The exposure of Czech firefighters to perfluoroalkyl substances and polycyclic aromatic hydrocarbons: CELSPAC - FIREexpo case-control human biomonitoring study.

The CELSPAC - FIREexpo biomonitoring study investigates the long-term effects of chemical exposure on firefighters' wellness and fitness. It aims to provide science-based measures to minimize the health risks of the firefighting occupation. Here, we present the study design, cohort profile, and first results with respect to internal per- and polyfluoroalkyl substances (PFAS) and polycyclic aromatic hydrocarbons (PAH) levels in study participants. Participants (n = 166) were divided into three subcohorts: i) newly recruited firefighters, ii) professional firefighters with several years' experience, and iii) the control group. Participants underwent physical performance tests, provided information on their lifestyle and diet, and urine and blood samples 1-4 times within an 11-week period. 12 serum PFAS and 10 urinary hydroxylated PAH (OH-PAH) levels were determined using HPLC-MS/MS and compared between subcohorts and samplings. The association of internal exposure with reported lifestyles and occupational factors was investigated using Spearman's correlation, principal component analysis, and multivariate regression analysis. ΣPFAS levels in firefighters were significantly higher than in the control group and were mostly associated with the length of firefighting career, age, blood donation, and population size. 10.9 % and 7.6 % of measurements exceeded the HBM-I or HBM-II value for PFOS and PFOA, respectively. Urinary ΣPAH levels increased significantly after training with burning wooden pallets, but none of them exceeded the no observed genotoxic effect level. Firefighters' occupational exposure, its sources, and pathways, need to be systematically monitored and investigated on a long-term and individual basis. The CELSPAC - FIREexpo study helps to clarify the degree of occupational exposure to the given compounds and the subsequent risks to firefighters.

Time-trends in human urinary concentrations of phthalates and substitutes DEHT and DINCH in Asian and North American countries (2009-2019).

BACKGROUND: Many phthalates are environmental pollutants and toxic to humans. Following phthalate regulations, human exposure to phthalates has globally decreased with time in European countries, the US and Korea. Conversely, exposure to their substitutes DEHT and/or DINCH has increased. In other countries, including China, little is known on the time-trends in human exposure to these plasticizers. OBJECTIVE: We aimed to estimate time-trends in the urinary concentrations of phthalates, DEHT, and DINCH metabolites, in general population from non-European countries, in the last decade. METHODS: We compiled human biomonitoring (HBM) data from 123 studies worldwide in a database termed "PhthaLit". We analyzed time-trends in the urinary concentrations of the excreted metabolites of various phthalates as well as DEHT and DINCH per metabolite, age group, and country/region, in 2009-2019. Additionally, we compared urinary metabolites levels between continents. RESULTS: We found solid time-trends in adults and/or children from the US, Canada, China and Taiwan. DEHP metabolites decreased in the US and Canada. Conversely in Asia, 5oxo- and 5OH-MEHP (DEHP metabolites) increased in Chinese children. For low-weight phthalates, the trends showed a mixed picture between metabolites and countries. Notably, MnBP (a DnBP metabolite) increased in China. The phthalate substitutes DEHT and DINCH markedly increased in the US. SIGNIFICANCE: We addressed the major question of time-trends in human exposure to phthalates and their substitutes and compared the results in different countries worldwide. IMPACT: Phthalates account for more than 50% of the plasticizer world market. Because of their toxicity, some phthalates have been regulated. In turn, the consumption of non-phthalate substitutes, such as DEHT and DINCH, is growing. Currently, phthalates and their substitutes show high detection percentages in human urine. Concerning time-trends, several studies, mainly in Europe, show a global decrease in phthalate exposure, and an increase in the exposure to phthalate substitutes in the last decade. In this study, we address the important question of time-trends in human exposure to phthalates and their substitutes and compare the results in different countries worldwide.

Personal care product use and lifestyle affect phthalate and DINCH metabolite levels in teenagers and young adults.

