Assessment of internal exposure risk from metals pollution of occupational and non-occupational populations around a non-ferrous metal smelting plant.

Non-ferrous metal smelting poses significant risks to public health. Specifically, the copper smelting process releases arsenic, a semi-volatile metalloid, which poses an emerging exposure risk to both workers and nearby residents. To comprehensively understand the internal exposure risks of metal(loid)s from copper smelting, we explored eighteen metal(loid)s and arsenic metabolites in the urine of both occupational and non-occupational populations using inductively coupled plasma mass spectrometry with high-performance liquid chromatography and compared their health risks. Results showed that zinc and copper (485.38 and 14.00 µg/L), and arsenic, lead, cadmium, vanadium, tin and antimony (46.80, 6.82, 2.17, 0.40, 0.44 and 0.23 µg/L, respectively) in workers (n=179) were significantly higher compared to controls (n=168), while Zinc, tin and antimony (412.10, 0.51 and 0.15 µg/L, respectively) of residents were significantly higher than controls. Additionally, workers had a higher monomethyl arsenic percentage (MMA%), showing lower arsenic methylation capacity. Source appointment analysis identified arsenic, lead, cadmium, antimony, tin and thallium as co-exposure metal(loid)s from copper smelting, positively relating to the age of workers. The hazard index (HI) of workers exceeded 1.0, while residents and control were approximately at 1.0. Besides, all three populations had accumulated cancer risks exceeding 1.0 × 10-4, and arsenite (AsIII) was the main contributor to the variation of workers and residents. Furthermore, residents living closer to the smelting plant had higher health risks. This study reveals arsenic exposure metabolites and multiple metals as emerging contaminants for copper smelting exposure populations, providing valuable insights for pollution control in non-ferrous metal smelting.

The development of rapid immunoassays for the urinary analysis of 1-hydroxypyrene glucuronide facilitate both laboratory and on-site polycyclic aromatic hydrocarbon biomonitoring.

Polycylic Aromatic Hydrocarbons (PAHs) are produced during the incomplete burning of organic materials. PAH sources include vehicle exhaust, tobacco smoke and waste incineration. Environmental and occupational exposures to PAHs are known to occur. Cancer is a significant endpoint of PAH exposure and several occupations associated with high PAH exposure have been classified by IARC as carcinogenic to humans (Group 1). Pyrene is a common component of PAH mixtures and metabolism of pyrene leads to the excretion of 1-hydroxypyrene glucuronide (1-OHPyrG) in urine. Laboratory measurement of urinary 1-OHPyrG is employed in occupational and environmental biomonitoring programmes. The production of an anti-1-OHPyrG monoclonal antibody would allow the development of a PAH biomonitoring ELISA facilitating large scale laboratory screening and routine testing. The development of a lateral flow immunoassay and the production of a field test (point of use test) would greatly increase the value of biomonitoring. A novel Lateral Flow has been developed which employs an anti-1-OHPyrG sheep monoclonal antibody (Mab) to capture the PAH metabolite. The captured metabolite is visualised through a second Mab raised against the Mab-1-OHPyrG immune complex. This sandwich assay provides a positive correlation between the assay signal and biomarker concentration. A Smartphone camera allows signal measurement and a carefully considered 'app' provides result interpretation and data analysis. Results are provided in an exposed/not-exposed format. Performance of the lateral flow was confirmed through a comparative study and field trial. The development of a lateral flow test provides "real-time" analysis to occupational health professionals. On-site screening allows the immediate confirmation of safe working practice, provides immediate reassurance to those involved in potentially hazardous activities and greatly increases the efficacy of biomonitoring.

A direct immersion-solid-phase microextraction method for the automated determination of 3- to 6-ring polycyclic aromatic hydrocarbons in saliva by gas-chromatography-tandem mass spectrometry.

