Phthalates in German daycare centers: Occurrence in air and dust and the excretion of their metabolites by children (LUPE 3)

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 194 ng/m³, respectively. In the dust, median values of 888 mg/kg for DEHP and 302 mg/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 44.7 μg/l for the DiBP monoester, 32.4 μg/l for the DnBP monoester, and 16.5 μg/l and 17.9 μg/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 14.1 μg/kg b.w. for DiNP and 11.9 μg/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.     

The influence of resource strategies on childhood phthalate exposure—The role of REACH in a zero waste society

The present study aims to investigate how resource strategies, which intend to reduce waste and increase recycling, influence on human exposure to hazardous chemicals from material recycling. In order to examine the flows of hazardous chemicals in recycled material, a mass flow analysis of plastics and paper at European level, including the flow of phthalates, i.e. di(2-ethylhexyl) phthalate (DEHP), di-n-butyl phthalate (DBP), and benzyl-butyl phthalate (BBP), has been performed. The result for the year 2012 shows that 26% of plastic wastes and 60% of paper consumed in Europe were recycled. This corresponds to the finding that approximately 4% of DEHP and BBP and 18% of DBP annual demands in Europe as raw material re-enter the product cycle with recycled plastics and paper. To examine the potential contribution of the phthalate exposure through recycled plastics and paper, a case study assessing the childhood exposures to phthalates from foods packed in recycled paper and plastics has been performed for 2-year-old children in Denmark. The result verifies that an increase in recycled paperboard and PET bottles in food packaging material causes a significant increase in childhood exposure to DBP corresponding to an additional exposure of 0.116–0.355 μg/kg bw/day; up to 18% of the total DBP exposure in Danish 2-year-olds. While most of the DEHP exposure can be explained, more than 50% of DBP and 70% of BBP exposure sources still remain to be identified. Finally, a conceptual framework for a circular economy based on sustainable and clean resource flows is proposed in order to increase material recycling without increasing adverse health effects.     

Considerable exposure to the endocrine disrupting chemicals phthalates and bisphenol-A in intensive care unit (ICU) patients

Critical care medicine has largely benefited from plastic-containing medical devices. However, bisphenol-A (BPA) and phthalates present in the plastics can leach from such devices. We hypothesized that intensive care unit (ICU) patients are exposed to BPA and phthalates through (plastic) medical devices. Serum (n = 118) and urine (n = 102) samples of adult ICU patients (n = 35) were analyzed for total BPA and phthalate metabolites (PMs). Our results showed that adult ICU patients are continuously exposed to phthalates, such as di(2-ethylhexyl)phthalate (DEHP), as well as to BPA, albeit to a lesser extent. This exposure resulted in detectable high serum and urinary levels in almost every patient and at every studied time point. Moreover, these levels were significantly higher than in controls or compared to referenced literature. The chronology of exposure was demonstrated: pre-operative urinary and serum levels of the DEHP metabolites were often below the detection limit. Plastic-containing medical devices were the main source of DEHP exposure: post-operative patients on hemofiltration, extracorporeal membrane oxygenation or both showed serum levels 100-or 1000-fold higher than the levels in the general population reported in the literature. The serum and some of the urinary levels of the DEHP metabolites are the highest ever reported in humans; some at biologically highly relevant concentrations of ≥ 10–50 μM. Despite the continuously tightening regulations, BPA and DEHP appear to be still present in (some) medical devices. Because patient safety is a concern in the ICU, further research into the (possibly toxic and clinical) effects of these chemicals released from medical devices is imperiously necessary.     

Radionuclide concentrations in soil and lifetime cancer risk due to gamma radioactivity in Kirklareli,Turkey