Humans are widely exposed to phthalates and their novel substitutes, and considering the negative health effects associated with some phthalates, it is crucial to understand population levels and exposure determinants. This study is focused on 300 urine samples from teenagers (aged 12-17) and 300 from young adults (aged 18-37) living in Czechia collected in 2019 and 2020 to assess 17 plasticizer metabolites as biomarkers of exposure. We identified widespread phthalate exposure in the study population. The diethyl phthalate metabolite monoethyl phthalate (MEP) and three di (2-ethylhexyl) phthalate metabolites were detected in the urine of >99% of study participants. The highest median concentrations were found for metabolites of low-molecular-weight (LMW) phthalates: mono-n-butyl phthalate (MnBP), monoisobutyl phthalate (MiBP) and MEP (60.7; 52.6 and 17.6 µg/L in young adults). 1,2-cyclohexanedicarboxylic acid diisononyl ester (DINCH) metabolites were present in 68.2% of the samples with a median of 1.24 µg/L for both cohorts. Concentrations of MnBP and MiBP were similar to other European populations, but 5-6 times higher than in populations in North America. We also observed large variability in phthalate exposures within the study population, with 2-3 orders of magnitude differences in urinary metabolites between high and low exposed individuals. The concentrations varied with season, gender, age, and lifestyle factors. A relationship was found between high levels of MEP and high overall use of personal care products (PCPs). Cluster analysis suggested that phthalate exposures depend on season and multiple lifestyle factors, like time spent indoors and use of PCPs, which combine to lead to the observed widespread presence of phthalate metabolites in both study populations. Participants who spent more time indoors, particularly noticeably during colder months, had higher levels of high-molecular weight phthalate metabolites, whereas participants with higher PCP use, particularly women, tended to have higher concentration of LMW phthalate metabolites.

Application of a pharmacokinetic model in characterizing sources of polychlorinated biphenyl exposure and determining threshold daily intakes for adverse health effects in infants and toddlers.

Characterization of PCB exposure sources for vulnerable population groups is essential to minimize the health effects of PCB exposure. At the same time, it is important to consolidate the knowledge on threshold intakes of PCBs for infants and toddlers to prevent health effects. We estimated total PCB concentrations from birth to 2 years of age in children from Slovak and Czech populations, which continue to have high PCB concentrations in breast milk. Using a pharmacokinetic (PK) model, we characterized dominant PCB exposure sources and estimated new threshold estimated daily intakes (TEDI) (above which adverse effects cannot be excluded) for postnatal PCB exposure in infants and toddlers. In the PK model, concentrations of seven indicator PCBs in breast milk and cord blood samples from 291 mother-child pairs from the Slovak birth cohort, and 396 breast milk samples from Czech mothers we used, together with their physiological characteristics and PCB concentrations from other exposure sources (food, dust, air). The estimated total PCB concentrations in children's blood at different ages were compared with threshold PCB concentrations of 500, 700 and 1000 ng·glipid-1 in serum proposed by the French Agency for Food, Environmental and Occupational Health & Safety (ANSES) and the German Environment Agency (UBA), above which possible adverse health effects may be expected. We estimated that up to 20.6% of Slovak children and up to 45.7% of Czech children at two years of age exceeded the threshold value of 700 ng·glipid-1 in blood. Mean TEDIs leading to values of 500 ng·glipid-1 in blood for children up to two years ranged between 110 and 220 ng·kg-1·bw·day-1, varying according to breastfeeding duration. Breast milk and prenatal exposure contributed to 71%-85% of PCBs exposure at two years of age. In contrast, the contributions of PCBs from dust and indoor air were negligible.

Dynamics of PCB exposure in the past 50 years and recent high concentrations in human breast milk: Analysis of influencing factors using a physiologically based pharmacokinetic model.

In this study we reconstruct the long-term exposure of Czech mothers to polychlorinated biphenyls (PCBs) and determine the causes of high contamination of breast milk by indicator PCBs (iPCBs). A data set containing information from more than 1000 primiparous women from the Czech Republic was used, including iPCB concentrations in breast milk, individual physiology and living characteristics. The time series of PCB intakes for the whole period from the beginning of PCB production in 1958 until 2011 were reconstructed. We estimated the individual lifetime exposure of mothers for all iPCBs, i.e. congeners 28, 52, 101, 118, 138, 153 and 180, using a physiologically based pharmacokinetic (PBPK) model. Various model scenarios were investigated to determine the influence of physiology, age at delivery, past dietary exposure, and food composition on concentrations in breast milk for all iPCBs. The highest contributions to the presence of iPCBs in breast milk were observed for food composition. The main factor determining the concentration of higher-chlorinated PCBs (138, 153 and 180) was past exposure. The most important parameter for identification of children's postnatal exposure through breast milk was the time-span from the maximum of the exposure peak to the birth of the child. The current concentrations of iPCBs in breast milk in the Czech population are still high because the maximum of the exposure peak occurred more than 10 years later than in other European countries and was very broad, e.g. covered more than 10 years.

