Sigrid Scharf

Bisphenol A: emissions from point sources

Bisphenol A is widely used for the production of epoxy resins and polycarbonate plastics. Special in vitro test systems and animal experiments showed a weak estrogenic activity for Bisphenol A. Based on in vitro receptor interaction studies, the activity was estimated to be 2 x 10(-3) lower than that of estradiol. Especially aquatic wildlife could be endangered by waste water discharges. To manage possible risks arising from Bisphenol A contamination, the major fluxes need to be obtained and the contributors to the contamination of municipal treatment plants need to be determined. In this study, industrial emitters and communal waste waters were monitored simultaneously. Mixed samples were taken over periods of one week at nine sample sites. The results showed that the concentrations and fluxes were variable. The paper industry was the major Bisphenol A contributor to the influent of the waste water treatment plant. All the other fluxes measured, including two household areas, were considerably low. About 90% of the total load was removed during the waste water treatment.

Occurrence of polycyclic musks in wastewater and receiving water bodies and fate during wastewater treatment

The occurrence of cashmerane (DPMI), celestolide, phantolide, traesolide (ATII), galaxolide (HHCB) and tonalide (AHTN) in sewage and surface waters and their fate during wastewater treatment and anaerobic sludge digestion is investigated. AHTN and HHCB are the most important representatives and influent concentrations of 0.41-1.8 and 0.9-13 μgL(-1) are observed. DPMI is detected in influent and effluent samples but in notably lower concentrations than AHTN and HHCB. Major sources of polycyclic musks are households, whereas industrial emitters seem to be of minor importance. This conclusion is supported by the analysis of selected industrial wastewaters (metal, textile and paper industry). Specific emissions of 0.36 ± 0.19 and 1.6 ± 1.0 mg cap(-1)d(-1) for AHTN and HHCB are calculated. Overall removal efficiencies between approx 50% and more than 95% are observed during biological wastewater treatment and removal with the excess sludge is the major removal pathway. Log K(D) values of 3.73-4.3 for AHTN, 3.87-4.34 for HHCB and 2.42-3.22 for DPMI are observed in secondary sludge. During sludge digestion no or only slight removal occurred. Mean polycyclic musk concentrations in digested sludge amounted to 1.9 ± 0.9 (AHTN), 14.2 ± 5.8 (HHCB), 0.8 ± 0.4 (ATII) and 0.2 ± 0.09 (DPMI) mgkg(-1) dry matter. In the receiving water systems a comparable distribution as during wastewater treatment is observed. AHTN, HHCB and DPMI are detected in surface waters (ND (not detected) - <0.04, ND - 0.32 and ND - 0.02 μg L(-1)) as well as AHTN and HHCB in sediments (ND - 20, ND - 120 μg kg(-1)). For HHCB an apparent K(OC) value of 4.1-4.4 is calculated for sediments. Major source for polycyclic musks in surface waters are discharges from wastewater treatment plants. For HHCB and DPMI 100% of the load observed in the sampled surface waters derive from discharges of treated wastewater.

Emissions of perfluorinated alkylated substances (PFAS) from point sources--identification of relevant branches.

Effluents of wastewater treatment plants are relevant point sources for the emission of hazardous xenobiotic substances to the aquatic environment. One group of substances, which recently entered scientific and political discussions, is the group of the perfluorinated alkylated substances (PFAS). The most studied compounds from this group are perfluorooctanoic acid (PFOA) and perfluorooctane sulphonate (PFOS), which are the most important degradation products of PFAS. These two substances are known to be persistent, bioaccumulative and toxic (PBT). In the present study, eleven PFAS were investigated in effluents of municipal wastewater treatment plants (WWTP) and in industrial wastewaters. PFOS and PFOA proved to be the dominant compounds in all sampled wastewaters. Concentrations of up to 340 ng/L of PFOS and up to 220 ng/L of PFOA were observed. Besides these two compounds, perfluorohexanoic acid (PFHxA) was also present in nearly all effluents and maximum concentrations of up to 280 ng/L were measured. Only N-ethylperfluorooctane sulphonamide (N-EtPFOSA) and its degradation/metabolisation product perfluorooctane sulphonamide (PFOSA) were either detected below the limit of quantification or were not even detected at all. Beside the effluents of the municipal WWTPs, nine industrial wastewaters from six different industrial branches were also investigated. Significantly, the highest emissions or PFOS were observed from metal industry whereas paper industry showed the highest PFOA emission. Several PFAS, especially perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluorododecanoic acid (PFDoA) and PFOS are predominantly emitted from industrial sources, with concentrations being a factor of 10 higher than those observed in the municipal WWTP effluents. Perfluorodecane sulphonate (PFDS), N-Et-PFOSA and PFOSA were not detected in any of the sampled industrial point sources.