The objective of this study is to evaluate and map soil radionuclides' activity concentrations and environmental outdoor gamma dose rates (terrestrial and cosmic) in Kirklareli, Turkey. The excess lifetime cancer risks are also calculated. Outdoor gamma dose rates were determined in 230 sampling stations and soil samples were taken from 177 locations. The coordinates of the readings were determined by the Global Positioning System (GPS). The outdoor gamma dose rates were determined by Eberline smart portable device (ESP-2) and measurements were taken in air for two minutes at 1 m from the ground. The average outdoor gamma dose rate was 118 ± 34 nGy h^?1. Annual effective gamma dose of Kirklareli was 144 μSv and the excess lifetime cancer risk of 5.0 × 10^?4. Soil samples were analyzed by gamma spectroscopy. The average ²²⁶Ra, ²³⁸U, ²³²Th, ¹³⁷Cs, and ⁴⁰K activities were 37 ± 18 Bq kg^?1, 28 ± 13 Bq kg^?1, 40 ± 18 Bq kg^?1, 8 ± 5 Bq kg^?1 and 667 ± 281 Bq kg^?1, respectively. The average soil radionuclides' concentrations of Kirklareli were within the worldwide range although some extreme values had been determined. Annual effective gamma doses and the excess lifetime risks of cancer were higher than the world's average.     

Personal exposure to HBCDs and its degradation products via ingestion of indoor dust

Personal exposures via ingestion of indoor dust to α-, β-, and γ-hexabromocyclododecanes (HBCDs) and the degradation products (pentabromocyclododecenes (PBCDs) and tetrabromocyclododecadienes (TBCDs)) were estimated for 21 UK adults. Under an average dust ingestion scenario, personal exposures ranged from 4.5 to 1851 ng ΣHBCDs day^? 1; while the range under a high dust ingestion scenario was 11 to 4630 ng ΣHBCDs day^? 1. On average, personal exposure to ΣHBCDs via dust ingestion in this study was 35% α-, 11% β-, and 54% γ-HBCD. However, while exposure to β-HBCD (4–18% of ΣHBCDs) was relatively consistent with the proportion of this diastereomer in the HBCD commercial formulation; exposures to α- and γ-isomers (11–58% and 29–82% of ΣHBCDs respectively) showed substantial variation from the commercial formulation pattern. Personal exposures to ΣTBCDs (median = 0.2 ng day^? 1 under an average dust ingestion scenario) and ΣPBCDs (1.4 ng day^? 1) were significantly lower (p < 0.05) than for ΣHBCDs (48 ng day^? 1). Despite this, the exposure of one participant to ΣPBCDs exceeded the exposure to ΣHBCDs received by 85% of the other participants. On average, house dust provided the major contribution to personal exposure via dust ingestion to all target compounds due to the large time fraction spent in houses. In contrast, although participants spent less time in cars than in offices, car dust makes a higher average contribution (17%) to ΣHBCDs exposure than office dust (13%).     

Increased levels of phthalates in very low birth weight infants with septicemia and bronchopulmonary dysplasia

Very low birth weight infants (VLBW; birth weight < 1500 g) are exposed to potentially harmful phthalates from medical devices during their hospital stay. We measured urinary phthalate concentrations among hospitalized VLBW infants participating in a nutritional study. Possible associations between different phthalates and birth weight (BW), septicemia and bronchopulmonary dysplasia (BPD) were evaluated. Forty-six VLBW infants were enrolled in this randomized controlled nutritional study. The intervention group (n = 24) received increased quantities of energy, protein, fat, essential fatty acids and vitamin A, as compared to the control group (n = 22). The concentrations of 12 urinary phthalate metabolites were measured, using high-performance liquid chromatography coupled to tandem mass spectrometry, at 3 time points during the first 5 weeks of life. During this study, the levels of di (2-ethylhexyl) phthalate (DEHP) metabolites decreased, whereas an increasing trend was seen regarding metabolites of di-iso-nonyl phthalate (DiNP). Significantly higher levels of phthalate metabolites were seen in infants with lower BW and those diagnosed with late onset septicemia or BPD. A significant positive correlation between the duration of respiratory support and DEHP metabolites was observed (p ≤ 0.01) at 2.9 weeks of age. Birth weight was negatively associated with urinary phthalate metabolite concentrations. Infants with lower BW and those diagnosed with septicemia or BPD experienced prolonged exposure from medical equipment containing phthalates, with subsequent higher levels of phthalate metabolites detected. Clinical Trial Registration no.: NCT01103219.     