This work presents a novel method for the analysis of polycyclic aromatic hydrocarbons (PAHs) in saliva samples using solid phase microextraction (SPME) coupled with gas chromatography-triple quadrupole mass spectrometry (GC-QqQ-MS). The protocol utilizes the latest commercially available overcoated fiber (PDMS/DVB/PDMS) for direct immersion extraction of the target analytes, enabling the determination of thirteen PAHs, including low-volatile compounds. The SPME extraction method was optimized using a central composite design (CCD). The evaluation of the fiber coating's robustness over time demonstrated excellent extraction performance with no significant degradation. The validation procedure confirmed good performance for all parameters, with LOQ values (100 ng/L for ten analytes and 500 ng/L for three analytes) comparable to other chromatographic methods. The environmental impact of the protocol was objectively assessed using two recently proposed metrics: the Green Analytical Procedure Index (GAPI) and the Analytical Greenness metric for sample preparation (AGREEprep). Both metrics indicated good overall environmental friendliness, with AGREEprep providing a satisfactory comprehensive score despite the use of highly impactful instrumentation. These characteristics make the developed method suitable for routine analysis in environmental and epidemiological monitoring.

Development and validation of multiresidue analysis method for biomonitoring of pesticides and metabolites in human blood and urine by LC-QToF-MS.

The widespread use of pesticides and their consequential presence in the environment is a growing concern due to the harmful health effects associated with pesticide exposure. For clinical and toxicology laboratories, a method for simultaneously determining these compounds and their metabolic products in body fluids, such as blood and urine, is important. In the present study, a rapid, sensitive and simultaneous LC-QToF-MS method for detecting multiclass pesticides and metabolites in blood and urine samples has been developed and validated. Four sample preparation procedures, protein precipitation and three different variants of QuEChERS-based extraction were evaluated to find a suitable, simple, and effective sample pretreatment technique. The final optimized sample preparation method (acetonitrile; 400 µl, MgSO4; 40 mg and NaCl; 10 mg) was validated for accuracy, precision, matrix effect, recovery, stability, carryover, and dilution integrity. Analyte recoveries ranged from 75.40 to 113.54 % while accuracy was evaluated in the range of 71.41-108.26 % and precision (%RSD) in the range of 0.01 %-16.85 %. The limit of quantification (LOQ) for all compounds was established in the range of 0.82-7.05 ng mL-1. The developed reliable, robust, and sensitive method was successfully applied for the quantification of target pesticides and metabolites in human blood and urine samples. Evaluated samples resulted in detection of eleven analytes (seven pesticides and four metabolites).

Microplastics in marine sponges (Porifera) along a highly urbanized estuarine gradient in Santos, Brazil.

Microplastics (MPs) are ubiquitously found in environmental matrices, particularly affecting aquatic systems. While several marine species have been widely used to assess MP contamination, sponges (Porifera) are less used. The MPs contamination was assessed in the sun sponge (Hymeniacidon heliophila) along a gradient at the Santos Estuarine System (Brazil). A 14-fold difference between concentrations (particles g-1) was verified between the most (1.40 ± 0.81) and least (0.10 ± 0.12) contaminated sites, confirming the local contamination gradient. The MPs found were primarily polypropylene, small (1.2-1000 µm), fibrous, and colored. Considering total concentrations, sizes and shapes these spatial patterns were similar those previously detected in molluscs obtained in the same sites. On the other hand, they differed in polymeric composition and color categories. Such findings give important initial insights into the potential role of marine sponges as putative sentinels of MPs contamination.

Benzene metabolism and health risk evaluation: insights gained from biomonitoring.

Metabolic conversion of benzene (Bz) is thought to be required for the hematotoxic effects observed following Bz exposures. Most safe exposure limits set for Bz utilize epidemiology data on the hematotoxic effects of Bz for the dose-response assessments. These hematotoxic effects occurred among workers exposed to elevated Bz levels, thus dose extrapolation is required for assessing relevant risks for populations exposed orders of magnitude lower. Thus, understanding how Bz is metabolized over a wide range of air Bz levels is an important topic for risk assessments for Bz. Here, we analyze biomonitoring data for workers exposed to Bz to make evaluations of how the metabolism of Bz varies across a wide range of exposures. Our analysis indicates that the presence of metabolites derived from exposures to sources other than Bz (nonspecific metabolites of Bz) are significant confounders among biomonitoring studies and this precludes making any assessments of how Bz metabolism differs below approximately 3 ppm air Bz exposures using such nonspecific metabolites.

