Citrinin (CIT), a mycotoxin known to exert nephrotoxicity, is a contaminant in food and feed. Since CIT contamination is not regularly analyzed, data on its occurrence and especially levels in food commodities are insufficient for conducting a conventional exposure assessment. Yet, human biomonitoring, i.e., an analysis of CIT and its metabolite dihydrocitrinone (DH-CIT) in urine samples allows to estimate exposure. This study investigated CIT exposure in young (2–14 years) and adult (24–61 years) residents of three federal states in Germany. A total of 179 urine samples from children and 142 from adults were collected and analyzed by a targeted LC-MS/MS based method for presence of CIT and DH-CIT. At least one of the biomarkers was detected and quantified in all urines, which indicated a widespread dietary exposure to the mycotoxin in Germany. Interestingly, the biomarker concentrations of CITtotal (sum of CIT and DH-CIT) were higher in children’s urine (range 0.05–7.62 ng/mL; median of 0.54 ng/mL) than in urines from adults (range 0.04–3.5 ng/mL; median 0.3 ng/mL). The biomarker levels (CITtotal) of individual urines served to calculate the probable daily CIT intake, for comparison to a value of 0.2 µg/kg bw/day defined as ‘level of no concern for nephrotoxicity’ by the European Food Safety Authority. The median exposure of German adults was 0.013 µg/kg b.w., with only one urine donor exceeding this provisional tolerable daily intake (pTDI) for CIT. The median exposure of children was 0.05 µg/kg bw per day (i.e., 25% of the pTDI); however, CIT exposure in 12 individuals (6.3% of our study group) exceeded the limit value, with a maximum intake of 0.46 µg/kg b.w. per day. In conclusion, these results show evidence for non-negligible exposure to CIT in some individuals in Germany, mainly in children. Therefore, further biomonitoring studies and investigations aimed to identify the major sources of CIT exposure in food commodities are required.

Since 2011 the German federal state North Rhine-Westphalia has been investigating the exposure of children aged 2 to 6 years to pollutants. Human biomonitoring data collected from 3 cycles (2011 to 2017) provide important information on children's exposure to pollutants. 23 biomarkers were identified that had a detection rate of more than 50 % in at least 2 cycles. For 8 of these biomarkers a statistically significant decrease in exposure was found. From the group of phthalates these include the metabolites mono-n-butyl phthalate (MnBP), mono-benzyl phthalate (MBzP), mono-(2-ethylhexyl) phthalate (MEHP) and 7oxo-mono-methyloctyl phthalate (oxoMINP), for the preservatives methyl paraben (MeP), ethyl paraben (EtP) and nPropyl paraben (nPrP) as well as glyphosate (GLY) from the group of herbicides. A significant increase in exposure was found for 3 biomarkers. These include cyclohexane-1,2-dicarboxylic acid mono- hydroxyisononylester (MINCH) from the group of plasticisers, N-methylmalonamic acid (NMMA) from the group of preservatives and 3-phenoxy-benzoic acid (3-PBA) from the group of insecticides. Overall the results show that children's exposure to many critical compound like phthalates and parabens is decreasing. For some others, however, exposure is increasing. Continued collection of human biomonitoring data is necessary to track the development of exposure in the future.

TPS 622: Exposure to flame retardants and plasticizers, Johan Friso Foyer, Floor 1, August 26, 2019, 3:00 PM - 4:30 PM Background/Aim: Children are frequently in contact with a range of consumer products which may contain plasticizers like phthalates. Many of these substances are concerning for health, for example toxic for reproduction. Compared to other age groups only few epidemiological studies about the internal phthalate exposure of preschool children are available. This study aims to assess the current phthalate exposure in German preschool children and to compare the obtained data with results from previous studies, focusing on the same age group, to detect tendencies of exposure. Furthermore, the data will be compared with health evaluation criteria. Methods: Within this cross-sectional study, the urine of 251 children (2-6 years) in North Rhine-Westphalia was collected in 2017/18 and analysed for ten metabolites of nine selected phthalates. The estimated daily intakes of the different phthalates were determined via back-calculation and compared to tolerable daily intakes (TDI). Results: Five metabolites showed values far predominantly below the limit of quantification. The highest median urinary concentration was found for mono-iso-butylphthalate (MiBP) (48 µg/L), followed by mono-n-butylphthalate (17 µg/L), mono(2-ethyl-5-hydrohexyl)phthalate (9,7 µg/L), mono(2-ethyl-5-oxohexyl)phthalate (7,5 µg/L), and 7-oxo-mono-iso-nonylphthalate (3,9 µg/L). Analyzing data from previous studies, a continuous decrease for the last 15 years was observed for all these metabolites with the exception of MiBP. The TDI for di-iso-butylpthalate (DiBP), the parent substance of MiBP, was exceeded in 10% of the study population. For all other parent substances of the metabolites the exposure fell below the specific TDI´s. Conclusions: A continuous decrease of exposure in the last 15 years was observed for most phthalate metabolites, though this tendency was not found for MiBP. Because a high proportion (10%) of our study population exceeds the TDI for DiBP the exposure to this harmful phthalate should be reduced, especially to protect the health of children between 2 and 6 years.