Long-term time trends in human intake of POPs in the Czech Republic indicate a need for continuous monitoring.

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) from the group of persistent organic pollutants are detected in human tissues years or even decades after their ban. Exposure to PCBs and OCPs can pose risks to human health. In the present study, we calculated the daily intakes of PCBs and OCPs in the Czech population and investigated the long-term trends of human exposure to POPs. Data on POP concentrations from a 16-year period of breast-milk monitoring were used. A toxicokinetic model with consideration of compound-specific elimination half-lives was used to calculate the mothers' daily intake of PCBs and OCPs representing the intake of POPs by all exposure routes. The calculated intakes were compared with dietary intakes calculated by the Czech National Institute of Public Health. The comparison shows good agreement of both intake estimates with decreasing intake trends of POPs in the Czech population in the time period studied. However, several fluctuations with peaks of higher levels were observed in both datasets which are not typical for the period after the ban of use and production of POPs. The available evidence suggests that the increases in chemical concentrations might be caused by food contamination. The calculated intakes of compounds with longer elimination half-lives, such as higher-chlorinated PCBs, were higher in older mothers. This "memory effect" was already observed in other studies and indicates higher exposure in earlier life periods of the mother. Our results suggest that exposure to POPs is still relevant for the Czech population in the period after the ban of the use and production of POPs (post-ban period), especially via food ingestion, though the intake trends are decreasing. Possible food contamination by POPs in the post-ban period requires further assessment.

Screening for halogenated flame retardants in European consumer products, building materials and wastes.

To fulfill national and international fire safety standards, flame retardants (FRs) are being added to a wide range of consumer products and building materials consisting of flammable materials like plastic, wood and textiles. While the FR composition of some products and materials has been identified in recent years, the limited global coverage of the data and the large diversity in consumer products necessitates more information for an overall picture of the FR composition in common products/materials. To address this issue, 137 individual samples of various consumer products, building materials and wastes were collected. To identify and characterize potential sources of FRs in indoor environment, all samples were analyzed for content of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDDs) and novel flame retardants (NFRs). The most frequently detected were HBCDDs (85%), with the highest median concentration of Σ4HBCDDs of 300 mg kg-1 in polystyrenes. The highest median concentration of Σ10PBDEs was found in recycled plastic materials, reaching 4 mg kg-1. The lowest concentrations were observed for NFRs, where the median of Σ12NFRs reached 0.4 mg kg-1 in the group of electrical & electronic equipment wastes. This suggests that for consumer products and building materials that are currently in-use, legacy compounds still contribute to the overall burden of FRs. Additionally, contrasting patterns of FR composition in recycled and virgin plastics, revealed using principle component analysis (PCA), suggest that legacy flame retardants are reentering the market through recycled products, perpetuating the potential for emissions to indoor environments and thus for human exposure.

Screening for perfluoroalkyl acids in consumer products, building materials and wastes.

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) are a large group of important chemical compounds with unique and useful physico-chemical properties, widely produced and used in many applications. However, due to the toxicity, bioaccumulation and long-range transport potential of certain PFASs, they are of significant concern to scientists and policy makers. To assess human exposure to PFASs, it is necessary to understand the concentrations of these emerging contaminants in our environment, and particularly environments where urban population spend most of their time, i.e. buildings and vehicles. A total of 126 samples of building materials, consumer products, car interior materials and wastes were therefore analyzed for their content of key PFASs - 15 perfluoroalkyl acids (PFAAs). At least one of the target PFAAs was detected in 88% of all samples. The highest concentration of Σ15PFAAs was found in textile materials (77.61 µg kg-1), as expected, since specific PFAAs are known to be used for textile treatment during processing. Surprisingly, PFAAs were also detected in all analyzed composite wood building materials, which were dominated by perfluoroalkyl carboxylic acids with 5-8 carbons in the chain (Σ4PFCAs up to 32.9 µg kg-1). These materials are currently widely used for building refurbishment, and this is the first study to find evidence of the presence of specific PFASs in composite wood materials. Thus, in addition to consumer products treated with PFASs, materials used in the construction of houses, schools and office buildings may also play an important role in human exposure to PFASs.

