•An UPLC-MS/MS 5-window-method enduring 22 min has been optimized.•This sensitive and accurate method allows to quantify 23 pesticides in human urine.•The optimization includes 3 further pesticide ...groups: neonicotinoids, carbamates and triazoles.•Pesticides still in use and others already banned by legislations are included.•This method is optimal as a HBM tool for health risk assessment in large population surveys.
An accurate and sensitive method for the determination of a total of 23 pesticides and their metabolites in human urine has been optimised. The methodology is based on a previously published method based on solid-phase extraction with methanol and acetone followed by ultra-performance liquid chromatography coupled to tandem mass spectrometry (UPLC-MS/MS) in the selected reaction mode (SRM) with both positive and negative electrospray ionization (ESI+/-). The detection settings of the previous method, which allowed to determine the metabolites from 6 organophosphate and 2 pyrethroid pesticides, were optimised in order to include further pesticide groups, such as 11 neonicotinoids, 3 carbamates/thiocarbamates and 2 triazoles. The 5-windows method enduring 22 min was optimized with acceptable results in relation to accuracy (recoveries >75 %), precision (coefficients of variation <26 %) and linearity (R2> 0.9915). The limits of detection ranged between 0.012 ng/mL and 0.058 ng/mL. Samples from the German External Quality Assessment Scheme (G-EQUAS) encompassing 2 pyrethroids, 2 organophosphate and one neonicotinoid (6-chloronicotinic acid, a common metabolite of imidacloprid and acetamiprid) were analysed, and the latter, included in this newest optimization, provided good reference results. The method is optimal as a human biomonitoring tool for health risk assessment in large population surveys.
Organophosphate (OP) and pyrethroid pesticides (PYR) are extensively used in agriculture, resulting in higher exposures among farmworkers. The present study reports the occurrence of 8 urinary OP and ...PYR metabolites in a sample of farmworkers and residents from Sucs (n = 87), a rural township in North West Catalonia (Spain). The aim of the present study was to examine differences in urinary pesticide metabolite concentrations between occupationally-exposed (farmworkers; n = 45) and environmentally-exposed subjects (n = 42) and to assess the relationship between pesticide's exposures and occupational activities in a real-case scenario.
Six OP and two PYR metabolites have been investigated, urine samples were extracted using SPE extraction and analyzed by UPLC-MS/MS. Three OP metabolites were commonly detectable in urine, namely TCPY (metabolite of chlorpyrifos), PNP (parathion) and DEAMPY (pirimiphos). Regarding pyrethroids, the two analyzed metabolites, 3-PBA and 4F-3-PBA, were detected in a high proportion of urine samples. Differences in concentrations between both groups were statistically significant for TCPY and 4F-3-PBA (Mann-Whitney U Test for independent groups, p < 0.05). In the case of TCPY, the concentrations were higher among the farmworkers, which is consistent with their occupational activity. The small differences found in DEAMPY, PNP, 3-PBA or even the significant higher concentrations of 4F-3-PBA among rural population suggest a general exposure to these compounds, even in those who do not carry an occupational activity.
Specific personal protective equipment (PPE) among farmworkers, such as the use of gloves and mask during mixing, showed a decrease in the exposure levels, although the differences were not statistically significant. However, a positive association was found between the use of a cap during mixing (for PNP and 3-PBA) and during application (only for 3-PBA). However, this piece of cloth is mainly used for sun protection, and when not cleaned after the handling of pesticides, it might represent a continuous source of exposure through dermal contact. Farmworkers using tractors with cabin had statistically significant lower concentrations of DEAMPY than those using a tractor without cabin. The previous results suggest that occupational protections should be encouraged among farmworkers and other potential workers handling with pesticides.
•Pesticides were analyzed in farmworkers and rural residents from Sucs (Catalonia).•Pyrethroids and organophosphate metabolites were commonly detectable in urine.•Farmworkers had higher pesticide levels due to occupationally exposures.•Use of personal protective equipment showed a decrease in the exposure levels.•The correct use of occupational protections are encouraged among farmworkers.