Flame retardants and organochlorines in indoor dust from several e-waste recycling sites in South China: Composition variations and implications for human exposure

Several classes of flame retardants, such as polybrominated diphenyl ethers (PBDEs), novel brominated flame retardants (NBFRs), dechlorane plus (DPs), and organophosphate flame retardants (PFRs), together with polychlorinated biphenyls (PCBs) were measured in indoor dust from five villages located in three e-waste recycling regions in Guangdong Province, South China. The medians of PBDEs, NBFRs, and PFRs in dust in five sites ranged from 685–67,500, 1460–50,010, and 2180–29,000 ng/g, respectively. These concentrations were much higher than the medians of PCBs (52–2900 ng/g). BDE 209 and decabromodiphenyl ethane (DBDPE) were the two major halogen flame retardants in dust, while tris-(1-chloro-2-propyl) phosphate (TCIPP) and triphenyl phosphate (TPHP) were the major PFRs. Principle component analysis revealed the different pollutant patterns among different sites. The estimated median human exposures of PBDEs, NBFRs, PFRs, and PCBs via dust ingestion were 1.1–24.1, 0.73–20.3, 1.36–23.5, and 0.04–0.93 ng/kg bw/day for adults, and 16.2–352, 10.7–296, 19.9–343, 0.05–0.61, 0.65–13.6 ng/kg bw/day for toddlers, respectively. Residents from Site 5 had the highest exposure (95 percentile levels and high dust ingestion for toddlers) of PBDEs (3920 ng/kg bw/day), NBFRs (3200 ng/kg bw/day), and PFRs (5280 ng/kg bw/day). More attention should be paid to the contamination with NBFRs and PFRs, instead of PCBs, in these e-waste recycling regions, and local public health threat from PBDE alternatives should remain of concern. To the best of our knowledge, this is the first study on human exposure assessment of PFRs at e-waste sites.     

Organic micropollutants in coastal waters from NW Mediterranean Sea: Sources distribution and potential risk

This study provides a first estimation on the sources, distribution and risk of organic micropollutants (OMPs) in coastal waters from NW Mediterranean Sea. Polycyclic aromatic hydrocarbons, polychlorinated biphenyls, organochlorinated pesticides, polybrominated diphenyl ethers, phthalates and alkylphenols were analyzed by solid phase extraction and gas chromatography coupled to tandem mass spectrometry (SPE–GC–EI-MS/MS). River waters and wastewater treatment plant effluents discharging to the sea were identified as the main sources of OMPs to coastal waters, with an estimated input amount of around of 25,800 g d^− 1. The concentration of ΣOMPs in coastal areas ranged from 17.4 to 8442 ng L^− 1, and was the highest in port waters, followed by coastal and river mouth seawaters. A summarized overview of the patterns and sources of OMP contamination on the investigated coastal sea waters of NW Mediterranean Sea, as well as of their geographical distribution was obtained by Principal Component Analysis of the complete data set after its adequate pretreatment. Alkylphenols, bisphenol A and phthalates were the main contributors to ΣOMPs and produced an estimated significant pollution risk for fish, algae and the sensitive mysid shrimp organisms in seawater samples. The combination of GC-MS/MS, chemometrics and risk analysis is proven to be useful for a better control and management of OMP discharges.     

Intake of phthalate-tainted foods and microalbuminuria in children: The 2011 Taiwan food scandal

BackgroundA major threat to public health involving phthalate-tainted foodstuffs occurred in Taiwan in 2011. Phthalates, mainly di-(2-ethylhexyl) phthalate (DEHP), were intentionally added to several categories of food commonly consumed by children. This study investigated the relationship between intake of the phthalate-tainted foods and renal function in children.MethodsChildren aged ≤ 10 years with possible phthalate exposure were enrolled in this study between August 2012 and January 2013. Questionnaires were used to collect details of exposure to phthalate-tainted foodstuffs, and blood and urine samples were collected for clinical biochemical workup. The clinical biomarkers of renal injury, including urinary microalbumin, N-acetyl-beta-d-glucosaminidase (NAG), and β2-microglobulin were measured. Exposure was categorized based on recommended tolerable daily intake level defined by the U.S. Environmental Protection Agency (0.02 mg/kg/day) and the European Food Safety Authority (0.05 mg/kg/day).ResultsWe analyzed intake and renal function of 184 children whose intake of DEHP-tainted foods was known. Higher DEHP exposure to DEHP-tainted foods was significantly associated with increase of urine albumin/creatinine ratio (ACR). Children in the high-exposed group (daily DEHP intake (DDI) > 0.05 mg/kg/day) had 10.395 times the risk of microalbuminuria than the low-exposed group (DDI ≤ 0.02 and > 0 mg/kg/day) and no-exposed group combined after adjustment (95% CI = 1.096–98.580, P = 0.04).ConclusionIntake of DEHP from phthalate-tainted foods may be a potential risk factor for microalbuminuria, a marker of glomerular injury in children.     

