poses a health concern (HQ < 1).

Biomonitoring of polycyclic aromatic hydrocarbons in the urine of lactating mothers: Urinary 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.

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

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 most important predictors of pesticide exposure. Pesticide risk assessment is estimated using two different strategies: one based on the pesticides' mode of action (MoA); and the other based on cumulative assessment groups (CAGs), proposed by EFSA. The estimated daily intakes (EDIs) ranged from 0.08 (chlorpyrifos) to 1.62 µg·kg bw-1 (λ-cyhalothrin). The MoA approach resulted in hazard quotients ranging from 0.01 (chlorpyrifos) to 0.65 (λ-cyhalothrin), and a hazard index for OPs lower than 1. Similarly, the risk assessment based on CAGs led to total margins of exposure (MOETs) far from 100. In conclusion, both risk assessment strategies does not reveal any evidence of a potential health risk due to pesticide exposure in Spanish children.

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

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 0.1 to 50 ng mL-1. The LOQ was 0.10 ng mL-1 for most of the analytes. The proposed method was successfully applied for the determination of these compounds in 10 breast milk samples from volunteer lactating mothers from the Valencian region (Spain). Among parabens, methyl paraben presented the highest detection frequency (80%) with a concentration range of 0.11-7.00 ng mL-1, while bisphenol A was detected more frequently than BPF and BPS (80% of detection frequency) with concentrations ranging from 0.13 to 1.62 ng mL-1.