Phthalates are a group of widely used chemicals and humans are exposed to them in their daily life. Some phthalates may affect the hormonal balance in both children and adults. The aim of this study ...was to assess the phthalate exposure and its determinants among children at age of 7 years from the Polish Mother and Child Cohort Study (REPRO_PL). 250 urine samples collected in 2014–2015 were analysed for 21 metabolites of 11 parent phthalates using on-line high performance liquid chromatography coupled to tandem mass spectrometry (HPLC-MS/MS). This represents the most extensive set of phthalate metabolites ever determined for Poland. Ten metabolites were quantifiable in 100% of the samples, another eight in >90%. The highest median concentrations were found for the primary monoester metabolites of di-iso-butyl (MiBP, 72.4 μg/l), di-n-butyl (MnBP, 56.3 μg/l) and diethyl (MEP, 42.0 μg/l) phthalate, followed by the sum of di-2-ethylhexyl (ΣDEHP, 89.3 μg/l) and di-iso-nonyl (ΣDiNP, 21.9 μg/l) phthalate metabolites. Metabolite concentrations were higher in children at 7 years than in the same children at age 2 or in their mothers during pregnancy. Generally, phthalate exposures in this study were much higher than exposures reported in other European populations. Multivariate regression models showed that body mass index, place of residence, breastfeeding duration, socio-economic status and parental education were associated with the metabolite levels in the 7-year old children. Daily intake and hazard index calculations revealed that a small percentage of children (around 3–10%) exceeded the tolerable daily intakes established by international institutions such as EFSA and U.S. EPA indicating that these children might be at risk of anti-androgenic effects from the individual and cumulative exposure to phthalates. Thus, further monitoring of this population, by educational programs and follow-up interventions, is required.
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•Phthalate exposures in children from Poland ranked among the highest.•The most prevalent phthalate metabolites were MEP, MiBP, MnBP, ΣDEHP and ΣDiNP.•BMI, place of residence and breastfeeding are associated with phthalate body burdens.•Exposures in the upper percentiles exceeded levels that cannot be regarded as safe.
A method for the calculation of the limits of detection (LD) and quantification (LQ) for the analysis of organochlorine compounds in serum is described. The method is based on the analysis of ...proficiency testing materials, an external quality assessment for selected pollutants, and the study of the signal/noise ratio of chromatograms obtained from GC-ECD injection. This method provides representative results for matrix effects, instrumental variability and extraction recoveries in the analysis of serum samples.
This study of the body burden and serum concentrations of organochlorine compounds (OCs), represents a general population in a cohort from Menorca Island (birth 1997–1998) of children at birth and at ...4 years of age; the study has shown that the concentrations of hexachlorobenzene (HCB), 4,4′-DDE, 4,4′-DDT, polychlorobiphenyl (PCB) congeners #153, #138 and #180 and total PCBs in sera collected at 4 years are much higher in breastfed children than in those fed with formula, e.g. HCB 0.48 vs 0.21
ng/ml, β-HCH 0.32 vs 0.24
ng/ml, total DDTs 2.2 vs 0.57
ng/ml and total PCBs 1.4 vs 0.52
ng/ml. Comparison of gender differences in 4 years old children shows higher concentrations of all examined OCs in females than in males with the exception of HCB and PeCB in breastfed children, which are higher in males than in females, e.g. β-HCH 0.34 vs 0.28
ng/ml, total DDTs 2.6 vs 1.7
ng/ml and total PCBs 1.6 vs 1.0
ng/ml for breastfed children and β-HCH 0.23 vs 0.19
ng/ml, total DDTs 0.59 vs 0.48
ng/ml and total PCBs 0.58 vs 0.45
ng/ml for formula fed children. Gender comparison of the body burden between children fed with breastmilk or formula also shows higher concentrations in females than in males, e.g. β-HCH 0.47 vs 0.35
μg, total DDTs 3.0 vs 1.8
μg and total PCBs 1.9 vs 1.2
μg for breastfed children, and β-HCH 0.39 vs 0.17
μg, total DDTs 0.48 vs 0.27
μg and total PCBs 0.66 vs 0.55
μg for formula fed children. The results may suggest a higher capacity in female children for the retention of OCs incorporated through breastfeeding. However, these results should be taken with caution because the differences of the gender averages have low statistically significance when evaluated with the Student test.
