•Assessment of the multiple exposure to pesticides of 93 French pregnant women.•First study analyzing pesticides from different classes in paired urine and hair samples.•16 to 27 (median = 22) ...pesticides were detected in each hair sample and 3 to 22 (median = 12) in urine.•Both parent and metabolites are detected in hair whereas only metabolites are detected in urine.•No correlation between hair and urine was observed for most biomarkers.
The quantitative assessment of human exposure to contaminants such as pesticides is a crucial step in the characterization of exposure-associated risk. For this purpose, biomonitoring is often privileged as it presents the advantage of integrating all the possible sources and routes of exposure and of being representative of the internal dose resulting from exposure. Although biological fluids such as urine and blood have been used to date for this purpose, increasing interest has also been observed over the past decade for hair analysis. The present work aimed at comparing the information obtained from the analysis of urine versus hair regarding exposure to pesticides in a pilot cohort of pregnant women.
In ninety-three pregnant women included in the pilot of the French cohort ELFE, one urine and one hair sample were collected simultaneously from each subject at the maternity. Samples were analyzed using GC–MS/MS analytical methods allowing for the detection of both parent pesticides and metabolites, and designed to be as similar as possible between urine and hair for reliable inter-matrix comparison. Fifty-two biomarkers of exposure were targeted, including parents and metabolites of organochlorines, organophosphates, pyrethroids, carbamates, phenylpyrazoles and other pesticides.
The number of different compounds detected ranged from 16 to 27 (median = 22) in hair, and from 3 to 22 (median = 12) in urine. In hair, 24 compounds were found in > 40% of the individuals, whereas only 12 compounds presented the same frequency of detection in urine. Among the chemicals detected in > 80% of both hair and urine samples, only one (pentachlorophenol) showed a signification correlation between hair and urine concentrations.
The present results highlight the multiple exposure of the pregnant women included in this cohort and suggest that hair provides more comprehensive information on pesticide exposure than urine analysis. This study thus supports the relevance of hair analysis in future epidemiological studies investigating association between exposure and adverse health effects.
•On average 21 different biomarkers (9–37) were detected per sample.•First values for 55 pesticides, 4 PCBs and 5 PBDEs in French children’s hair.•Important differences were observed between children ...living in the same area.•Results showed that exposure is stronger in boys and in younger children.•Specific local contamination would not be the main contributor to exposure.
Children represent one of the most vulnerable parts of the population regarding the effects of pollutants exposure on health. In this study, hair samples were collected between October 2013 and August 2015 from 142 French children originating from different geographical areas (urban and rural) and analysed with a GC/MS-MS method, allowing for the detection of 55 biomarkers for pesticides and metabolites both persistent and non-persistent from different families, including: organochlorines, organophosphates, pyrethroids, azoles, dinitroanilines, oxadiazines, phenylpyrazoles and carboxamidas; 4 polychlorobiphenyls (PCBs) and 5 polybromodiphenylethers (PBDEs). The number of compounds detected in each sample ranged from 9 up to 37 (21 on average), which clearly highlighted the cumulative exposure of the children. The results also showed a wide range of concentration of the pollutants in hair (often more than 100 times higher in the most exposed child compared to the less exposed), suggesting significant disparities in the exposure level, even in children living in the same area. In addition to the detection of currently used chemicals, the presence of persistent organic pollutants (POPs) in children also suggests that the French population is still exposed to POPs nowadays. PCP, DEP, PNP, 3Me4NP, trans-Cl2CA, 3PBA, fipronil and fipronil sulfone, presented statistically significant higher concentration in the hair of boys compared to girls. PCP, PNP and 3Me4NP presented statistically significant higher concentration in younger children. Finally, this study also suggests that local environmental contamination would not be the main source of exposure, and that individual specificities (habits, diet…) would be the main contributors to the exposure to the pollutants analysed here. The present study strongly supports the relevance of hair for the biomonitoring of exposure and provides the first values of organic pollutant concentration in the hair of French children.