Longitudinal study and predictive modelling of urinary pesticide metabolite concentrations in residents of Guangzhou, China.

Continuous human biomonitoring and predictive modelling of urinary pesticide metabolites are critical for evaluating pesticide exposure trends and associated health risks. We conducted repeat cross-sectional surveys to determine the urinary concentrations of eight pesticide metabolites in the residents of Guangzhou, China, from 2018 to 2022. We longitudinally analyzed the changes in these metabolite concentrations over the years and assessed the potential non-carcinogenic risks by calculating the hazard quotient and hazard index. No significant differences were observed in the total urinary pesticide metabolite concentrations over the 5 years (9.16-12.99 µg/L). The urinary concentrations of 3,5,6-trichloro-2-pyridinol and 2,4-dichlorophenoxyacetic acid reached their lowest levels in 2020 (1.47 and 0.11 µg/L). Conversely, urinary para-nitrophenol concentrations exhibited an inverse trend, peaking in 2020 (6.16 µg/L). The composition profiles of urinary pesticide metabolites showed that para-nitrophenol consistently constituted the largest proportion each year. Males consistently showed higher median concentrations of total urinary pesticide metabolites and individual metabolites of 3,5,6-trichloro-2-pyridinol, trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylic acid, and para-nitrophenol than females. The concentrations of cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylic acid in adults' urine were significantly higher than those in minors' urine each year. The total pesticide metabolite concentrations in adults' urine were significantly higher than those in minors' urine in 2018 and 2020, whereas no significant differences were observed in other years. No significant differences in urinary pesticide metabolite concentrations were observed among different BMI groups. Results showed that 14.17% of the population had hazard index values above 1, indicating a higher risk of health hazards. Three predictive models were employed to predict urinary pesticide metabolite concentrations for 2023-2024, revealing an increasing trend in 3,5,6-trichloro-2-pyridinol concentrations while other metabolites are expected to decrease. The study showed the concentration of para-nitrophenol peaked in 2020 while 3,5,6-trichloro-2-pyridinol and 2,4-dichlorophenoxyacetic acid reached their lowest levels, suggests that the COVID-19 pandemic may have influenced pesticide exposure patterns.

Cumulative Health Risk from Exposure Load (CHREL): Looking at multi-chemical exposures through the lens of biomonitoring guidance values.

Exposure load (EL) is an indicator of multiple chemical exposures based on human biomonitoring data. We used EL methodology and human biomonitoring health-based guidance values (HB2GVs) as exposure thresholds to create a new metric called Cumulative Health Risk from Exposure Load (CHREL). HB2GVs are derived by calculating the concentration of a biomarker consistent with a health protective exposure guidance value. CHREL analysis was conducted using Canadian Health Measures Survey (CHMS) cycle 3 and 4 biomonitoring data. Based on 18 chemicals, more than half of the Canadian population had an estimated CHRELTOTAL of 1 or more, indicative of chemical exposures potentially above selected exposure guidance values. Females had a significantly lower CHRELTOTAL compared to males, 12-19 year olds had a lower CHRELTOTAL compared to older age groups (significant compared to 40-59 year olds), and nonsmokers had a significantly lower CHRELTOTAL than smokers. Small segments of the population had a CHRELLIVER or a CHRELNERV of 1 or more, indicating exposures potentially above guideline levels for chemicals affecting the liver or nervous system. CHRELCANC was calculated based on 6 chemicals with HB2GVs derived for cancer endpoints. At the 10-5 risk level, most people had an estimated CHRELCANC of 3, indicative of multiple chemicals that may exceed negligible cancer risk. The most important contributors to exposures above HB2GVs were inorganic arsenic, mercury, acrylamide, xylenes, benzene and triclosan. Keeping certain assumptions, uncertainties and limitations in mind, the CHREL indicator can be used to obtain a picture of potential cumulative health risks from combined chemical exposures in a population, and as a comparative measure between subpopulations, including vulnerable subgroups.

Polybrominated diphenyl ethers in paired dust-breast milk samples: Levels, predictors of contamination, and health risk assessment for infants and mothers.