Annual dynamics of perfluorinated compounds in sediment: A case study in the Morava River in Zlín district, Czech Republic.

Two groups of perfluorined compounds (PFCs), i.e. perfluoroalkyl sulfonates (PFASs) and perfluoroalkyl carboxylates (PFCAs) were analysed during a period of 1 year in monthly collected riverbed sediment samples from five sampling sites in an industrial region in Morava River catchment in Czech Republic. Levels of PFCs determined in sediment samples were up to 6.8 µg kg(-1) of dry weight. Among PFCs analysed, mainly short-chain PFASs (C6 to C8) including PFOS were found in sediment samples and their levels were similar to those found in comparable river basins in other parts of Europe. Concentrations of PFCs were correlated with organic carbon content and their variations were mainly correlated by high flow events on Morava River and its tributaries. The changes in PFC concentrations were induced by displacing of PFCs containing particles to the river sediment during these elevated flow events.

The influence of tree species composition on the storage and mobility of semivolatile organic compounds in forest soils.

Soil contamination with PCBs and PAHs in adjacent forest plots, characterized by a distinct composition in tree species (spruce only, mixed and beech only), was analyzed to investigate the influence of ecosystem type on contaminant mobility in soil under very similar climate and exposure conditions. Physical-chemical properties and contaminant concentrations in litter (L), organic (F, H) and mineral (A, B) soil horizons were analyzed. Contaminant distribution in the soil core varied both in relation to forest type and contaminant group/properties. Contaminant mobility in soil was assessed by examining the ratios of total organic carbon (TOC)-standardized concentrations across soil horizons (Enrichment factors, EFTOC) and the relationship between EFTOC and the octanol-water equilibrium partitioning coefficient (KOW). Contaminant distribution appeared to be highly unsteady, with pedogenic/biogeochemical drivers controlling contaminant mobility in organic layers and leaching controlling accumulation in mineral layers. Lighter PCBs displayed higher mobility in all forest types primarily controlled by leaching and, to a minor extent, diffusion. Pedogenic processes controlling the formation of soil horizons were found to be crucial drivers of PAHs and heavier PCBs distribution. All contaminants appeared to be more mobile in the soil of the broadleaved plot, followed by mixed canopy and spruce forest. Increasing proportion of deciduous broadleaf species in the forest can thus lead to faster degradation or the faster leaching of PAHs and PCBs. The composition of humic substances was found to be a better descriptor of contaminant concentration than TOC.

Development and comparison of regression models for the uptake of metals into various field crops.

Field crops represent one of the highest contributions to dietary metal exposure. The aim of this study was to develop specific regression models for the uptake of metals into various field crops and to compare the usability of other available models. We analysed samples of potato, hop, maize, barley, wheat, rape seed, and grass from 66 agricultural sites. The influence of measured soil concentrations and soil factors (pH, organic carbon, content of silt and clay) on the plant concentrations of Cd, Cr, Cu, Mo, Ni, Pb and Zn was evaluated. Bioconcentration factors (BCF) and plant-specific metal models (PSMM) developed from multivariate regressions were calculated. The explained variability of the models was from 19 to 64% and correlations between measured and predicted concentrations were between 0.43 and 0.90. The developed hop and rapeseed models are new in this field. Available models from literature showed inaccurate results, except for Cd; the modelling efficiency was mostly around zero. The use of interaction terms between parameters can significantly improve plant-specific models.

The variability of standard artificial soils: effects on the survival and reproduction of springtail (Folsomia candida) and potworm (Enchytraeus crypticus).

