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- Alves, Andreia, et al.
(författare)
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Case Study on Screening Emerging Pollutants in Urine and Nails
- 2017
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Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 51:7, s. 4046-4053
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Tidskriftsartikel (refereegranskat)abstract
- Alternative plasticizers and flame retardants (FRs) have been introduced as replacements for banned or restricted chemicals, but much is still unknown about their metabolism and occurrence in humans. We identified the metabolites formed in vitro for four alternative plasticizers (acetyltributyl citrate (ATBC), bis(2-propylheptyl) phthalate (DPHP), bis(2-ethylhexyl) terephthalate (DEHTP), bis(2ethylhexyl) adipate (DEHA)), and one FR (2,2-bis (chloromethyl)-propane-1,3-diyltetrakis(2-chloroethyl) bisphosphate (V6)). Further, these compounds and their metabolites were investigated by LC/ESI-Orbitrap-MS in urine and finger nails collected from a Norwegian cohort. Primary and secondary ATBC metabolites had detection frequencies (% DF) in finger nails ranging from 46 to 95%. V6 was identified for the first time in finger nails, suggesting that this matrix may also indicate past exposure to FRs as well as alternative plasticizers. Two isomeric forms of DEHTP primary metabolite were highly detected in urine (97% DF) and identified in finger nails, while no DPHP metabolites were detected in vivo. Primary and secondary DEHA metabolites were identified in both matrices, and the relative proportion of the secondary metabolites was higher in urine than in finger nails; the opposite was observed for the primary metabolites. As many of the metabolites present in in vitro extracts were further identified in vivo in urine and finger nail samples, this suggests that in vitro assays can reliably mimic the in vivo processes. Finger nails may be a useful noninvasive matrix for human biomonitoring of specific organic contaminants, but further validation is needed.
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- Bui, Thuy T., et al.
(författare)
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Human exposure, hazard and risk of alternative plasticizers to phthalate esters
- 2016
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Ingår i: Science of the Total Environment. - : Elsevier BV. - 0048-9697 .- 1879-1026. ; 541, s. 451-467
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Tidskriftsartikel (refereegranskat)abstract
- Alternative plasticizers to phthalate esters have been used for over a decade, but data regarding emissions, human exposure and health effects are limited. Here we review 20 alternative plasticizers in current use and their human exposure, hazard and risk. Physicochemical properties are collated for these diverse alternatives and log K-OW values range over 15 orders of magnitude and log K-AW and log K-OA values over about 9 orders of magnitude. Most substances are hydrophobic with low volatility and are produced in high volumes for use in multiple applications. There is an increasing trend in the total use of alternative plasticizers in Sweden compared to common phthalate esters in the last 10 years, especially for DINCH. Evaluative indoor fate modeling reveals that most alternatives are distributed to vertical surfaces (e.g. walls or ceilings). Only TXIB and GTA are predicted to be predominantly distributed to indoor air. Human exposure data are lacking and clear evidence for human exposure only exists for DEHT and DINCH, which show increasing trends in body burdens. Human intake rates are collected and compared with limit values with resulting risk ratios below 1 except for infant's exposure to ESBO. PBT properties of the alternatives indicate mostly no reasons for concern, except that TEHPA is estimated to be persistent and TCP toxic. A caveat is that non-standard toxicological endpoint results are not available and, similar to phthalate esters, the alternatives are likely pseudo-persistent. Keydata gaps for more comprehensive risk assessment are identified and include: analytical methods to measure metabolites in biological fluids and tissues, toxicological information regarding non-standard endpoints such as endocrine disruption and a further refined exposure assessment in order to consider high risk groups such as infants, toddlers and children.
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- Giovanoulis, Georgios, et al.