TPS 623: Exposures to pesticides, Johan Friso Foyer, Floor 1, August 26, 2019, 3:00 PM - 4:30 PM Background/Aim: Pesticides are frequently used in agriculture and consumer products. In order to determine human exposure to these pesticides, their metabolites or the parent substance are usually analyzed in urine samples. Only for a few pesticides specific biomarkers are available which means that they can be used for a health based risk assessment on the basis of Acceptable Daily Intakes (ADIs). The aim of this study is to assess the internal exposure of German preschool children to various pesticide groups. For those pesticides with specific biomarkers the daily intake should be calculated and compared to ADIs. Methods: The urine of 95 german preschool children between 3 and 6 years was analysed for 8 metabolites of organophosphate insecticides, 8 metabolites of pyrethroids, 4 metabolites of neonicotinoids and glyphosate. With an established toxicokinetic model we calculated the intake for compounds for which a specific biomarker is available. Results: The highest concentrations in our urine samples could be found for the metabolites of organophosphate insecticides followed in order by pyrethroides, neonicotinoides and glyphosate. Quantitatively most relevant are the organophosphate insecticides dimethylthiophosphate, dimethylphosphate, trichloro-2-pyridinol (TCPy) and nitrophenol with median levels between 1.3 and 4.5 µg/L. The urinary concentrations of the specific biomarker TCPy showed that approximately 5 % of our study group succeeded the ADI for chlorpyrifos. The estimated daily intake values for the pyrethroid deltamethrin and glyphosate were found to be far below their corresponding ADI. Conclusion: Preschool children from Germany were found to be exposed to a wide variety of pesticides. Of the compounds we studied, organophosphate insecticides showed the highest relevance. Unfortunately, most of the measured pesticide metabolites are considered as nonspecific biomarkers and therefore cannot be used for health risk assessment. Exposure to the organophosphate insecticide chlorpyrifos may pose a public health concern for some children in preschool age.

Exposure to polychlorinated biphenyls (PCBs) from indoor air can lead to a significant increase in lower chlorinated congeners in human blood. Lower chlorinated congeners with short biological half-lives can exhibit an indirect genotoxic potential via their highly reactive metabolites. However, little is known about their occurrence in indoor air and, therefore, about the effects of possible exposure to these congeners. We analyzed all mono-, di-, and trichlorinated biphenyls in the indoor air of 35 contaminated offices, as well as in the blood of the 35 individuals worked in these offices for a minimum of 2 years. The median concentration of total PCB in the indoor air was 479 ng/m3 . The most prevalent PCBs in the indoor air samples were the trichlorinated congeners PCB 31, PCB 18, and PCB 28, with median levels of 39, 31, and 26 ng/m3 , respectively. PCB 8 was the most prevalent dichlorinated congener (median: 9.1 ng/m3 ). Monochlorinated biphenyls were not detected in relevant concentrations. In the blood samples, the most abundant congener was PCB 28; nearly 90% of all mono-, di-, and trichlorinated congeners were attributed to this congener (median: 12 ng/g blood lipid).