An integrated study on the levels of 7 polybrominated diphenyl ethers (PBDEs) in house dust and breast milk samples from women (N = 30) living in these households was conducted. ∑PBDEs ranged from

Internal blood lead exposure levels in permanent residents of Jiangxi Province and its effects on routine hematological and biochemical indices.

Background: Lead exposure levels are closely linked to human health and can cause damage to multiple organ systems, including the blood system and liver. However, due to insufficient evidence, the effects of lead exposure on hematological and biochemical indices have not been fully established. Objective: This study aims to explore the blood lead levels of permanent residents in Jiangxi Province and analyze the factors affecting blood lead levels and the impact of blood lead levels on hematological and biochemical indices. Methods: We conducted a cross-sectional study including questionnaires, health examinations, and blood sample examinations on 720 randomly selected permanent residents (3-79 years) in Jiangxi Province in 2018. The blood lead levels were measured using inductively coupled plasma mass spectrometry. Routine hematological and biochemical tests were determined by qualified medical institutions using automated hematology analyzers and biochemistry analyzers. Results: The geometric mean of blood lead concentration in permanent residents of Jiangxi Province was 20.45 µg/L. Gender, age, annual household income, smoking, and hypertension were the influencing factors for blood lead levels. For each 1 µg/L increase in blood lead, the risks of elevated red blood cell count (from low to high), platelet volume distribution width, alkaline phosphatase (from low to high), and cholesterol increased by 2.4, 1.6, 3.6, and 2.3%, respectively, whereas the risks of elevation of direct bilirubin and total bilirubin both decreased by 1.7%. Conclusion: The blood lead level in permanent residents of Jiangxi Province is higher than the national average. Higher blood lead levels were found in men than in women; blood lead levels were positively correlated with age but negatively correlated with annual household income; smoking and hypertension are risk factors for elevated blood lead; and blood lead levels affect routine hematological and biochemical markers such as red blood cell count, platelet volume distribution width, direct bilirubin, total bilirubin, alkaline phosphatase, and cholesterol.

Kinetic Considerations in the Interpretation of Biomonitoring of 1,3-Butadiene Exposure by Determination of Urinary Mercapturic Acids.

1,3-Butadiene (BD) is classified as a human carcinogen, and occupational exposure should be minimized. This study examined the effectiveness of personal protective equipment (PPE) during the clean-up and repair of a storage tank containing sludge contaminated with BD. A total of 66 workers participated, providing repeat urine samples before and after the shift. Overall, 1286 samples were analyzed for 1,2-dihydroxy-4-(N-acetylcysteinyl)butane (DHBMA) and the isomers 2-hydroxy-1-(N-acetylcysteinyl)-3-butene and 1-hydroxy-2-(N-acetylcysteinyl)-3-butene (MHBMA). Both DHBMA and MHBMA are urinary metabolites of BD and serve as biomarkers for recent BD exposure. Established correlations between the urinary concentrations of these biomarkers and airborne BD levels allowed for exposure assessment. However, conclusions regarding the exceedances of occupational exposure limits can vary depending on whether DHBMA or MHBMA levels are considered. This study investigated this discrepancy by estimating the apparent urinary half-lives of DHBMA and MHBMA using sequential individual post- and pre-shift samples. The results indicated that the longer urinary half-life of MHBMA (19.7 ± 3.1 h) led to its accumulation during the work week, in contrast to DHBMA, which has a shorter half-life (10.3 ± 1.9 h) and showed limited accumulation. When the kinetic information was used to adjust for the MHBMA build-up over the week, the discrepancy with DHBMA resolved, confirming that exposure limit values were not exceeded and validating the effectiveness of the PPE used. In the context of biomonitoring, this study provides valuable insights into biomarker selection based on specific objectives. MHBMA is recommended for scenarios with uncertain exposure timing and activities, whereas DHBMA is the preferred biomarker for evaluating the effectiveness of protective measures in known exposure settings.

How can exposure assessment for pesticides in epidemiological studies be improved? Insights from the IMPRESS project.