Human biomonitoring of phthalate exposure in Austrian children and adults and cumulative risk assessment.

Phthalates are a class of chemicals widely used as plasticisers in a multitude of common consumer products. Through contact with such products, people are regularly exposed to phthalates, which are suspected to contribute to adverse health effects, particularly in the reproductive system. In the present study, 14 urinary phthalate metabolites of 10 parent phthalates were analysed by HPLC-MS/MS among the Austrian population aged 6-15 and 18-81 years in order to assess phthalate exposure. In the total study population, ranges of urinary phthalate metabolite concentrations were n.d.-2,105 μg/l (median 25 μg/l) for monoethyl phthalate (MEP), n.d.-88 μg/l (10 μg/l) for mono-n-butyl phthalate (MnBP), n.d.-248 μg/l (28 μg/l) for mono-isobutyl phthalate (MiBP), n.d.-57 μg/l (1.8 μg/l) for mono-benzyl phthalate (MBzP), n.d.-20 μg/l (n.d.) for mono-(2-ethylhexyl) phthalate (MEHP), n.d.-80 μg/l (2.6 μg/l) for mono-(2-ethyl-5-hydroxyhexyl) phthalate (5OH-MEHP), n.d.-57 μg/l (1.9 μg/l) for mono-(2-ethyl-5-oxohexyl) phthalate (5oxo-MEHP), n.d.-219 μg/l (11 μg/l) for mono-(5-carboxy-2-ethylpentyl) phthalate (5cx-MEPP), n.d.-188 μg/l (1.6 μg/l) for 3-carboxy-mono-proply phthalate (3 cx-MPP), n.d.-5.5 μg/l (n.d.) for mono-cyclohexyl phthalate (MCHP), n.d.-4.5 μg/l (n.d.) for mono-n-pentyl phthalate (MnPeP), n.d.-3.4 μg/l (n.d.) for mono-n-octyl phthalate (MnOP), n.d.-13 μg/l (n.d.) for mono-isononyl phthalate (MiNP), and n.d.-1.1 μg/l (n.d.) for mono-isodecyl phthalate (MiDP). Generally, children exhibited higher levels of exposure to the majority of investigated phthalates, except to MEP, which was found in higher concentrations in adults and senior citizens at a maximum concentration of 2,105 μg/l. Individual daily intakes were estimated based on urinary creatinine and urinary volume excretion and were then compared to acceptable exposure levels, leading to the identification of exceedances of mainly the Tolerable Daily Intakes (TDI), especially among children. The execution of a cumulative risk assessment based on Hazard Indices showed cause for concern mainly for children, as well as in rare cases for adults. Although phthalate exposure seems to have decreased in previous years, the wide distribution and existing exceedances of acceptable levels indicate that phthalate exposure should be further monitored in order to identify exposure sources and enable appropriate minimisation measures.

Sources and behaviour of bismuth active substances (BiAS) in a municipal sewage treatment plant

Non-ionic surfactants are widely used for household and industrial purposes. For different reasons the metabolites, e.g. 4-nonylphenol, nonylphenol monoethoxylate, nonylphenol diethoxylate and 4-tert-octylphenol, are especially considered to be endocrine disruptive and thus potentially harmful for the environment. In this study, field samples of raw wastewater from different point sources, including industrial effluents, household effluents, the influent and secondary effluent of a wastewater treatment plant that treats this wastewater were monitored simultaneously. Composite samples were taken five times over periods of 1 week at nine sample sites. The results showed that the concentrations and fluxes were varying. In addition industrial, influent and effluent samples were investigated for nonylphenol (NP). The highest concentrations of bismuth active substances (BiAS) were obtained by wastewater samples from a chemical and a cloth washing company ranging from 10,200 to 65,600 microg/l and 14,600 to 33,900 microg/l BiAS, respectively. Although the concentration of BiAS in the wastewater of the paper production was only between 460 and 1200 microg/l BiAS, the NP/BiAS ratio of 0.51% was considerably higher than in other industrial effluents. The BiAS concentration in wastewater samples from households ranged from 2200 to 7900 microg/l BiAS, but the NP concentration was quite low, 0.01% of BiAS. This could be due to the effort within the EU to phase out nonylphenol polyethoxylates in household detergents. Influent concentrations between 700 and 2200 microg/l BiAS with removal rates in the WWTP ranging from 70.7 to 99.4% with an average of 92.2% could be measured.