Recent studies have documented significant variability in the basic properties of artificial soil which is used as a standard medium in soil bioassays. Variability in key soil properties could confound the interpretation of toxicity data and bias the output of bioassays. The main aims of this study were (i) to identify the variability in the endpoints survival and reproduction of Folsomia candida and Enchytraeus crypticus related to the artificials soils prepared in different laboratories and (ii) to identify the specific physico-chemical properties of the artificial soils which influence the bioassays results. The results of reproduction tests showed that nearly all tested artificial soils were suitable for the survival and reproduction of both organisms as the validity criteria from the test standards were fulfilled. However, numbers of juveniles varied significantly among soils. The most important factor for F. candida performance was a coarser soil structure. C:N ratio (<22.6) were important for the reproduction of E. crypticus. Both species tolerated a pH (KCl) of artificial soils in the range of 4.27-6.8 and even low TOC (1.5%). Thus, it is possible to reduce peat content in artificial soils, which may increase the comparability of results to those for natural soils.

Accumulation kinetics and equilibrium partitioning coefficients for semivolatile organic pollutants in forest litter.

Soils are important stores of environmentally cycling semivolatile organic contaminants (SVOCs) and represent relevant atmospheric secondary sources whenever environmental conditions favor re-emission. The exchange between air and soil is controlled by resistances posed by interfacial matrices such as the ubiquitously distributed vegetation litter. For the first time, this study focused on the experimental characterization of accumulation parameters for SVOCs in litter under real field conditions. The logarithm of the litter-air equilibrium partitioning coefficient ranged 6.8-8.9 and had a similar dependence on logKOA as that of plant foliage and soil data. Uptake and release rates were also KOA dependent with values (relevant for real environmental conditions) ranging 30,000-150,000 d(-1) and 0.0004-0.0134 d(-1), respectively. The overall mass transfer coefficient v controlling litter-air exchange (0.03-1.4 cm s(-1)) was consistent with previously reported data of v for foliage in forest canopies after normalization on leaf area index. Obtained data suggest that litter holds the potential for influencing atmospheric fugacity in proximity to soil, likely affecting overall exchange of SVOCs between the soil reservoir and the atmosphere.

Influence of climate and land use change on spatially resolved volatilization of persistent organic pollutants (POPs) from background soils.

The subject of this study is the assessment of the influence of climate and land use change on the potential re-emission of organochlorine pesticides (OCPs) from background and agricultural soils. A deterministic spatially and temporally explicit model of the air-surface exchange was created, fed with distributed data of soil and atmospheric concentrations from real measurements, and run under various scenarios of temperature and land use change for a case study area representative of central European conditions. To describe land use influence, some important features were implemented including effect of plowing, influence of land cover, temperature of soil, and seasonal changes of air layer stability. Results show that volatilization of pesticides from soil largely exceeded dry gas deposition in most of the area. Agricultural soils accounted for more than 90% of the total re-emissions both because of the generally higher soil fugacities (higher loads of chemicals and relatively low organic carbon content), but also due to physical characteristics and land management practices enhancing the dynamics of the exchange. An increase of 1 °C in air temperature produced an increase of 8% in the averaged total volatilization flux, however this effect can be neutralized by a change of land use of 10% of the arable lands to grassland or forest, which is consistent with projected land use change in Europe. This suggests that future assessment of climate impact on POP fate and distribution should take into consideration land use aspects.

Variability of standard artificial soils: Physico-chemical properties and phenanthrene desorption measured by means of supercritical fluid extraction.

The study is focused on artificial soil which is supposed to be a standardized "soil like" medium. We compared physico-chemical properties and extractability of Phenanthrene from 25 artificial soils prepared according to OECD standardized procedures at different laboratories. A substantial range of soil properties was found, also for parameters which should be standardized because they have an important influence on the bioavailability of pollutants (e.g. total organic carbon ranged from 1.4 to 6.1%). The extractability of Phe was measured by supercritical fluid extraction (SFE) at harsh and mild conditions. Highly variable Phe extractability from different soils (3-89%) was observed. The extractability was strongly related (R(2)=0.87) to total organic carbon content, 0.1-2mm particle size, and humic/fulvic acid ratio in the following multiple regression model: SFE (%)=1.35*sand (%)-0.77*TOC (%)2+0.27*HA/FA.