A comparative assessment of human exposure to tetrabromobisphenol A and eight bisphenols including bisphenol A via indoor dust ingestion in twelve countries

Tetrabromobisphenol A (TBBPA) and eight bisphenol analogues (BPs) including bisphenol A (BPA) were determined in 388 indoor (including homes and microenvironments) dust samples collected from 12 countries (China, Colombia, Greece, India, Japan, Kuwait, Pakistan, Romania, Saudi Arabia, South Korea, U.S., and Vietnam). The concentrations of TBBPA and sum of eight bisphenols (ƩBPs) in dust samples ranged from < 1 to 3600 and from 13 to 110,000 ng/g, respectively. The highest TBBPA concentrations in house dust were found in samples from Japan (median: 140 ng/g), followed by South Korea (84 ng/g) and China (23 ng/g). The highest ∑ BPs concentrations were found in Greece (median: 3900 ng/g), Japan (2600 ng/g) and the U.S. (2200 ng/g). Significant variations in BPA concentrations were found in dust samples collected from various microenvironments in offices and homes. Concentrations of TBBPA in house dust were significantly correlated with BPA and ∑ BPs. Among the nine target chemicals analyzed, BPA was the predominant compound in dust from all countries. The proportion of TBBPA in sum concentrations of nine phenolic compounds analyzed in this study was the highest in dust samples from China (27%) and the lowest in Greece (0.41%). The median estimated daily intake (EDI) of ∑ BPs through dust ingestion was the highest in Greece (1.6–17 ng/kg bw/day), Japan (1.3–16) and the U.S. (0.89–9.6) for various age groups. Nevertheless, in comparison with the reported BPA exposure doses through diet, dust ingestion accounted for less than 10% of the total exposure doses in China and the U.S. For TBBPA, the EDI for infants and toddlers ranged from 0.01 to 3.4 ng/kg bw/day, and dust ingestion is an important pathway for exposure accounting for 3.8–35% (median) of exposure doses in China.     

Phthalates dietary exposure and food sources for Belgian preschool children and adults

Numerous studies have indicated that for phthalates, the intake of contaminated foods is the most important exposure pathway for the general population. Up to now, data on dietary phthalate intake are scarce and – to the authors' knowledge – not available for the Belgian population. Therefore, the purpose of this study was: (1) to assess the long-term intake of the Belgian population for eight phthalates considering different exposure scenarios (benzylbutyl phthalate (BBP); di-n-butyl phthalate (DnBP); dicyclohexyl phthalate (DCHP); di(2-ethylhexyl) phthalate (DEHP); diethyl phthalate (DEP); diisobutyl phthalate (DiBP); dimethyl phthalate (DMP), di-n-octyl phthalate (DnOP)); (2) to evaluate the intake of BBP, DnBP, DEP and DEHP against tolerable daily intake (TDI) values; and (3) to assess the contribution of the different food groups to the phthalate intake. The intake assessment was performed using two Belgian food consumption databases, one with consumption data of preschool children (2.5 to 6.5 years old) and another of adults (≥ 15 years old), combined with a database of phthalate concentrations measured in over 550 food products sold on the Belgian market. Phthalate intake was calculated using the ‘Monte Carlo Risk Assessment’ programme (MCRA 7.0). The intake of DEHP was the highest, followed by DiBP. The intake of BBP, DnBP and DEP was far below the TDI for both children and adults. However, for DEHP, the 99th percentile of the intake distribution of preschoolers in the worst case exposure scenario was equal to 80% of the TDI, respectively. This is not negligible, since other exposure routes of DEHP exist for children as well (e.g. mouthing of toys). Bread was the most important contributor to the DEHP intake and this may deserve further exploration, since the origin of this phthalate in bread remains unclear.     