(författare)
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Analysis of PFAS, phthalates, alternative plasticizers and organophosphate esters in sludge
- 2020
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Rapport (övrigt vetenskapligt/konstnärligt)abstract
- Wastewater treatment plants (WWTPs) can be considered a water pollution point source as all potential pollutants from household as well as from certain industry production passes the WWTPs. Therefore, sludge from WWTPs may be enriched with pollutants and is a relevant matrix for screening for both known and hitherto unknown potential hazardous chemicals. If the sludge from municipal WWTPs is to be used as a source of nutrient or other purposes, then it could be necessary to employ methods for removal of micropollutants in the sludge. The present study constitutes an addition to a large-scale experiment focusing on the reduction of pharmaceuticals, antibiotics and hormones in sewage sludge stored over a period of a year.The objective of the present study was to analyse the presence of per- and polyfluoroalkyl substances (PFAS), organophosphate esters, phthalates and alternative plasticizers and their potential degradation/reduction in mesophilic anaerobic digested sludge in different treatments. This study is part of a larger on-going project on reduction of pharmaceuticals and organic pollutants in sludge. Extracts of sludge samples were analysed using three instrumental methods: liquid chromatography coupled to both tandem mass spectrometry (LC-MS/MS) and high-resolution mass spectrometry (LC-HRMS) and gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). Target analysis of several compounds (PFASs, organophosphate esters, phthalates and alternative plasticizers), analysis of total oxidizable precursors of PFASs and a suspect-screening of more than 1000 PFAS were performed at IVL. Extractable organic fluorine (EOF) was also performed on combustion ion chromatography at Stockholm University for quantification of potential unknown fluorinated compounds in the sludge.Decreasing trends for concentrations of organophosphate esters, phthalates, alternative plasticizers and PFAS could be observed in composted sludge over the storage time while the non-composted showed variable time trends for different substance classes. For PFAS, the sum concentrations of target analytes increased by almost an order of magnitude during 12 months of storage in the non-composted sludge. Furthermore, the results from TOP and EOF furthermore suggested that the sludge from both treatment experiments contained a significant fraction PFAS that could not be quantified by the targeted analysis.
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6. |
- Giovanoulis, Georgios, et al.
(författare)
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Evaluation of exposure to phthalate esters and DINCH in urine and nails from a Norwegian study population
- 2016
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Ingår i: Environmental Research. - : Elsevier BV. - 0013-9351 .- 1096-0953. ; 151, s. 80-90
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Tidskriftsartikel (refereegranskat)abstract
- Phthalate esters (PEs) and 1,2-cyclohexane dicarboxylic acid diisononyl ester (DINCH) used as additives in numerous consumer products are continuously released into the environment, leading to subsequent human exposure which might cause adverse health effects. The human biomonitoring approach allows the detection of PEs and DINCH in specific populations, by taking into account all possible routes of exposure (e.g. inhalation, transdermal and oral) and all relevant sources (e.g. air, dust, personal care products, diet). We have investigated the presence of nine PE and two DINCH metabolites and their exposure determinants in 61 adult residents of the Oslo area (Norway). Three urine spots and fingernails were collected from each participant according to established sampling protocols. Metabolite analysis was performed by LC-MS/MS. Metabolite levels in urine were used to back-calculate the total exposure to their corresponding parent compound. The primary monoesters, such as monomethyl phthalate (MMP, geometric mean 89.7 ng/g), monoethyl phthalate (MEP, 104.8 ng/g) and mono-n-butyl phthalate (MnBP, 893 ng/g) were observed in higher levels in nails, whereas the secondary bis(2-ethylhexyl) phthalate (DEHP) and DINCH oxidative metabolites were more abundant in urine (detection frequency 84-100%). The estimated daily intakes of PEs and DINCH for this Norwegian population did not exceed the established tolerable daily intake and reference doses, and the cumulative risk assessment for combined exposure to plasticizers with similar toxic endpoints indicated no health concerns for the selected population. We found a moderate positive correlation between MEP levels in 3 urine spots and nails (range: 0.56-0.68). Higher frequency of personal care products use was associated with greater MEP concentrations in both urine and nail samples. Increased age, smoking, wearing plastic gloves during house cleaning, consuming food with plastic packaging and eating with hands were associated with higher levels in urine and nails for some of the metabolites. In contrast, frequent hair and hand washing was associated with lower urinary levels of monoisobutyl phthalate (MiBP) and mono(2-ethyl-5-hydroxyhexyl) phthalate (5-OH-MEHP), respectively.
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7. |
- Giovanoulis, Georgios, et al.