Semivolatile compounds in schools and their influence on cognitive performance of children

ObjectivesWHO’s Children’s Environment and Health Action Plan for Europe (CEHAPE) focuses on improvements of indoor environments where children spend most of their time. To investigate the relationship between school indoor air pollutants and cognitive performance in elementary school children, a multidisciplinary study was planned in all-day schools in Austria.Materials and MethodsIn a cross-sectional study (LuKi study: Air and Children) indoor air pollutants were monitored in nine elementary all-day schools in urban and rural regions of Austria. In addition, school dust and suspended particulates (PM10, PM2.5) were measured, focusing on semivolatile compounds (e.g. phthalates, phosphororganic compounds [POC]). Health status and environmental conditions were determined by parents’ questionnaire, cognitive function was measured by Standard Progressive Matrices (SPM).ResultsOverall, 596 children (6–8 years of age) were eligible for the study. Cognitive tests were performed in 436 children. Analysis showed significant correlations of tris(2-chlorethyl)-phosphate (TCEP) in PM10 and PM2.5 and school dust samples with cognitive performance. Cognitive performance decreased with increasing concentrations of TCEP. Furthermore, cognitive function decreased significantly with increasing CO2 levels.ConclusionsPOC are widely used as plasticizers, flame retardants and floor sealing. This is the first report of a correlation between TCEP in indoor air samples and impairment of cognitive performance in school children. As a precautionary measure, it is recommended to prohibit the use of toxic chemicals and those suspected of a toxic potential in children’s environments such as schools.

Life without plastic: A family experiment and biomonitoring study

Exposure to bisphenol-A (BPA) and phthalates has been associated with negative health outcomes in animal and human studies, and human bio-monitoring studies demonstrate widespread exposure in the US and Europe. Out of concern for the environment and health, individuals may attempt to modify their environment, diet, and consumer choices to avoid such exposures, but these natural experiments are rarely if ever quantitatively evaluated. The aim of the study was to evaluate the difference in urinary concentrations of BPA and phthalate metabolites following an exposure reduction intervention among an Austrian family of five. Urine samples were taken shortly after the family had removed all plastic kitchenware, toys, and bathroom products, and started a concerted effort to eat less food packaged in plastic. Two-months later, urine samples were collected at a follow-up visit, and concentrations of BPA and phthalate metabolites were compared. Shortly after removal of plastic urinary concentrations of BPA were below limit of quantification in all samples. Phthalate concentrations were low, however, 10 of 14 investigated metabolites could be found above limit of quantification. After the two-month intervention, phthalate urinary concentrations had declined in some but not all family members. In the mother most phthalate metabolites increased. The low levels might be partly due to the environmentally conscious lifestyle of the family and partly due to the fact that body levels had dropped already because of the delay of four days between finishing removal and first measurement. Further two months avoidance of dietary exposure and exposure to environmental plastics reduced urinary concentrations for all but one metabolite in the oldest son only, but decreased somewhat in all family members except the mother.