Associations between PBDEs in office air,dust, and surface wipes

Increased use of flame-retardants in office furniture may increase exposure to PBDEs in the office environment. However, partitioning of PBDEs within the office environment is not well understood. Our objectives were to examine relationships between concurrent measures of PBDEs in office air, floor dust, and surface wipes.We collected air, dust, and surface wipe samples from 31 offices in Boston, MA. Correlation and linear regression were used to evaluate associations between variables. Geometric mean (GM) concentrations of individual BDE congeners in air and congener specific octanol–air partition coefficients (K_oa) were used to predict GM concentrations in dust and surface wipes and compared to the measured concentrations.GM concentrations of PentaBDEs in office air, dust, and surface wipes were 472 pg/m³, 2411 ng/g, and 77 pg/cm², respectively. BDE209 was detected in 100% of dust samples (GM = 4202 ng/g), 93% of surface wipes (GM = 125 pg/cm²), and 39% of air samples. PentaBDEs in dust and air were moderately correlated with each other (r = 0.60, p = 0.0003), as well as with PentaBDEs in surface wipes (r = 0.51, p = 0.003 for both dust and air). BDE209 in dust was correlated with BDE209 in surface wipes (r = 0.69, p = 0.007). Building (three categories) and PentaBDEs in dust were independent predictors of PentaBDEs in both air and surface wipes, together explaining 50% (p = 0.0009) and 48% (p = 0.001) of the variation respectively. Predicted and measured concentrations of individual BDE congeners were highly correlated in dust (r = 0.98, p < 0.0001) and surface wipes (r = 0.94, p = 002). BDE209 provided an interesting test of this equilibrium partitioning model as it is a low volatility compound.Associations between PentaBDEs in multiple sampling media suggest that collecting dust or surface wipes may be a convenient method of characterizing exposure in the indoor environment. The volatility of individual congeners, as well as physical characteristics of the indoor environment, influence relationships between PBDEs in air, dust, and surface wipes.     

Determination of heavy metals in indoor dust from Istanbul,Turkey: Estimation of the health risk

Levels of eight potentially toxic heavy metals in indoor dust from homes and offices in Istanbul were investigated. The concentrations of heavy metals in indoor dust from homes + office ranged from 62 to 1800 μg g^− 1 for Cu, 3–200 μg g^− 1 for Pb, 0.4–20 μg g^− 1 for Cd, 210–2800 μg g^− 1 for Zn, 2.8–460 μg g^− 1 for Cr, 8–1300 μg g^− 1 for Mn, 2.4–25 μg g^− 1 for Co, 120–2600 μg g^− 1 for Ni. Results of the study were comparable to other studies conducted on indoor dust and street dust from a variety of cities globally. Considering only ingestion + inhalation, the carcinogenic risk level of Cr for adults and children (3.7 × 10^− 5 and 2.7 × 10^− 5) in Istanbul was in the range of EPA's safe limits (1 × 10^− 6 and 1 × 10^− 4), indicating that cancer risk of Cr due to exposure to indoor dust in Istanbul can be acceptable. According to calculated Hazard Quotient (HQ), for non-cancer effects, the ingestion of indoor dust appears to be the major route of exposure to the indoor dust that results in a higher risk for heavy metals, followed by dermal contact and inhalation pathways. However, compared to ingestion and dermal contact exposure, exposure through inhalation is almost negligible. Hazard Index (HI) values for all studied elements were lower than safe limit of 1 and this result suggested that none of the population groups would likely to experience potential health risk due to exposure to heavy metals from indoor dust in the study area.     

Positive association between concentration of phthalate metabolites in urine and microparticles in adolescents and young adults