(författare)
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Evaluation of exposure to phthalate esters and DINCH in urine and nails from a Norwegian study population
- 2016
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Ingår i: Environmental Research. - 0013-9351 .- 1096-0953. ; :151, s. 80-90
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Tidskriftsartikel (refereegranskat)abstract
- Phthalate esters (PEs) and 1,2-cyclohexane dicarboxylic acid diisononyl ester (DINCH) used as additives innumerous consumer products are continuously released into the environment, leading to subsequenthuman exposure which might cause adverse health effects. The human biomonitoring approach allows thedetection of PEs and DINCH in specific populations, by taking into account all possible routes of exposure(e.g. inhalation, transdermal and oral) and all relevant sources (e.g. air, dust, personal care products, diet). We have investigated the presence of nine PE and two DINCH metabolites and their exposure determi-nants in 61 adult residents of the Oslo area (Norway). Three urine spots andfingernails were collectedfrom each participant according to established sampling protocols. Metabolite analysis was performed byLC-MS/MS. Metabolite levels in urine were used to back-calculate the total exposure to their correspondingparent compound. The primary monoesters, such as monomethyl phthalate (MMP, geometric mean89.7 ng/g), monoethyl phthalate (MEP, 104.8 ng/g) and mono-n-butyl phthalate (MnBP, 89.3 ng/g) wereobserved in higher levels in nails, whereas the secondary bis(2-ethylhexyl) phthalate (DEHP) and DINCHoxidative metabolites were more abundant in urine (detection frequency 84–100%). The estimated daily intakes of PEs and DINCH for this Norwegian population did not exceed the established tolerable dailyintake and reference doses, and the cumulative risk assessment for combined exposure to plasticizers withsimilar toxic endpoints indicated no health concerns for the selected population. We found a moderatepositive correlation between MEP levels in 3 urine spots and nails (range: 0.56–0.68). Higher frequency ofpersonal care products use was associated with greater MEP concentrations in both urine and nail samples.Increased age, smoking, wearing plastic gloves during house cleaning, consuming food with plasticpackaging and eating with hands were associated with higher levels in urine and nails for some of themetabolites. In contrast, frequent hair and hand washing was associated with lower urinary levels ofmonoisobutyl phthalate (MiBP) and mono(2-ethyl-5-hydroxyhexyl) phthalate (5-OH-MEHP), respectively.
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- Giovanoulis, Georgios, et al.
(författare)
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Hand Wipes: A Useful Tool for Assessing Human Exposure to Poly- and Perfluoroalkyl Substances (PFASs) through Hand-to-Mouth and Dermal Contacts
- 2019
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Ingår i: Environmental Science and Technology. - 0013-936X .- 1520-5851.
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Tidskriftsartikel (refereegranskat)abstract
- The indoor environment contributes considerably to human exposure to poly- and perfluoroalkyl substances (PFASs). This study estimated the human exposure to PFASs from the indoor environment through hand-to-mouth and dermal contacts using hand wipes. An analytical method was developed to determine 25 PFASs in hand wipe samples collected as a composite sample from both hands of 60 adults. Polyfluoroalkyl phosphate esters (PAPs) were the predominant PFASs in the hand wipe samples (medians between 0.21 and 0.54 ng per sample). Positive and significant correlations were observed between PAPs, perfluorooctanesulfonate (PFOS), and perfluorooctanoate (PFOA) in hand wipes. Low frequency of daily hand washing (≤8 times day–1) was associated with 30–50% higher concentrations of PFOS, PFOA, and 8:2diPAP in hand wipes. Further, significant correlations between paired hand wipes and house dust samples were observed for PFOS, PFOA, and 6:2diPAP. Also, a significant correlation between PFOS in hand wipes and EtFOSE in indoor air was found. This finding indicates either a common source of exposure or a transformation of EtFOSE to PFOS in the environment or on the hands. The contributions of direct and indirect exposure to perfluoroalkyl acids (PFAAs) showed that PFOA contributed the highest exposure to adults via hand-to-mouth and dermal contacts, followed by PFOS. The median of estimated daily intakes via hand-to-mouth and dermal contacts (for hands only) for PFOA were 0.83 and 0.50 pg·kg bw–1·day–1, respectively. This study gives a first indication that PFAS concentrations in hand wipes can be used as a proxy for the exposure to PFASs from indoor environments, but further studies are needed to confirm this.
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