The IMPRoving Exposure aSSessment Methodologies for Epidemiological Studies on Pesticides (IMPRESS) project (http://www.impress-project.org/) aimed to further the understanding of the performance of pesticide exposure assessment methods (EAMs). To achieve this the IMPRESS project used two approaches to assess EAM performance, using existing and newly collected data from five studies from three different countries and use of published secondary data to undertake three meta-analyses for selected chronic health outcomes. Based on the findings of the IMPRESS project we provide in this paper insights on the overarching research question "How can exposure assessments for pesticides in epidemiological studies be improved"? Exposure assessment is a critical component of pesticide epidemiological studies. EAMs used and epidemiological practices employed need to reflect the changing nature and complexities of pesticide exposure in various occupational settings. To properly assess the association between exposure and selected health outcomes, the choice of EAM should provide a clear exposure contrast within the study population. Acquiring a practical understanding of the pesticide use practices is crucial to determine whether factors such as frequency or intensity of exposure have to be considered in planned analyses. Biomonitoring may be more beneficially applied intensively in a focussed exposure assessment analysis of a particular cohort, which can be used to determine the most relevant exposure factors within that cohort-specific context. Overall, improving pesticide exposure assessment in epidemiological studies requires a multi-disciplinary approach. A next step for the wider scientific community may be to consider the development of a decision tree to aid the selection of suitable EAMs. Such a decision tree would need to consider and be based on multiple parameters including, but not limited to, study type, health endpoint, socio-demographic context, farming system, pesticide used, and application methods.

Multiple mycotoxin exposure assessment through human biomonitoring in an esophageal cancer case-control study in the Arsi-Bale districts of Oromia region of Ethiopia.

BACKGROUND: Esophageal cancer (EC) is a malignancy with a poor prognosis and a five-year survival rate of less than 20%. It is the ninth most frequent cancer globally and the sixth leading cause of cancer-related deaths. The incidence of EC has been found to vary significantly by geography, indicating the importance of environmental and lifestyle factors along with genetic factors in the onset of the disease. In this work, we investigated mycotoxin exposure in a case-control study from the Arsi-Bale districts of Oromia regional state in Ethiopia, where there is a high incidence of EC while alcohol and tobacco use - two established risk factors for EC - are very rare. METHODS: Internal exposure to 39 mycotoxins and metabolites was assessed by liquid chromatography-tandem mass spectrometry in plasma samples of EC cases (n = 166) and location-matched healthy controls (n = 166) who shared similar dietary sources. Demographic and lifestyle data were collected using structured questionnaires. Principal Component Analysis and machine learning models were used to identify the most relevant demographic, lifestyle, and mycotoxin (co-)exposure variables associated with EC. Multivariate binary logistic regression analysis was used to assess EC risk. RESULT: Evidence of mycotoxin exposure was observed in all plasma samples, with 10 different mycotoxins being detected in samples from EC cases, while only 6 different mycotoxins were detected in samples from healthy controls. Ochratoxin A was detected in plasma from all cases and controls, while tenuazonic acid was detected in plasma of 145 (87.3%) cases and 71 (42.8%) controls. Using multivariable logistic regression analysis, exposure to tenuazonic acid (AOR = 1.88 [95% CI: 1.68-2.11]) and to multiple mycotoxins (AOR = 2.54 [95% CI: 2.10-3.07]) were positively associated with EC. CONCLUSION: All cases and controls were exposed to at least one mycotoxin. Cases were exposed to a statistically significantly higher number of mycotoxins than controls. Exposure to tenuazonic acid and to multiple mycotoxins were associated with increased risk of EC in the study population. Although aflatoxin B1-lysine and the ratio of sphinganine to sphingosine (as a biomarker of effect to fumonisin exposure) were not assessed in this study, our result emphasizes the need to characterize the effect of mycotoxin co-exposure as part of the exposome and include it in risk assessment, since the current mycotoxin safety levels do not consider the additive or synergistic effects of mycotoxin co-exposure. Moreover, a prospective study design with regular sampling should be considered in this high incidence area of EC in Ethiopia to obtain conclusive results on the role of mycotoxin exposure in the onset and development of the disease.

Studies on the content of toxic metals in teeth: A narrative review of literature.