A first gas chromatography–tandem mass spectrometry (GC–MS/MS) method was designed for analysis of four tetrahydroxylated benzoapyrene metabolites (benzoapyrene-r-7,t-8,t-9,c-10-tetrahydrotetrol, ...benzoapyrene-r-7,t-8,t-9,t-10-tetrahydrotetrol, benzoapyrene-r-7,t-8,c-9,c-10-tetrahydrotetrol, and benzoapyrene-r-7,t-8,c-9,t-10-tetrahydrotetrol) in hair. Hair powder extract was submitted to liquid–solid extraction, followed by C₁₈ solid-phase purification. The analytes were derivatized with use of N-methyl-N-(trimethylsilyl)trifluoroacetamide and then analyzed by GC–MS/MS in negative chemical ionization mode. The calibration curve was linear from the limit of quantification (LOQ) to 20 pg/mg in hair. The coefficient of determination of the calibration curve was more than 0.975 for all the analytes investigated. The LOQs ranged from 0.075 to 0.2 pg/mg in hair. The method was afterward applied to the analysis of hair of 16 rats randomly allocated to experimental groups receiving 16 polycyclic aromatic hydrocarbons solubilized in oil at 0 or 0.8 mg/kg body weight by oral administration three times per week for 90 days. The analysis of monohydroxylated and dihydroxylated benzoapyrenes was conducted in parallel by GC–MS/MS on the same samples. All tetrahydroxylated benzoapyrene isomers were detected in hair samples collected from rats exposed to polycyclic aromatic hydrocarbons. Benzoapyrene-r-7,t-8,t-9,c-10-tetrahydrotetrol, the most abundant isomer in hair of treated rats, was also the principal isomer released in DNA adduct hydrolysis in humans. Moreover, the benzoapyrene-r-7,t-8,t-9,c-10-tetrahydrotetrol concentrations in hair were significantly greater than those of 2-hydroxybenzoapyrene, 1-hydroxybenzoapyrene, 7-hydroxybenzoapyrene, and 4-hydroxybenzoapyrene and similar to those of 9-hydroxybenzoapyrene and 3-hydroxybenzoapyrene. The method was also sufficiently sensitive to monitor environmental levels of exposure because two hair specimens in the eight analyzed from smokers were above the LOQ for benzoapyrene-r-7,t-8,t-9,c-10-tetrahydrotetrol and benzoapyrene-r-7,t-8,c-9,t-10-tetrahydrotetrol. This study therefore demonstrated that tetrahydroxylated benzoapyrenes in hair might be a useful biomarker for the assessment of both the general population and occupationally exposed workers. Graphical Abstract GC-NCI-MS/MS analysis of tetrahydroxylated benzoapyrene metabolites in hair of rat under controlled exposure to benzoapyrene (10 mg/kg, 28 days)
Urine and plasma have been used to date for the biomonitoring of exposure to pollutants and are still the preferred fluids for this purpose; however, these fluids mainly provide information on the ...short term and may present a high level of variability regarding pesticide concentrations, especially for nonpersistent compounds. Hair analysis may provide information about chronic exposure that is averaged over several months; therefore, this method has been proposed as an alternative to solely relying on these fluids. Although the possibility of detecting pesticides in hair has been demonstrated over the past few years, the unknown linkage between exposure and pesticides concentration in hair has limited the recognition of this matrix as a relevant tool for assessing human exposure. Based on a rat model in which there was controlled exposure to a mixture of pesticides composed of lindane, β-hexachlorocyclohexane, β-endosulfan, p,p′-DDT, p,p′-DDE, dieldrin, pentachlorophenol, diazinon, chlorpyrifos, cyhalothrin, permethrin, cypermethrin, propiconazole, fipronil, oxadiazon, diflufenican, trifluralin, carbofuran, and propoxur, the current work demonstrates the association between exposure intensity and resulting pesticide concentration in hair. We also compared the results obtained from a hair analysis to urine and plasma collected from the same rats. Hair, blood, and urine were collected from rats submitted to 90-day exposure by gavage to the aforementioned mixture of common pesticides at different levels. We observed a linear relationship between exposure intensity and the concentration of pesticides in the rats’ hair (
R
Pearson
0.453–0.978,
p
< 0.01). A comparison with results from urine and plasma samples demonstrated the relevance of hair analysis and, for many chemicals, its superiority over using fluids for differentiating animals from different groups and for re-attributing animals to their correct groups of exposure based on pesticide concentrations in the matrix. Therefore, this study strongly supports hair analysis as a reliable tool to be used during epidemiological studies to investigate exposure-associated adverse health effects.
The assessment of human exposure to fast-elimination endocrine disruptors (ED) such as phthalates, bisphenols or pesticides is usually based on urinary biomarkers. The variability of biomarkers ...concentration, due to rapid elimination from the body combined with frequent exposure is however pointed out as a major limitation to exposure assessment. Other matrices such as hair, less sensitive to short-term variations in the exposure, have been proposed as possible alternatives. Nevertheless, no study compared the information obtained from hair and urine respectively in a follow-up allowing to assess biomarkers variability over time in these two matrices, and to compare the correlation between them.
