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•Temporal variability in urinary neonicotinoid concentrations was examined.•Seven neonicotinoids/metabolites were detected in 75–100% of urine samples.•Intraclass correlation ...coefficients for urinary neonicotinoids ranged 0.02–0.42.•Minimum number of samples required to predict individual’s exposure was 16–172.•Urinary levels of neonicotinoids/metabolites were associated with oxidative stress.
Human exposure to neonicotinoid insecticides (hereafter “neonics”) is a concern. Spot urine samples have been widely used in the assessment of exposure to neonics. Urinary concentrations, however, can vary greatly over time due to variable exposure, potentially leading to exposure misclassification. In this study, within- and between-individual variability of urinary concentrations of 13 neonics and their metabolites collected consecutively for up to 44 days from 19 individuals were examined. We also measured seven oxidative stress biomarkers (OSBs) in repeated urine samples to elucidate their relationship with neonic exposure by mixed regression models. Intraclass correlation coefficients (ICCs, a ratio of between-individual variance to total variance) were used to assess the reproducibility of neonic/metabolite concentrations. Sensitivity and specificity were used to evaluate how well spot urine samples determined an individual’s average exposure over 44 days. A fair to good reproducibility was observed for N-desmethyl-acetamiprid (ICC = 0.42), whereas thiamethoxam, imidacloprid, clothianidin, imidaclothiz, 6-chloronicotinic acid, and sulfoxaflor showed poor reproducibility (ICC = 0.02–0.37). Use of single-spot urine samples to classify high (top 33%) exposure showed higher specificities (0.68–0.92) than sensitivities (0.32–0.88). The minimum number of specimens (k) required to estimate participant-specific mean for neonic exposures within 20% of the “true” values ranged from 16 to 172. Significant positive correlations were found between some of neonic and OSB concentrations. The high variability found in the urinary concentrations of most neonics/metabolites suggests that a single measurement can result in exposure misclassification.
•A PLE-MEPS-GC–MS/MS method was developed to determine BDEs in sewage sludge.•MEPS provides sensitivity enhancement, resulting in a decrease of detection limits.•Automated on-line extract clean-up ...improves detection and protects GC–MS from dirt.•Sewage sludge from La Rioja showed BDE levels between 53.9 and 76.8ngg−1.
In this work, a method based on selective pressurised liquid extraction followed by microextraction by packed sorbents (MEPS) for the determination of brominated diphenyl ethers (BDEs) in sewage sludge is presented. The factors affecting the MEPS procedure were optimised. Acetone:water (25:75) sPLE extracts were drawn-ejected 10 times through C18 cartridges at 5μLs−1. The cartridge was dried five times with 250μL of air and the BDEs were eluted at 25μLs−1 with 100μL of n-hexane that were directly injected at 13μLs−1 in the GC–MSMS system. Under these conditions, there were no carry-over effects. The method was characterised in terms of limits of detection, repeatability, intermediate precision and accuracy. The use of MEPS for the determination of BDEs in sewage sludge means an improvement of the limits of detection due to the preconcentration and clean-up performed before the injection of the whole elute in the PTV injector. The GC–MSMS LODs (25pgmL−1) were improved with MEPS to less than 3pgmL−1. RSD less than 7% and recovery values from 92% to 102% were shown. Finally, the method was applied to the sPLE extract analyses of sewage sludge from several wastewater treatment plants in La Rioja. To our knowledge, this is the first time that the MEPS technique has been applied to the analysis of BDEs, and the first time that it has been used for the analysis of extracts from a solid sample.