The presence of toxic metals in the human environment can have detrimental effects on people's wellbeing. This literature review examines the ways in which various environmental and non-environmental factors can contribute to the accumulation of heavy metals in hard dental tissues. It is of the utmost importance to ensure the safety of the environment by restricting the presence of toxic metals originating from both industrial and non-industrial sources. The aim of this study is to analyze current research and identify the primary sources of heavy metal exposure and the mechanisms by which these metals are deposited in dental tissues. Moreover, the objective of this review is to synthesize data from various studies to determine the main environmental and non-environmental sources of toxic metal exposure that contribute to their presence in dental tissues, as well as the biological and chemical processes that are responsible for the deposition of heavy metals in hard dental tissues. Additionally, the review aims to assess the impact of heavy metal accumulation on dental health and its potential systemic effects on overall well-being. The accumulation of heavy metals in the teeth is influenced by a number of factors, such as age, systemic conditions, the nutritional status, and dental caries. The presence of supernumerary teeth results in altered levels of microelements, including an increase in cadmium (Cd) and copper (Cu). Additionally, smoking exacerbates toxic metal accumulation, especially Cd and lead (Pb), and disrupts the balance of essential minerals within the teeth. These findings underscore the impact of environmental pollution on dental health and highlight the potential of teeth as biomarkers of environmental exposure, emphasizing the need for continued research to address the health risks associated with environmental toxins.

Oil spill impact on Brazilian coral reefs based on seawater polycyclic aromatic hydrocarbon contamination, biliary fluorescence and enzymatic biomarkers in damselfish Stegastes fuscus (Teleostei, Pomacentridae).

The crude oil contamination along the Brazilian Northeast coast significantly impacted reef ecosystems. This study assessed polycyclic aromatic hydrocarbons (PAHs) in seawater, fluorescence of bile PAHs, and biochemical biomarkers in damselfish Stegastes fuscus across four coral reef areas pre- and post-oil contamination. Serrambi (SE) and Japaratinga (JP1) were identified as suitable reference areas. PAH concentrations significantly increased in water post-contamination, predominantly 2 to 3 ring parent and alkylated PAHs. Biliary PAHs naphthalene, phenanthrene, chrysene, pyrene and benzo(a)pyrene increased on Paiva post-spill versus pre-spill to 173 %, 449 %, 334 %, 331 % and 131 %, respectively. Significant increases in ethoxy-resorufin-O-deethylase (EROD) (852 %), catalase (CAT) (139 %) and decrease in lipid peroxidation (LPO) (40 %) and acetylcholinesterase (AChE) (75 %) were verified in Paiva samples. Biliary PAHs and biochemical biomarkers were altered in S. fuscus after exposure to PAHs dissolved from the oil. Stegastes fuscus emerges as a promising sentinel organism for coastal reef oil pollution monitoring.

Synthesis and characterization of the trans- and cis-isomers of N-acetyl-S-(4-hydroxy-2-buten-1-yl)-L-cysteine and their attempted detection in human urine.

1,3-Butadiene (BD) is a carcinogenic air pollutant. N-acetyl-S-(4-hydroxy-2-buten-1-yl)-L-cysteine (MHBMA3 or 4HBeMA), an urinary BD metabolite with unspecified configuration, is considered the most sensitive BD biomarker and has been used in routine biomonitoring since 2012. However, two issues remain unaddressed: why its concentrations are unusually high relative to other urinary BD biomarkers and why some authors reported no detection of the biomarker whereas other authors readily quantitated it. To address the issues, we synthesized and structurally characterized the authentic trans- and cis-isomers of MHBMA3 (designated NE and NZ, respectively), developed an isotope-dilution LC-MS/MS method for their quantification, and examined 67 urine samples from barbecue restaurant personnel (n = 47) and hotel administrative staff (n = 20). The restaurant personnel were exposed to barbecue fumes, which contain relatively high concentrations of BD. The results showed that NE and NZ had highly similar NMR spectra, and were difficult to be well separated chromatographically. The NMR data showed that the MHBMA3 isomer investigated in most previous studies was NE. We did not detect NE and NZ in any samples; however, an interfering peak with varying heights was observed in most samples. Notably, under the chromatographic conditions used in the literature, the peak exhibited indistinguishable retention time from that of NE. Thus, it is highly likely that the interfering peak has been mis-identified as NE in previous studies, providing a reasonable explanation for the high MHBMA3 concentration in urine. The contradiction in the presence of MHBMA3 in urine was also caused by the mis-identification, because the researchers who reported the absence of MHBMA3 were actually detecting NZ. Thus, we clarified the confusion on MHBMA3 in previous studies through correctly identifying the two MHBMA3 isomers. The presence of NE and NZ in human urine warrants further investigations.