In the present study, hair and urine samples were collected from 16 volunteers over a 6 months follow-up. All in all, 92 hair samples and 805 urines samples were collected and analyzed for the presence of 16 phthalate metabolites, 4 bisphenols and 8 pesticides/metabolites.
All the biomarkers analyzed were detected in at least one of the two matrices. 21 biomarkers were more frequently detected in hair, 6 in urine, and 1 was equivalent. Biomarkers intraclass correlation coefficients (ICC) ranged from 0.1 to 0.8 (ten above 0.4) in hair, and from 0.09 to 0.51 in urine (two above 0.4). The concentrations of biomarkers in hair and urine were significantly correlated for only one compound.
This study highlights the complexity of assessing exposure to fast-elimination ED and suggests considering with caution the specificity of the matrix in data interpretation. The results document the respective advantages and limitations of urine and hair, and provide new insight in the understanding of the information provided by these biological matrices and their relevance for the assessment of human exposure to fast elimination contaminants.
92 hair and 805 urine samples collected from 16 volunteers over 6 months, tested for phthalate metabolites, bisphenols and pesticides. 19 biomarkers (in hair) and 24 (in urine) were detected in >50% of the samples.
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•Hair and urine samples were repeatedly collected from 16 volunteers over 6 months.•16 phthalate metabolites, 4 bisphenols, 8 pesticides were tested in 94 hair and 805 urine samples.•19 biomarkers (in hair) and 24 (in urine) were detected in >50% of the samples.•Biomarkers ICC ranged from 0.1 to 0.8 (10 above 0.4) in hair and from 0.09 to 0.51 in urine (2 above 0.4).•No correlation between hair and urine was observed for most biomarkers.
► This work reviews the state of the art in organic pollutants analysis in human hair. ► The influence of methods sensitivity on results interpretation was highlighted. ► We investigate the relevance ...of hair as representative of subjects levels of exposure. ► Critical evaluation of the literature and focus on current limitations was done. ► Future needs for promoting the use of hair in epidemiological studies were identified.
This paper presents the current state of the art in human hair analysis for the detection of organic pollutants associated with environmental and occupational exposure. The different chemical classes are reviewed with a special focus set on compounds that were only recently investigated. The importance of methods sensitivity and particularly the influence of this parameter on the results presented in previous publications is highlighted. This report also investigates the relevance of hair analysis as an indicator of subjects’ level of exposure and underlines limitations that are still associated with this matrix. This study also presents a critical assessment of some specific aspects presented in the literature as well as future needs to strengthen the position of hair as a relevant biomarker of exposure to be used in epidemiological studies.
Mechanisms governing chemicals’ incorporation in hair are incompletely understood, and gaps remain to link the concentration of chemicals in hair to level of exposure and internal dose present in the ...body. This study assesses the relevance of hair analysis for the biomonitoring of exposure to fast-elimination compounds and investigates the role of pharmacokinetics (PK) in their incorporation in hair. Rats were administered with pesticides, bisphenols, phthalates, and DINCH over 2 months. Hairs were analyzed for 28 chemicals/metabolites to investigate correlations between their concentration in hair and the dose administered to the animals. Urine collected over 24 h after gavage was used to determine chemicals’ PK and to investigate their influence on incorporation into hair by means of linear mixed models (LMMs). Eighteen chemicals presented a significant correlation between concentration in hair and level of exposure. In models combining all chemicals, agreement between concentration in hair predicted by LMM and experimental values was moderate (R 2 = 0.19) but significantly increased when PK were included in the models (R 2 = 0.37), and even more when chemical families were considered separately (e.g., R 2 = 0.98 for pesticides). This study shows that pharmacokinetics mediate incorporation of chemicals in hair and suggests the relevance of hair for assessing exposure to fast-elimination chemicals.
•“Hair analysis was used to assess exposure of 204 Chinese women to multiclass pesticides.•71 pesticides and 23 metabolites were found in at least one subject.•In each subject the number of detected ...chemicals ranged from 25 to 50.•38 biomarkers presented significantly different concentration between the 2 cities.•Age, BMI, cooking frequency and regions affected concentrations of pesticides in hair.”