•An UPLC-MS/MS method for analysis of urine organophosphate metabolites was developed.•An UPLC-MS/MS method for analysis of human urine pyrethroid metabolites was developed.•The use of synthetic ...urine afforded calibration straight lines with lower detection limits.•Detection limits were in the range of 14–69pg/ml.•Organophosphate concentrations in farmworkers was twofold than in urban populations.
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Isotope dilution solid phase extraction UPLC-MS/MS has been used to develop a robust and rapid methodology for the determination of eight specific metabolites of organophosphate and pyrethroid pesticides in human urine. The use of methanol:acetone (25:75v/v) affords an improvement in extraction efficiency in comparison to these individual solvents. The use of synthetic urine improves selectivity and limits of detection for the calibration straight lines. The method provides detection limits of 14–69pg/ml and 18–19pg/ml for the organophosphate and pyrethroid metabolites, respectively. Urine analyses of these metabolites in urban non-occupationally exposed individuals and farm workers shows that ingestion of these pesticides occurred in both populations. The concentrations of organophosphate pesticide metabolites in the latter were twofold than those from non-exposed populations.
•Organochlorine body burdens are higher in four-years old children than in newborns.•Organochlorine levels in four-years old children mostly depend on maternal transfer.•All hydrophobic compounds ...show the same infant gain/maternal transfer rates.•Children’s concentrations are correlated with maternal levels and lactation period.•The more volatile compounds encompass lower infant gain/maternal transfer rates.
Breastfed children absorb persistent and toxic chemicals such as organohalogen compounds (OHCs) during the entire lactation period. Nursing is a main contributor to the burden of these pollutants in the first years of life, hence further assessments on the OHC load processes are needed.
To identify the determinants of OHC increase in children at four years of age, considering concentration gains, maternal venous concentrations and breastfeeding time.
Concentrations of 19 organochlorine compounds (OCs) and 14 polybrominated diphenyl ethers (PBDEs) were analyzed in maternal venous (n = 466), cord blood (n = 326) and children venous serum at four years of age (n = 272) in the Asturias INMA cohort representing the Spanish general population. Data were evaluated considering the socio-demographic and individual information collected at recruitment and follow up surveys, as well as the OHC physical-chemical constants.
The four years-old children concentration gains of the most abundant OHCs showed strong correlations (R2 = 0.65–0.93) with the maternal concentrations during pregnancy and lactation period. The child gain/maternal transfer rates of most correlated pollutants were similar.
Between 65 and 93% of the variance of OCs in four years-old children was explained by the maternal concentrations during pregnancy and the lactation period. The compounds with log(Kow) > 3.7 (hydrophobic) showed analogous child gain/maternal transfer rates indicating similar processes of membrane lipid dissolution and passive diffusion from the epithelial cells into the milk. Molecular weight of these pollutants did not influence on these rates. Compounds with low log(Koa) such as hexachlorobenzene are more volatile and less retained, involving lower child gain/maternal transfer rates. These results may be useful to anticipate the increase of the concentrations of OCs in children using the maternal concentration of these compounds during pregnancy and the planned lactation period and to implement prophylactic measures in mothers with high venous pollutant concentrations.
Recent studies have described genetic mutations that affect the risk of thrombosis as a result of abnormal levels of such hemostatic parameters as protein C, protein S, and the activated protein C ...resistance ratio. Although these mutations suggest that genes play a part in determining variability in some hemostasis-related phenotypes, the relative importance of genetic influences on these traits has not been evaluated.
The relative contributions of genetic and environmental influences to a panel of hemostasis-related phenotypes were assessed in a sample of 397 individuals in 21 extended pedigrees. The effects of measured covariates (sex, age, smoking, and exogenous sex hormones), genes, and environmental variables shared by members of a household were quantified for 27 hemostasis-related measures. All of these phenotypes showed significant genetic contributions, with the majority of heritabilities ranging between 22% and 55% of the residual phenotypic variance after correction for covariate effects. Activated protein C resistance ratio, activated partial thromboplastin time, and Factor XII showed the strongest heritabilities, with 71.3%, 83.0%, and 67.3%, respectively, of the residual phenotypic variation attributable to genetic effects.