Polychlorinated biphenyls (PCBs) are a substance group of 209 theoretically possible compounds. The human body burden of PCBs is commonly calculated based on so-called indicator congeners such as PCB 138, PCB 153 and PCB 180, which are analyzed in human blood. The German "Human Biomonitoring (HBM) Commission" assumes that the sum of these indicator congeners multiplied by a factor of 2 represents the total PCB burden. This norm is based on data obtained from exposure studies after dietary intake. Data from indoor air shows a different congener pattern, which might lead to a relatively higher intake of lower chlorinated PCBs by inhalation. In two independent studies with adult participants from two regions in Germany, we measured all 209 PCB congeners in 44 whole blood and 42 plasma samples. Participants from the whole blood study group had additional exposure to PCBs via indoor air. With our analytical method, 141 individual PCB congeners, 27 coeluted pairs of PCB congeners and 2 records of 3 and 4 coeluted PCBs could be determined. Thus, 172 analysis results were reported per sample. In the whole blood samples, 50 congeners showed values below the limit of quantification (LOQ), whereas 94 congeners could not be detected in any of plasma samples. Total PCB concentrations (Σ 209 PCB congeners, incl. ½ LOQ) in the whole blood samples ranged from 99 to 2152ng PCB/g lipid (Median: 454ng/g lipid; 95th Percentile: 1404ng/g lipid). The sum of all 209 measured PCB (incl. ½ LOQ) in plasma samples showed levels between 52 and 933ng PCB/g lipid (Median: 226ng/g lipid; 95th Percentile: 642ng/g lipid). Our results show that the burden of PCBs on the human body is caused mainly by the three highly chlorinated indicator congeners PCB 138, PCB 153 and PCB 180. In median approximately 50% of the total PCB content in human whole blood or plasma samples can be attributed to these congeners. Total PCB, calculated by multiplying the sum of the three indicator congeners by 2, showed a strong and highly significant correlation to the sum of all 209 measured congeners for each sample. A slightly stronger correlation in the whole blood samples could be achieved by choosing six indicator congeners, including the lower chlorinated congeners (PCB 28, 52 and 101) into the calculation. Although this difference is very small, it must be considered that higher PCB levels in indoor air than those measured in the present study might be associated with a higher burden of indoor-air-related congeners in exposed individuals. For precautionary reasons, it could therefore be recommended that the assessment of individuals exposed to PCB via indoor air should be carried out based on the sum of the 6 indicator congeners PCB 28, PCB 52, PCB 101, PCB 138, PCB 153 and PCB 180 multiplied by a factor of 2.

In a study of three German Bundeslander (LUPE 3 study) the indoor air of 63 daycare centers was analysed for carbon dioxide (CO2), airborne particulate matter (PM10 and PM2,5) and volatile organic compounds (VOC). The median daily CO2 concentrations in the individual facilities ranged from 670 ppm to 3,958 ppm (median: 1,297 ppm). The airborne particulate matter, colloquially known as fine dust, were measured with optical aerosol spectrometers. The median values in the group rooms were 146 mu g/m(3) (range: 48 to 368 mu g/m(3)) for PM10 and 21 mu g/m(3) (range: 7 to 60 mu g/m(3)) for PM2,5. The median TVOC value was 179 mu g/m(3) with a 95th percentile value of 617 mu g/m(3). The most frequently identified substances belong to the group of glycol ethers, terpenes and alcohols. Overall, the VOC concentrations were relatively low and comparable to those found in classrooms of schools. Reduction is recommended only in individual cases. The improvement of indoor quality should also be aimed for in the common rooms of daycare centers.

In the present study, plasticizers were measured both in the unsieved (total dust) and the sieved dust (< 63 microns sieve fraction) from 47 house dust samples (vacuum cleaner bags) collected in 47 daycare centers in Germany. Predominantly higher contents were found in the sieved dust fraction compared to the unsieved dust. The medians of concentration ratios unsieved to sieved are about 50 %. In addition, the concentrations in the extracts from vacuum cleaner bags were compared with those of dust samples which were collected directly with ALK dust sampling heads in one group room in each daycare center. The concentrations in the extracts from the different sample collection and preparation methods are comparable with respect to the whole of the facilities. However, wide differences are to be expected when comparing concentrations in extracts from different sample collection and preparation methods looking at an individual facility. Thus, the sample collection and preparation method has to be specified when reporting or using results from house dust analysis.

Plasticizers have been widely used for decades in diverse applications. Therefore indoor air and settled dust samples from 63 daycare centers in Germany were analyzed for the presence of 11 phthalate diesters, 4 adipates, di-isononyl cyclohexane-1,2-dicarboxylate (DINCH), di(2-ethylhexyl) terephthalate (DEHT), acetyl tri-n-butyl citrate (ATBC), and trioctyl trimellitate (TOTM). 10 primary and secondary phthalate metabolites were quantified in urine samples of 663 children (1.7 to 6.7 years old) after they attended the facilities. Moreover, 4 metabolites of DINCH were quantified in urine samples of 208 children. Di-isobutyl phthalate (DiBP), dibutyl phthalate (DnBP), di-2-ethylhexyl phthalate (DEHP), and DINCH were present in the highest concentrations in the indoor air, with median values of 468, 227, 194, and 108 ng/m³, respectively. In dust, median values of 888 mg/kg for DEHP, 302 mg/kg for DINCH, and 302 mg/kg for di-isononyl phthalate (DiNP) were detected. The highest median values observed in urine were 44.7 µg/l for the monoester of DiBP, 32.4 µg/l for that of DnBP, and 16.5 µg/l and 17.9 µg/l for the two secondary DEHP metabolites. The three secondary metabolites of DINCH were observed with median values between 1.1 and 1.7 µg/l.