The high use of pesticides worldwide and the constant exposure of humans to these toxic-by-design chemicals have drawn the attention on the possible consequences on human health. However, information on the exposure of the general population to pesticides remain very limited in most countries, especially in urban areas. In the present work, hair analysis was conducted to investigate the exposure of 204 urban women living in two Chinese cities (Baoding and Dalian) to 110 pesticides and 30 metabolites of the following families: organochlorines, organophosphates, carbamates, pyrethroids, neonicotinoids, phenylpyrazoles, acid herbicides, urea herbicides and azoles. Results showed that 71 pesticides and 23 metabolites were found in the hair samples, with concentrations ranging up to 1070 pg/mg in hair. In each hair sample, the number of detected chemicals ranged from 25 to 50, demonstrating the cumulative exposure to pesticides among Chinese women in the studied regions. The concentrations of 38 chemicals (e.g., p-nitrophenol, diethyldithiophosphate, λ-cyhalothrin, permethrin, carbendazim and tebuconazole) were significantly different between women in Baoding and Dalian, indicating the regional differences in exposure to pesticide. Using a multiple regression analysis, we found that concentrations of a few dominant pesticides were associated with age, body mass index (BMI), cooking frequency and regions. These results can provide baseline information on exposure of female adult Chinese population to multiple pesticides and support future studies focused on the health effects associated with pesticide exposure.
The impact of pollution on children's health has been increasingly pointed out in numerous studies which emphasized their increased vulnerability compared to adults. This pilot study investigated the ...relevance of hair analysis for the assessment of children exposure to pollution and to environmental tobacco smoke (ETS). The methodology based on GC–MS/MS and LC-MS/MS, is the first one to investigate simultaneously parent PAH (n = 15), PAH metabolites (n = 56), nicotine and cotinine in a biological matrix. The method was applied to hair samples collected from 25 children, aged from 2 to 11 years, living in Paris, France, selected as densely populated area with urban pollution including vehicle exhausts, and Yeu Island, a French island in the Atlantic ocean, selected as control area with low population density and no fuel powered vehicles. Nicotine and cotinine were detected in all the samples at concentrations up to 2275 pg/mg and 110 pg/mg respectively, suggesting exposure to ETS in the two areas. 10 parent PAH and 10 metabolites were detected in 100% and in >90% of the samples respectively. Eight of these biomarkers presented a significantly higher concentration in children from Paris than from Yeu Island. The results suggest association between PAH exposure and estimated time of exposure to vehicle exhaust as well as higher exposure to both PAH and ETS in the youngest children. Although these findings need to be confirmed on wider populations, the results obtained in this pilot study strongly support the relevance of hair analysis for the biomonitoring of children exposure to urban pollution and ETS.
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•Assessment of children exposure to pollution with hair analysis•Nicotine in 100% of the children indicates exposure to environmental tobacco smoke.•First method to analyse PAH parent (15) and metabolites (56) in a biological matrix•10 parent PAH detected in 100% and 10 metabolites detected in >90% of subjects•Significant differences in exposure depending on children living area
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•First biomonitoring study on a group representative of the adult general population in Luxembourg.•34 persistent and 33 non-persistent pollutants were analyzed in hair samples from ...497 adults.•17 pollutants were detected in >50% of the subjects.•15 pollutants presented significant associations with sex, age and/or body mass index.
Environmental exposure of humans to pollutants has been associated with adverse health outcomes, but few studies have evaluated the multiple exposure of general populations. In the present study, we used hair analysis to assess the exposure of a general adult population (n = 497) in Luxembourg to 34 persistent and 33 non-persistent organic pollutants from 11 chemical families, such as polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), organochlorine pesticides (OCPs), organophosphate pesticides (OPPs), and pyrethroid pesticides (PYRs). We detected 24 persistent and 29 non-persistent organic pollutants, with 17 pollutants being detected in more than 50% of hair samples. The median concentrations for pollutants detected in 100% of the samples were 0.37 pg/mg for lindane (γ-HCH), 0.15 pg/mg for hexachlorobenzene (HCB), 14.1 pg/mg for p-nitrophenyl (PNP), and 0.10 pg/mg for trifluralin. Each participant in this study had detectable levels of at least 10 of the pollutants analyzed, and 50% of participants had 19 or more, suggesting the simultaneous exposure to numerous different pollutants among our study population. Significant correlations were often found between pollutants from the same family, with the strongest being found between two PYR metabolites, trans/cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-carboxylic acid (Cl2CA) and 3-phenoxybenzoic acid (3-PBA). Results from multiple linear regression analyses showed that sex, age and/or body mass index were significantly associated with 15 out of the 17 frequently detected pollutants. The current study is the first nationwide biomonitoring investigating organic contaminants in the Luxembourg population using hair analysis.
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