Di-(2-ethylhexyl) phthalate (DEHP) has been used worldwide in various products for many years. In vitro studies have shown that exposure to DEHP and its metabolite mono(2-ethylhexyl) phthalate (MEHP) induces endothelial cell apoptosis. Moreover, exposure to DEHP had been linked to cardiovascular risk factors and cardiovascular diseases in epidemiological studies. Circulating microparticles have been known to be indicators of vascular injury. However, whether DEHP or its metabolites are independently associated with microparticles in humans remains unknown. From 2006 to 2008, we recruited 793 subjects (12–30 years) from a population-based sample to participate in this cardiovascular disease prevention examination. Each participant was subjected to interviews and biological sample collection to determine the relationship between concentrations of DEHP metabolites MEHP, mono(ethyl-5-hydroxyhexyl) phthalate, and mono(2-ethly-5-oxoheyl) phthalate in urine and concentrations of endothelial microparticles (CD62E and CD31 +/CD42a −), platelet microparticles (CD62P and CD31 +/CD42a +), and CD14 in serum. Multiple linear regression analysis revealed that an ln-unit increase in MEHP concentration in urine was positively associated with an increase in serum microparticle counts/μL of 0.132 (± 0.016) in CD31 +/CD42a − (endothelial apoptosis marker), 0.117 (± 0.023) in CD31 +/CD42a + (platelet apoptosis marker), and 0.026 (± 0.007) in CD14 (monocyte, macrophage, and neutrophil activation marker). There was no association between DEHP metabolite concentration and CD62E or CD62P. In conclusion, a higher MEHP concentration in urine was associated with an increase in endothelial and platelet microparticles in this cohort of adolescents and young adults. Further studies are warranted to clarify the causal relationship between exposure to DEHP and atherosclerosis.     

Sources and human exposure implications of concentrations of organophosphate flame retardants in dust from UK cars,classrooms, living rooms,and offices

Concentrations of a number of organophosphate flame retardants (PFRs) were measured in floor dust collected from UK living rooms (n = 32), cars (n = 21), school and child daycare centre classrooms (n = 28), and offices (n = 61). While concentrations were overall broadly within the range of those reported previously for North America, Japan, and other European countries, median concentrations of TCIPP in all UK microenvironments exceeded those reported elsewhere in the world. Moreover, concentrations of TCIPP and TDCIPP in 2 UK car dust samples were – at 370 μg g^− 1 and 740 μg g^− 1 respectively – amongst the highest reported globally in indoor dust to date. Consistent with this, concentrations of TDCIPP in dust from UK cars exceed significantly those detected in the other microenvironments studied. Concentrations of EHDPP were shown for the first time to be significantly higher in classroom dust than in samples from other microenvironments. When compared to concentrations of PBDEs determined previously in the classroom dust samples; concentrations of all target PFRs exceeded substantially those of those PBDEs that are the principal constituents of the Penta- and Octa-BDE formulations. Moreover, while mass-based concentrations of BDE-209 exceeded those of most of our target PFRs, they still fell below those of TCIPP and EHDPP. In line with a previous observation in Sweden that indoor air contamination with TNBP was significantly lower in newer buildings; concentrations of TNBP in classroom dust were significantly higher in older compared to more recently-constructed schools. Consistent with the reported extensive use of TCIPP and TDCIPP in polyurethane foam, the highest concentrations of both TCIPP and TDCIPP in the classrooms studied, were observed in rooms containing the highest numbers of foam chairs (n = 31 and 18 respectively). Exposure to PFRs of both adults and young children via ingestion of indoor dust was estimated. While even our high-end exposure estimate for young children was ~ 100 times lower than one previously reported health-based limit (HBLV) value for TCIPP; the margin of safety was only 5-fold when compared to another HBLV for this contaminant.     

Causes of variability in concentrations and diastereomer patterns of hexabromocyclododecanes in indoor dust

The temporal evolution of concentrations of α-, β-, and γ-hexabromocyclododecanes (HBCDs), and pentabromocyclododecenes (PBCDs — degradation products of HBCDs) was studied in separate aliquots of a well-homogenized indoor dust sample. These were: (a) exposed to natural light, and (b) kept in the dark. Results revealed a rapid photolytically-mediated shift from γ-HBCD to α-HBCD that was complete after 1 week of exposure, and a slower degradative loss of HBCDs via elimination of HBr. Under the specific conditions studied in this experiment, calculated half-lives (t_1/2) showed the decay in ΣHBCDs concentration was faster in light-exposed samples (t_1/2 = 12 weeks), than in light-shielded dust (t_1/2 = 26 weeks). Within-room spatial and temporal variability in concentrations and diastereomer patterns were studied in six and three rooms respectively. While in some rooms, little variability was detected, in others it was substantial. In one room, concentrations of ΣHBCDs and the relative abundance of γ-HBCD declined dramatically with increasing distance from a TV. The same TV appears to have influenced strongly the temporal variation in that room; with higher concentrations observed in its presence and when the TV was moved closer to the area sampled. Significant negative correlation was observed in one room between concentrations of ΣHBCDs and dust loading (g dust m^? 2 floor), implying “dilution” occurs at higher dust loadings.     