Pesticide contamination patterns in Montagu's harrier (Circus pygargus) chicks.

Biomonitoring of persistent pesticides in birds of prey has been carried out for decades, but few studies have investigated their relevance for the monitoring of non-persistent pesticides. Herein, we determined the contamination patterns of multiple pesticides in Montagu's harrier (Circus pygargus) chicks in an intensive farming area of southwestern France. Blood samples from 55 chicks belonging to 22 nests in 2021 were assessed for 104 compounds (herbicides, fungicides, insecticides, safeners and synergists). All chicks had at least one herbicide in their blood, and half had at least two compounds. The 28 compounds detected comprised 10 herbicides, 12 fungicides, 5 insecticides and 1 synergist. Mixtures in blood were predominantly composed of herbicides, and six chicks presented a mixture of the three pesticide classes. The most prevalent compounds were sulcotrione (96% of chicks), tebutam (44%) and chloridazon (31%), of which the latter two had been banned in France for 19 and 3 years, respectively, at the time of sampling. Most compounds are considered non-acutely toxic, but sulcotrione is potentially carcinogenic, mutagenic and reprotoxic, raising questions about the effects on the health of nestlings. Biomonitoring of multiple pesticides through Montagu's harrier chicks in agroecosystems is clearly relevant because it reflects the general pattern of agricultural pesticide use in the study area. It also raises questions about exposure pathways in chicks, and further investigations are needed to disentangle the roles of dietary routes and maternal transfer for the established pesticide contamination patterns.

Short occupational exposure to glyphosate and its biomonitoring via urinary levels of glyphosate and metabolite AMPA (Amino-MethylPhosphonic acid), in Italian vineyard workers.

Glyphosate, an herbicide largely used in various contexts, can have adverse effects on human health. Although it is currently the most applied pesticide worldwide, few studies evaluated the extent of human exposure via biomonitoring. To expand such information, biological monitoring of exposure to glyphosate was conducted. The study has a before-and-after design to demonstrate the immediate impact of short-term interventions. Accordingly, the urine concentrations of glyphosate and its main biodegradation product (amino-methylphosphonic acid- AMPA) were measured before and the day after the single herbicide application in 17 male winegrowers. Urine samples were analyzed by high performance liquid chromatography coupled with a triple quadrupole mass spectrometer equipped with an electrospray ionization source. Glyphosate and AMPA were not detectable in pre-application urine samples (limit of quantification for glyphosate (LOQG) was 0.1 µg/L; limit of quantification for AMPA (LOQAMPA) was 0.5 µg/L). After application, glyphosate urinary levels were above LOQG in all workers. The median, min, and max values were 2.30, 0.51, and 47.2 µg/L, respectively. The same values were found for 50 %, 5 % and 95 % percentiles. After assigning numerical values, such as one half the LOQ, to each of the non-detects, the "z" of Wilcoxon matched-pairs signed-ranks test was -3.62 (p = 0.0003), suggesting the pre-application values being significantly lower than the post-application urinary glyphosate concentration. A similar analysis was not feasible with AMPA urinary levels, which were detectable only in 3 workers, after application. 12 (71 %) workers were significantly exposed to glyphosate, but adherence to the adoption of personal protective equipment was good: 14 (82 %) workers used gloves, 13 (76 %) used overalls and 13 (76 %) facial masks. Our data show that glyphosate can be absorbed by the workers after a single application and confirms the usefulness of biomonitoring in exposed workers. Further studies are needed in larger working populations and with multiple glyphosate applications, as well as to evaluate the correlations of glyphosate urine levels with exposure questionnaire data, in order to assess the actual relevance of risk and protection factors.

Pesticide residues and polyphenols in urine - A combined LC-HRMS screening to reveal intake patterns.