Phthalate Metabolites, Consumer Habits and Health Effects

Phthalates are multifunctional chemicals used in a wide variety of consumer products. The aim of this study was to investigate whether levels of urinary phthalate metabolites in urine samples of Austrian mothers and their children were associated with consumer habits and health indicators. Within an Austrian biomonitoring survey, urine samples from 50 mother-child pairs of five communities (two-stage random stratified sampling) were analysed. The concentrations of 14 phthalate metabolites were determined, and a questionnaire was administered. Monoethyl phthalate (MEP), mono-n-butyl phthalate (MnBP), mono-isobutyl phthalate (MiBP), monobenzyl phthalate (MBzP), mono-(2-ethylhexyl) phthalate (MEHP), mono-(2-ethyl-5-hydroxyhexyl) phthalate (5OH-MEHP), mono-(2-ethyl-5-oxohexyl) phthalate (5oxo-MEHP), mono-(5-carboxy-2-ethylpentyl) phthalate (5cx-MEPP), and 3-carboxy-mono-propyl phthalate (3cx-MPP) could be quantified in the majority of samples. Significant correlations were found between the use of hair mousse, hair dye, makeup, chewing gum, polyethylene terephthalate (PET) bottles and the diethyl phthalate (DEP) metabolite MEP. With regard to health effects, significant associations of MEP in urine with headache, repeated coughing, diarrhoea, and hormonal problems were observed. MBzP was associated with repeated coughing and MEHP was associated with itching.

Austrian reference values for phthalate metabolite exposure in children/adolescents and adults

Reference values (RV95) are statistically derived values comprising the rounded 95th percentiles within the 95% confidence interval and indicate the upper margin of background exposure to chemical substances in a population at a given time period. Based on representative national human biomonitoring data on several urinary phthalate metabolites in children, adolescents and adults from 2010 to 2011, RV95 were derived for the Austrian population based on a IUPAC guideline and the recommendation of the German Human Biomonitoring Commission. The RV95 (rounded values) for phthalate metabolites in children and adolescents aged 6-15 years are 110 μg/l (confidence interval of 95th population percentile: 83.7-163) for mono-ethyl phthalate (MEP), 45 μg/l (40.9-60.6) for mono-n-butyl phthalate (MnBP), 130 μg/l (126-161) for mono-isobutyl phthalate (MiBP), 25 μg/l (17.8-33.6) for mono-benzyl phthalate (MBzP), 100 μg/l (94.0-126) for the sum of the di(2-ethylhexyl) phthalate (DEHP) metabolites including mono(2-ethylhexyl) phthalate (MEHP), mono(2-ethyl-5-hydroxyhexyl) phthalate (5OH-MEHP), mono(2-ethyl-5-oxohexyl) phthalate (5oxo-MEHP) and mono(2-ethyl-5-carboxypentyl) phthalate (5cx-MEPP), and 1.5 μg/l (0.64-1.6) for mono-cyclohexyl phthalate (MCHP). In adults aged 18-81 years, RV95 are 440 μg/l (353-636) for MEP, 40 μg/l (33.1-52.1) for MnBP, 110 μg/l (87.3-118) for MiBP, 10 μg/l (7.2-11.8) for MBzP, 50 μg/l (44.6-68.3) for the sum of MEHP, 5OH-MEHP, 5oxo-MEHP and 5cx-MEPP, and 1.5 μg/l (0.95-1.8) for MCHP. For almost all investigated metabolites, children and adolescents exhibit higher RV95 than adults, with the exceptions being MEP and MCHP. Compared to available RV95 for Germany and Canada, Austrian values are lower for all investigated population groups.

Research Article. Perfluoroalkylated substances in human urine: results of a biomonitoring pilot study

Abstract Perfluoroalkylated substances (PFASs) are a class of synthetic chemicals used in a wide range of processes and products due to their unique physicalchemical properties. Through intake of PFASs via food or several consumer products, humans can be exposed. Long-chain PFASs have been associated with adverse effects in laboratory animals, and there is also evidence for adverse health effects in humans. Although investigations of human exposure are mainly conducted in blood samples, some studies have shown that especially short-chain PFASs can be detected in human urine. In the present study, a sensitive analytical method was adapted for the measurement of 12 PFASs in human urine samples by HPLC-MS/MS. For verifying this method, concentrations in 11 male and female participants aged 25-46 years were analysed. In the study population, ranges of urinary PFASs concentrations were n.d.- 8.5 ng/l for perfluoropentanoic acid, <LOQ-3.0 ng/l for perfluorohexanoic acid, n.d.-1.8 ng/l for perfluorohexane sulphonate, n.d.-0.99 ng/l for perfluoroheptanoic acid, 0.79-5.1 ng/l for perfluorooctanoic acid, <LOQ-4.9 ng/l for perfluorooctane suphonate, and <LOQ-0.57 ng/l for perfluorononanoic acid. For the other investigated PFASs, no urinary exposure could be identified in any of the samples. The present study shows that several shortchain PFASs are detectable in human urine.