Exposure of humans to pesticides is widespread. Measurement of urinary levels of pesticides and their metabolites is often used in the assessment of body burdens and exposure doses to these ...chemicals. An understanding of temporal variability in urinary levels of pesticides within individuals is critical for accurate exposure assessment. We examined within- and between-individual variability in concentrations of nine organophosphate and pyrethroid insecticides as well as two phenoxy herbicides in urine collected consecutively for up to 44 days from 19 individuals. Seven oxidative stress biomarkers also were measured in urine samples to elucidate their relationship with pesticide exposure. Intraclass correlation coefficients (ICCs) were calculated to assess reproducibility in urinary pesticide concentrations from repeated measures. Sensitivity and specificity analyses were performed to evaluate the suitability of spot urine to characterize average exposures. Data analysis was further limited to seven pesticides and their metabolites, which had a detection frequency of >60%. Poor reproducibility was found for the seven pesticides and their metabolites in both spot (ICCs ≤0.24) and first-morning-void (FMV) samples (ICCs <0.38) collected during the 44-day study period. Use of single-spot or FMV sample to classify high (top 33%) concentrations showed high specificities (0.73–0.85) but low sensitivities (0.45–0.70). The minimum number of samples (k) required per individual to estimate participant-specific mean value for pesticides (within 20% of the “true” values) were 28–140 and 18–119 for spot and FMV samples, respectively. Repeated longitudinal measurements of these pesticides and their metabolites in urine showed considerable within-individual variability in both spot and FMV samples. Urinary concentrations of seven pesticides and their metabolites were significantly correlated with oxidative damage to lipids, proteins, and DNA.
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•Temporal variability in urinary pesticide concentrations was examined.•Notable within-individual variability was found for pesticides in urine.•Sensitivity analysis of urinary pesticide concentrations showed poor predictability.•Minimum number of urine samples required to predict exposures was 10s to 100s.•Urinary concentrations of pesticides were associated with oxidative stress.
RESUMEN Introducción: en los intentos de canulación del colédoco durante la colangiopancreatografía retrógrada endoscópica (CPRE) la guía puede entrar en el conducto pancreático. No está definido qué ...maniobra es más eficaz para canular la vía biliar y prevenir la pancreatitis tras pasar la guía al Wirsung. Objetivo: estudiar la tasa de canulación coledociana y de pancreatitis post-CPRE cuando en la primera ocasión en que la guía pasó al conducto pancreático de forma involuntaria se insertó una prótesis pancreática. Material y métodos: análisis retrospectivo de pacientes a los que se realizó una CPRE para drenaje biliar e incluidos de forma prospectiva en una base de datos. Tras la inserción involuntaria de una guía en el conducto pancreático se insertó una prótesis plástica recta de 5 Fr y 4 cm de longitud, sin topes internos para facilitar su expulsión. El colédoco se intentó canular por encima de la prótesis. En los pacientes mayores de 60 años se realizó una esfinterotomía pancreática antes de insertar la prótesis. Resultados: en un grupo de 154 CPRE se insertaron 46 prótesis pancreáticas (29,8%) y en estos casos el colédoco se canuló en el 95,6% (44/46) de las ocasiones. Se realizaron 21/46 (45,6%) esfinterotomías pancreáticas. Hubo 1/46 (2,17%) pancreatitis leves. La mayoría de las prótesis se expulsaron de forma espontánea. Conclusiones: en este estudio, la inserción de una prótesis pancreática plástica cuando la guía ha pasado al conducto pancreático de forma involuntaria en los intentos de canulación del colédoco ayudó a canular la vía biliar en la mayoría de las ocasiones, sin que la inserción de las prótesis produjera efectos adversos.
The development and characterisation of a method based on reverse-phase ultra-performance liquid chromatography (UPLC) coupled to a quadrupole-time of flight mass spectrometer (Q-TOF-MS) with ...negative electrospray ionisation (ESI) to determine perfluorinated compounds (PFCs) in packaging is presented in this paper. Analytes were quantitatively recovered from packaging with methanol in only one PLE cycle of 6min at 100°C. The UPLC allowed the successful separation of the studied PFCs in less than 4min. The whole method presented good precision, with RSDs below 8%, LODs from 0.6 to 16ngg−1; and excellent recovery values, around 100% in all cases, were achieved. The PLE–UPLC–MS method was applied to the analysis of popcorn packaging for microwave cooking. Besides the most commonly studied PFCs: PFOA and PFOS, the presence of other perfluorocarboxylic acids (PFCAs) in popcorn packaging is evidenced in this work.