Obstetrical outcomes and biomarkers to assess exposure to phthalates: A review

Studies of the effects on pregnancy outcomes of in utero exposure to phthalates, contaminants that are widely present in the environment, have yielded conflicting results. In addition, the mode of assessment of exposure varies between studies. The aim of this review was therefore to establish a current state of knowledge of the phthalates and metabolites involved in unfavorable pregnancy outcomes. Extant data were analyzed to determine which biomarker is the best suited to assess the relation between in utero exposure to phthalates and pregnancy outcomes.This review of the literature was conducted using the database of PubMed. A search was made of studies investigating exposure to phthalates and the following birth outcomes: preterm birth (gestational age < 37 weeks), change in gestational age, change in body size at birth (birth weight, length, head circumference), anti-androgenic function, decreased anogenital distance, cryptorchidism, hypospadias and congenital malformation. The methodological approach adopted in each study was examined, in particular the methods used for exposure assessment (biomarkers and/or questionnaire).Thirty-five studies were included. Premature birth and decreased anogenital distance were the most commonly reported outcomes resulting from a moderate level of exposure to phthalates. The principal metabolites detected and involved were primary metabolites of di-2(ethylhexyl)-phthalate (DEHP) and di-n-butyl-phthalate (DnBP). No clear conclusion could be drawn with regard to gestational age at birth, body size at birth and congenital malformations. In epidemiological studies, maternal urine is the most suitable matrix to assess the association between in utero exposure to phthalates and pregnancy outcomes: in contrast to other matrices (cord blood, amniotic fluid, meconium and milk), sampling is easy, non-invasive and, can be repeated to assess exposure throughout pregnancy. Oxidative metabolites are the most relevant biomarkers since they are not prone to external contamination.Further epidemiological studies are required during pregnancy to i) determine the role of phthalates other than DEHP [currently replaced by various substitution products, in particular diisononyl-phthalate (DiNP)]; ii) establish the effect of phthalates on other outcomes (body size adjusted for gestational age, and congenital malformations); iii) determine the pathophysiological pathways; and iv) identify the most suitable time for biomarker determination of in utero exposure to phthalates.     

From the shop to the drain — Volatile methylsiloxanes in cosmetics and personal care products

Organosiloxanes are widely used in the formulation of a broad range of cosmetic and personal care products (PCPs), including creams and lotions, bath soaps, shampoo and hair care products to soften, smooth, and moisten. In fact, the intensive and widespread use of organosiloxanes combined with their lipophilic nature, makes them interesting targets for future research, particularly in the toxicology area.This study focused on determining the concentration levels of these compounds in the bestselling brands of PCPs in the Oporto region (Portugal), allowing the estimation of dermal and inhalation exposure to siloxanes and the evaluation of the quantities released to the environment “down-the-drain” and to air. To accomplish this task, a QuEChERS technique (“Quick, Easy, Cheap, Effective, Rugged, and Safe”) was employed to extract the siloxanes from the target PCPs, which has never been tested before. The resulting extract was analysed by gas chromatography–mass spectrometry (GC–MS). The limits of detection varied between 0.17 (L2) and 3.75 ng g^− 1 (L5), being much lower than any values reported in the literature for this kind of products. In general, satisfactory precision (< 10%) and accuracy values (average recovery of 84%) were obtained.123 PCPs were analysed (moisturizers, deodorants, body and hair washes, toilet soaps, toothpastes and shaving products) and volatile methylsiloxanes were detected in 96% of the samples, in concentrations between 0.003 μg g^− 1 and 1203 μg g^− 1. Shampoo exhibited the highest concentration for cyclic and aftershaves for linear siloxanes. Combining these results with the daily usage amounts, an average daily dermal exposure of 25.04 μg kg_bw^− 1 day^− 1 for adults and 0.35 μg kg_bw^− 1 day^− 1 for baby/children was estimated. The main contributors for adult dermal exposure were body moisturizers, followed by facial creams and aftershaves, while for babies/children were body moisturizers, followed by shower gel and shampoo. Similarly, the average daily inhalation exposure was also estimated. Values of 1.56 μg kg_bw^− 1 day^− 1 for adults and 0.03 μg kg_bw^− 1 day^− 1 for babies/children were calculated. An estimate of the siloxanes amount released “down-the-drain” into the sewage systems through the use of toiletries was also performed. An emission per capita between 49.25 and 9574 μg day^− 1 (mean: 1817 μg day^− 1) is expected and shampoo and shower gel presented the higher mean total values (1008 μg day^− 1 and 473.3 μg day^− 1, respectively). In the worst-case scenario, D5 and D3 were the predominant siloxanes in the effluents with 3336 μg day^− 1 and 3789 μg day^− 1, respectively. Regarding the air emissions per capita, values between 8.33 and 6109 μg day^− 1 (mean: 1607 μg day^− 1) are expected and D5 and D6 were the predominant siloxanes.     