Children are a very susceptible subgroup of the general population and therefore health authorities have a special interest to prevent them from health hazards. In a study of 3 German Bundesländer the indoor air and dust samples of altogether 63 German daycare centres were analysed for the presence of phthalate diesters in 2011/12 (LUPE 3 study). Inhalable dust and gas phases were collected with a glass fibre filter and polyurethane foam over approximately 6 h while children were attending these facilities. Settled dust was collected by vacuuming the floor of the room using an ALK dust sampler. Indoor air and dust were analysed using a GC/MS system. Median values in the dust samples were 888 mg/kg for di-2-ethylhexyl phthalate (DEHP), 302 mg/kg for diisononyl phthalate (DiNP), 34 mg/kg for diisodecyl phthalate (DiDP), 21 mg/kg for di-n-butyl phthalate (DnBP), and 20 mg/kg for diisobutyl phthalate (DiBP). For DEHP and DiNP maximum values of 10,086 mg/kg and 7,091 mg/kg were observed, respectively. DEHP and DiNP were responsible for 70% and 24% of the total phthalate concentration in the dust. In indoor air phthalates are found mainly in the particulate phase of the filters. Only the more volatile phthalates dimethyl phthalate and diethyl phthalate were found also in the gas phase. The median values in the indoor air were 470 ng/m³ for DiBP, 230 ng/m³ for DnBP, 190 ng/m³ for DEHP, and 100 ng/m³ for DiNP. DnBP and DiBP were together responsible for 55% of the total phthalate concentration in the indoor air. Overall, our study showed that the concentrations of phthalates in indoor air of daycare centers are slightly higher and in dust samples lower compared with schools.

Phthalates have been used for decades in large quantities, leading to the ubiquitous exposure of the population. In an investigation of 63 German daycare centers, indoor air and dust samples were analyzed for the presence of 10 phthalate diesters. Moreover, 10 primary and secondary phthalate metabolites were quantified in urine samples from 663 children attending these facilities. In addition, the urine specimens of 150 children were collected after the weekend and before they went to daycare centers. Di-isobutyl phthalate (DiBP), dibutyl phthalate (DnBP), and di-2-ethylhexyl phthalate (DEHP) were found in the indoor air, with median values of 468, 227, and 194ng/m(3), respectively. In the dust, median values of 888mg/kg for DEHP and 302mg/kg for di-isononyl phthalate (DiNP) were observed. DnBP and DiBP were together responsible for 55% of the total phthalate concentration in the indoor air, whereas DEHP and DiNP were responsible for 70% and 24% of the total phthalate concentration in the dust. Median concentrations in the urine specimens were 44.7μg/l for the DiBP monoester, 32.4μg/l for the DnBP monoester, and 16.5μg/l and 17.9μg/l for the two secondary DEHP metabolites. For some phthalates, we observed significant correlations between their concentrations in the indoor air and dust and their corresponding metabolites in the urine specimens using bivariate analyses. In multivariate analyses, the concentrations in dust were not associated with urinary metabolite excretion after controlling for the concentrations in the indoor air. The total daily "high" intake levels based on the 95th percentiles calculated from the biomonitoring data were 14.1μg/kg b.w. for DiNP and 11.9μg/kg b.w. for DEHP. Compared with tolerable daily intake (TDI) values, our "high" intake was 62% of the TDI value for DiBP, 49% for DnBP, 24% for DEHP, and 9% for DiNP. For DiBP, the total daily intake exceeded the TDI value for 2.4% of the individuals. Using a cumulative risk-assessment approach for the sum of DEHP, DnBP, and DiBP, 20% of the children had concentrations exceeding the hazard index of one. Therefore, a further reduction of the phthalate exposure of children is needed.

Das Landesamt für Gesundheit und Soziales, das Landeslabor Berlin-Brandenburg, das Bayerische Landesamt für Gesundheit und Lebensmittelsicherheit (LGL) und das Landesamt für Natur, Umwelt und Verbraucherschutz Nordrhein-Westfalen (LANUV) untersuchten in einem gemeinsamen Programm untersuchten in einem gemeinsamen Programm das Vorkommen von bestimmten Weichmachern, den sogenannten Phthalaten, in Kindertagesstätten. Untersuchungen des BUND von Hausstaub aus 160 deutschen Kindertagesstätten, die in den Jahren 2010 und 2011 durchgeführt wurden, ergaben teilweise hohe Belastungen mit Phthalaten in diesem Medium. Der BUND kommt zu dem Schluss, dass in einigen Fällen die Belastung so hoch ist, dass der Kita-Besuch zu einer erheblichen Belastung der Kinder mit Weichmachern führt und Grenzwerte für eine gesundheitliche Unbedenklichkeit überschritten werden.