► PLE–UPLC–MS/MS method for PFCs in pop-corn packaging. ► PFCs quantitatively recovered in one 6-min PLE cycle with methanol at 100°C. ► UPLC separation in less than 4min. ► Levels of PFCAs (different from PFOA) in packaging reported for the first time. ► QTOF mass spectrometry conditions reported for the first time.
Objective
The purpose of this study was to investigate the associations of urinary phthalates and bisphenols at age 6 years old with body fat and cardiovascular risk factors at 6 and 10 years and ...with the change from 6 to 10 years.
Methods
Among 471 Dutch children, the phthalates and bisphenols urinary concentrations at 6 years and BMI, fat mass index, android fat mass, blood pressure, glucose, insulin, and lipids blood concentrations at 6 and 10 years were measured.
Results
An interquartile range increase in di‐n‐octyl phthalate (DNOP) metabolites concentrations at 6 years was associated with an increased risk of overweight at 6 and 10 years (odds ratio: 1.44; 95% CI: 1.11‐1.87, and 1.43; 95% CI: 1.09‐1.86, respectively). Also, higher DNOP metabolites concentrations were associated with higher fat mass index at 6 years, higher systolic blood pressure at 10 years, a decrease in high‐density lipoprotein cholesterol, and an increase in triglycerides concentrations from 6 to 10 years (P < 0.05). Higher total bisphenols and bisphenol A concentrations were associated with a decrease in BMI from 6 to 10 years (P < 0.01).
Conclusions
DNOP metabolites are associated with overweight and an adverse cardiovascular profile in childhood. Total bisphenols and bisphenol A are associated with a decrease in BMI from 6 to 10 years.
Fetal exposure to phthalates and bisphenols might have long-lasting effects on growth and fat development. Not much is known about the effects on general and organ fat development in childhood. We ...assessed the associations of fetal exposure to phthalates and bisphenols with general and organ fat measures in school-aged children.
In a population-based, prospective cohort study among 1128 mother-child pairs, we measured maternal urinary phthalate metabolites and bisphenol concentrations in first, second, and third trimester. Offspring body mass index, fat mass index by dual-energy X-ray absorptiometry, and visceral and pericardial fat indices and liver fat fraction were measured by magnetic resonance imaging at 10 years.
After adjustment for confounders and correction for multiple testing, an interquartile range increase in first trimester phthalic acid concentrations remained associated with a 0.14 (95% confidence interval: 0.05, 0.22) standard deviation score increase in pericardial fat index. We also observed tendencies for associations of higher maternal low molecular weight phthalate urinary concentrations in second trimester with childhood pericardial fat index, but these were not significant after adjustment for multiple testing. High molecular weight phthalate, di-2-ethylhexyl phthalate, and di-n-octyl phthalate concentrations were not associated with childhood outcomes. Maternal urinary bisphenol concentrations were not associated with childhood adiposity.
Maternal first trimester phthalic acid concentrations are associated with increased childhood pericardial fat index at 10 years of age, whereas maternal bisphenol concentrations are not associated with childhood adiposity. We did not find significant sex-specific effects. These findings should be considered as hypothesis generating and need further replication and identification of underlying mechanisms.