Exposure assessment issues in epidemiology studies of phthalates

PurposeThe purpose of this paper is to review exposure assessment issues that need to be addressed in designing and interpreting epidemiology studies of phthalates, a class of chemicals commonly used in consumer and personal care products. Specific issues include population trends in exposure, temporal reliability of a urinary metabolite measurement, and how well a single urine sample may represent longer-term exposure. The focus of this review is on seven specific phthalates: diethyl phthalate (DEP); di-n-butyl phthalate (DBP); diisobutyl phthalate (DiBP); butyl benzyl phthalate (BBzP); di(2-ethylhexyl) phthalate (DEHP); diisononyl phthalate (DiNP); and diisodecyl phthalate (DiDP).MethodsComprehensive literature search using multiple search strategies.ResultsSince 2001, declines in population exposure to DEP, BBzP, DBP, and DEHP have been reported in the United States and Germany, but DEHP exposure has increased in China. Although the half-lives of various phthalate metabolites are relatively short (3 to 18 h), the intraclass correlation coefficients (ICCs) for phthalate metabolites, based on spot and first morning urine samples collected over a week to several months, range from weak to moderate, with a tendency toward higher ICCs (greater temporal stability) for metabolites of the shorter-chained (DEP, DBP, DiBP and BBzP, ICCs generally 0.3 to 0.6) compared with those of the longer-chained (DEHP, DiNP, DiDP, ICCs generally 0.1 to 0.3) phthalates. Additional research on optimal approaches to addressing the issue of urine dilution in studies of associations between biomarkers and different type of health effects is needed.ConclusionsIn conclusion, the measurement of urinary metabolite concentrations in urine could serve as a valuable approach to estimating exposure to phthalates in environmental epidemiology studies. Careful consideration of the strengths and limitations of this approach when interpreting study results is required.     

Priority and emerging flame retardants in rivers: Occurrence in water and sediment,Daphnia magna toxicity and risk assessment

The occurrence, partitioning and risk of eight polybrominated diphenyl ethers (PBDEs), nine new brominated (NBFRs) and ten organophosphorus flame retardants (OPFRs) were evaluated in three Spanish rivers suffering different anthropogenic pressures (Nalón, Arga and Besòs). OPFRs were ubiquitous contaminants in water (ΣOPFRs ranging from 0.0076 to 7.2 μg L^− 1) and sediments (ΣOPFRs ranging 3.8 to 824 μg kg^− 1). Brominated flame retardants were not detected in waters, whereas ΣPBDEs ranged from 88 to 812 μg kg^− 1 and decabromodiphenyl ethane (DBDPE) reached 435 μg kg^− 1 in sediments from the River Besòs, the most impacted river. The occurrence of flame retardants in river water and sediment was clearly associated with human activities, since the highest levels occurred near urban and industrial zones and after wastewater treatment plants discharge. Daphnia magna toxicity was carried out for OPFRs, the most ubiquitous flame retardants, considering individual compounds and mixtures. Toxicity of nine tested OPFRs differed largely among compounds, with EC₅₀ values ranging over three magnitude orders (0.31–381 mg L^− 1). Results evidenced that these compounds act by non-polar narcosis, since their toxicity was proportional to their lipophilicity (K_ow). Furthermore, their joint toxicity was additive, which means that single and joint toxicity can be predicted knowing their concentration levels in water using quantitative structure activity relationships (QSARs) and predictive mixture models. Based on these results, a risk assessment considering joint effect was performed calculating and summing risk quotients (RQs) for the water and sediment samples. No significant risk to D. magna (ΣRQs < 1) was observed for any of the monitored rivers.