Human exposure to pesticides in the general population occurs mainly through food consumption. However, specific dietary habits or food products that contribute to pesticide exposure are often unknown. In this study, we propose a combined screening for polyphenols and pesticide residues by liquid chromatography coupled to high-resolution mass spectrometry (LC-HRMS) to assess the diet and the associated pesticide exposure. We measured 587 urine samples from women around the 34th week of pregnancy of a prospective mother-child cohort. A non-targeted screening for flavonoid-like compounds related to fruit and vegetable consumption was performed, prioritizing 164 features and identifying a total of 46 features by spectral library search. Based on a subset of markers, k-means clustering was performed, leading to four clusters with presumably similar dietary habits. The clusters were compared against food questionnaire data collected within the period of sample collection. Suspect screening of more than 500 pesticide residues including metabolites was performed, with a total of 40 residues being reported for 27 different pesticides. The detection of pesticide residues was compared across the different clusters of dietary habits. Indications were found that pyrimethanil metabolites might be associated with the consumption of citrus fruits or derivate products. We demonstrate that the method used has the potential to reveal patterns of pesticide intake from specific food commodities.

Exposure to bisphenol A in European women from 2007 to 2014 using human biomonitoring data - The European Joint Programme HBM4EU.

BACKGROUND: Bisphenol A (BPA; or 4,4'-isopropylidenediphenol) is an endocrine disrupting chemical. It was widely used in a variety of plastic-based manufactured products for several years. The European Food Safety Authority (EFSA) recently reduced the Tolerable Daily Intake (TDI) for BPA by 20,000 times due to concerns about immune-toxicity. OBJECTIVE: We used human biomonitoring (HBM) data to investigate the general level of BPA exposure from 2007 to 2014 of European women aged 18-73 years (n = 4,226) and its determinants. METHODS: Fifteen studies from 12 countries (Austria, Belgium, Denmark, France, Germany, Greece, Israel, Luxembourg, Slovenia, Spain, Sweden, and the United Kingdom) were included in the BPA Study protocol developed within the European Joint Programme HBM4EU. Seventy variables related to the BPA exposure were collected through a rigorous post-harmonization process. Linear mixed regression models were used to investigate the determinants of total urine BPA in the combined population. RESULTS: Total BPA was quantified in 85-100 % of women in 14 out of 15 contributing studies. Only the Austrian PBAT study (Western Europe), which had a limit of quantification 2.5 to 25-fold higher than the other studies (LOQ=2.5 µg/L), found total BPA in less than 5 % of the urine samples analyzed. The geometric mean (GM) of total urine BPA ranged from 0.77 to 2.47 µg/L among the contributing studies. The lowest GM of total BPA was observed in France (Western Europe) from the ELFE subset (GM=0.77 µg/L (0.98 µg/g creatinine), n = 1741), and the highest levels were found in Belgium (Western Europe) and Greece (Southern Europe), from DEMOCOPHES (GM=2.47 µg/L (2.26 µg/g creatinine), n = 129) and HELIX-RHEA (GM=2.47 µg/L (2.44 µg/g creatinine), n = 194) subsets, respectively. One hundred percent of women in 14 out of 15 data collections in this study exceeded the health-based human biomonitoring guidance value for the general population (HBM-GVGenPop) of 0.0115 µg total BPA/L urine derived from the updated EFSA's BPA TDI. Variables related to the measurement of total urine BPA and those related to the main socio-demographic characteristics (age, height, weight, education, smoking status) were collected in almost all studies, while several variables related to BPA exposure factors were not gathered in most of the original studies (consumption of beverages contained in plastic bottles, consumption of canned food or beverages, consumption of food in contact with plastic packaging, use of plastic film or plastic containers for food, having a plastic floor covering in the house, use of thermal paper…). No clear determinants of total urine BPA concentrations among European women were found. A broader range of data planned for collection in the original questionnaires of the contributing studies would have resulted in a more thorough investigation of the determinants of BPA exposure in European women. CONCLUSION: This study highlights the urgent need for action to further reduce exposure to BPA to protect the population, as is already the case in the European Union. The study also underscores the importance of pre-harmonizing HBM design and data for producing comparable data and interpretable results at a European-wide level, and to increase HBM uptake by regulatory agencies.