Human exposure to phthalates is ubiquitous and has received considerable attention due to their association with adverse health outcomes, including type 2 diabetes mellitus (T2DM). Nevertheless, ...earlier studies that link phthalate exposure to T2DM yielded ambiguous results. Furthermore, studies that associate phthalate exposure with oxidative stress and then with T2DM are scant. In this diabetic case-control study, urine samples collected from 101 individuals aged 28–68 years from Jeddah, Saudi Arabia, were analyzed to determine 20 phthalate metabolites (PhMs) and seven oxidative stress biomarkers (OSBs). Unconditional logistic regression was used to estimate odds ratios for the association between diabetes and urinary PhMs and OSBs in participants, stratified by age, gender, nationality, smoking status, occupation, and urinary creatinine. Twelve PhMs and five OSBs were found at detection rates above 50%, with geometric mean concentrations of 0.61–100 and 0.35–10.7 ng/mL (1.04–171 and 0.61–18.6 μg/g creatinine), respectively. Almost all exposures were significantly higher in diabetic cases than in controls. The 12 PhMs were positively associated with higher urinary concentrations of 8-hydroxy-2′-deoxyguanosine (8-OHdG) and 8-iso-prostaglandin F2α (8-PGF2α). Individuals in the 3rd and/or 4th quartile(s) for urinary concentrations of PhMs and OSBs showed 3.7- and 7.3-fold increase, respectively, in the odds of having diabetes compared with those in the 1st quartile. The rank order of association of PhMs/OSBs with diabetes followed the order of: mEP ≈ mBP > mEHP > mCPP > mECPP ≈ mEOHP ≈ mEHHP ≈ mIBP ≈ mMP > mCMHP ≈ mBzP and 8-OHdG > 8-PGF2α ≈ 15-PGF2α. The relationship between phthalate exposure and risk of developing T2DM was mediated in part by phthalate-induced oxidative stress, especially 8-OHdG. Our study suggests that human exposure to phthalates is associated with increased oxidative stress which mediates the development of T2DM.
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•20 PhMs and 7 OSBs were analyzed in urine of diabetic case-control population.•12 PhMs were positively associated with 8-OHdG and 8-PGF2α levels in urine.•Urinary mEP, mBP and mEHP levels were strongly associated with diabetes.•Odds ratios for diabetes were significant for 8-OHdG, 8-PGF2α and 15-PGF2α.•Mediation effect of 8-OHdG was significant between phthalate exposure and T2DM.
•Phthalates are related with fetal growth restriction and preterm birth.•Phthalates may have trimester specific effects on fetal growth and birth outcomes.•Limiting prenatal phthalate exposure is ...crucial to prevent suboptimal fetal growth.
Exposure to phthalates may affect fetal growth, but previous studies are inconsistent and have not explored the trimester-specific effects of phthalates on repeated measures of fetal growth.
To assess the associations of maternal phthalate metabolites urine concentrations with fetal growth measures and birth outcomes and identify potential windows of vulnerability to exposure.
Population-based prospective cohort study, the Generation R Study (2002–2006). Data analysis was performed from November 2019 to June 2020.
Rotterdam, the Netherlands.
1379 pregnant women.
Maternal phthalate metabolites urine concentrations in first, second and third trimester.
Fetal head circumference, length and weight measured in the second and third trimester by ultrasound and at birth and preterm birth and small size for gestational age at birth.
Higher pregnancy-averaged phthalic acid, low molecular weight phthalate (LMWP), high molecular weight phthalate (HMWP) and di-2-ethylhexylphthalate (DEHP) concentrations tended to be associated with lower fetal weight SDS across gestation. The associations of phthalic acid and LMWP with fetal weight became stronger as pregnancy progressed (differences −0.08 (95% CI −0.14 to −0.02) SDS and −0.09 (95% CI −0.16 to −0.02) SDS at 40 weeks per interquartile range increase in phthalic acid and LMWP, respectively). Higher concentrations of specific LMWP, HMWP and DEHP metabolites were also associated with smaller head circumference and lower length SDS at birth and an increased risk of preterm birth and small size for gestational age at birth (p-values < 0.05). We observed differences by timing of exposure in these associations.
Higher maternal phthalate metabolites urine concentrations seem to be related with fetal growth restriction and preterm birth. Phthalates may have trimester specific effects on fetal growth and birth outcomes. Further studies are needed to explore the underlying mechanisms and long-term consequences.
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