These results clearly demonstrate the importance of genetic factors in determining variation in hemostasis-related phenotypes that are components of the coagulation and fibrinolysis pathways and that have been implicated in risk for thrombosis. The presence of such strong genetic effects suggests that it will be possible to localize previously unknown genes that influence quantitative variation in these hemostasis-related phenotypes that may contribute to risk for thrombosis.
The present study reports total mercury (THg) and methylmercury (MeHg) concentrations in 32 different lean fish species from the Western Mediterranean Sea, with a special focus on the Balearic ...Islands. The concentrations of THg ranged between 0.05mg/kg ww and 3.1mg/kg ww (mean 0.41mg/kg ww). A considerable number of the most frequently fish species consumed by the Spanish population exceed the maximum levels proposed by the European legislation when they originate from the Mediterranean Sea, such as dusky grouper (100% of the examined specimens), common dentex (65%), conger (45%), common sole (38%), hake (26%) and angler (15%), among others. The estimated weekly intakes (EWI) in children (7–12 years of age) and adults from the Spanish population (2.7µg/kg bw and 2.1µg/kg bw, respectively) for population only consuming Mediterranean fish were below the provisional tolerable weekly intake (PTWI) of THg established by EFSA in 2012, 4µg/kg bw. However, the equivalent estimations for methylmercury, involving PTWI of 1.3µg/kg bw, were two times higher in children and above 50% in adults. For hake, sole, angler and dusky grouper, the most frequently consumed fish, the estimated weekly intakes in both children and adults were below the maximum levels accepted. These intakes correspond to maximum potential estimations because fish from non-Mediterranean origin is often consumed by the Spanish population including the one from the Balearic Islands.
•Mediterranean fish from the first trophic level had Hg concentrations below EU limits.•Hg in many widely consumed Mediterranean fish species was above EU limits.•The estimated Hg weekly intakes were below the provisional tolerable weekly intakes.•The estimated MeHg weekly intakes were above the provisional tolerable weekly intakes.•In hake, sole, angler and grouper the estimated weekly intakes were below EU limits.
Transplacental transfer and breastfeeding are the main transport routes of organic pollutants into children at the beginning of life. Although pollutant transmission through these mechanisms ...primarily depends on the maternal pollution burden, its impact may be modulated by physiological effects.
We have examined whether gestational weight gain (GWG) exerts an influence on the content of lipophilic low volatile pollutants in breast milk.
Colostrum from mothers from the INMA cohorts of Sabadell and Gipuzkoa (n = 256 and 119, respectively) with low GWG as defined by the Institute of Medicine (IOM) from the US National Academies of Sciences, Engineering and Medicine had significantly higher concentrations of polychlorobiphenyls (PCBs) and 4,4′-DDE than colostrum in mothers who gained weight within IOM recommendations or in those who exceeded this threshold. Statistically significant differences were also found in the colostrum:maternal serum ratios of these compounds. Women with low GWG retained higher pollutant amounts in colostrum. These observations are consistent with previously described higher concentrations of these pollutants in infant cord blood from mothers with low GWG by IOM standards. They indicate that mobilization of lipophilic organic pollutants by metabolic pregnant changes not only leads to higher fetal transfer but to higher accumulation into the mammary system upon low GWG. Conclusions: The present results show that insufficient GWG, besides increasing in utero exposure, also enhances pollutant transfer to infants during breastfeeding which considerably extends the significance of this physiological change for the pollutant children intake in early life.
•Women with low gestational weight gain retained higher pollutant amounts in colostrum.•Mobilization of lipophilic pollutants leads to accumulation into the mammary system.•Colostrum from low gestational weight mothers transfer more pollutants to infants.•The low volatile pollutants, eg. DDT and PCB, are the ones that accumulate more.•This finding extends the early life period of pollutant incorporation into children.
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