Alkyl protocatechuates as novel urinary biomarkers of exposure to p-hydroxybenzoic acid esters (parabens)

Human exposure to p-hydroxybenzoic acid esters (parabens) is a concern, owing to adverse health effects of these compounds. Parabens are metabolized and eliminated from the human bodies within a few hours of exposure. In this study, for the first time, methyl- and ethyl-protocatechuates (OH-MeP and OH-EtP) and their parent compounds, methyl- (MeP) and ethyl-parabens (EtP), were determined in urine samples collected from U.S. children and adults. Alkyl protocatechuates were found in almost all urine samples, with median concentrations of 11.8 (OH-MeP) and 2.90 ng/mL (OH-EtP) in adults, and 5.43 (OH-MeP) and 0.85 ng/mL (OH-EtP) in children. In adults, the concentrations of urinary OH-MeP and OH-EtP were higher than the corresponding concentrations of MeP and EtP. Significant correlation between OH-MeP/OH-EtP and MeP/EtP was observed. This is the first report to document hydroxylation of parabens in humans, and to propose hydroxylated metabolites (i.e., alkyl protocatechuates) as alternative biomarkers of exposure to parabens in human biomonitoring studies. The rates of transformation of parabens between children and adults appeared to be different, as evidenced from the slopes of regression between alkyl protocatechuates and parabens. In addition to alkyl protocatechuates, hydroxybenzoic acid (4-HB) and 3,4-dihydroxybenzoic acid (3,4-DHB) were found at considerable levels in the urine samples. The occurrence of a significant proportion of alkyl protocatechuates and 3,4-DHB suggests the need for inclusion of these derivatives in accurate estimation of human exposure to parabens and in epidemiological studies that associate paraben exposure to health outcomes in populations.     

A survey of parabens in commercial pharmaceuticals from China and its implications for human exposure

Parabens are widely used as antimicrobial preservatives during pharmaceutical production. However, little information is available regarding the occurrence of parabens in commercial pharmaceuticals and their implications for human exposure. In this study, six commonly used parabens were analyzed by ultra-performance liquid chromatography-tandem mass spectrometry with 100 commercial pharmaceuticals collected from China. Almost all of the pharmaceutical samples contained at least one kind of parabens with the detection frequency of 97%. The concentrations of Σ₆parabens (sum of the six parabens) ranged from below MDL to 1256 ng/g, with mean and median values of 94.8 and 119 ng/g, respectively. Methyl paraben (MeP), ethyl paraben (EtP) and propyl paraben (PrP) were the predominant compounds. Significant positive correlation was observed between concentrations of MeP and PrP, indicating their co-applications in pharmaceuticals. Levels of Σ₆parabens varied in different categories of pharmaceuticals and increased with their shelf lives. Based on the measured concentrations and daily ingestion rates of pharmaceuticals, the estimated daily intake (EDI) of parabens was calculated. The median values of EDI_{pharmaceutical} for male adults, female adults and children were 4.05, 4.75 and 9.73 ng/kg-bw/day, respectively, which were three orders of magnitude lower than those from foodstuffs and personal care products (PCPs). It was firstly reported that the total exposure dose was 0.326 mg/kg-bw/day via foodstuffs, PCPs, and pharmaceuticals for Chinese female adults.     

Occurrence of parabens in foodstuffs from China and its implications for human dietary exposure

Parabens are alkyl esters of p-hydroxybenzoic acid and are used as antimicrobial preservatives in a range of consumer products, including cosmetics, pharmaceuticals, and foodstuffs. Despite their widespread use, prior to this study, paraben concentrations in foodstuffs from China and human dietary exposure to these chemicals have been unknown. In this study, concentrations of six parabens were determined in 13 categories of food samples (n = 282), including cereals and cereal products, meat, fish and seafood, eggs, dairy products, bean products, fruits, vegetables, cookies, beverages, cooking oils, condiments, and others, collected from nine cities in China. Almost all (detection rate: 99%) food samples contained at least one of the parabens analyzed, and the total concentrations (ΣParabens; sum of six parabens) ranged from below limit of quantification (LOQ) to 2530 ng/g fresh weight, with an overall mean value of 39.3 ng/g. Methyl paraben (MeP), ethyl paraben (EtP), and propyl paraben (PrP) were the major paraben analogs found in foodstuffs, and these compounds accounted for 59%, 24%, and 10%, respectively, of ΣParaben concentrations. Although the mean concentrations of ΣParabens varied among different categories of food items (from 0.839 ng/g in beverages to 100 ng/g in vegetables), the concentrations were not statistically significant among the 13 food categories, including canned foodstuffs. Estimated daily intake (EDI) of parabens was based on the measured concentrations in foods and the corresponding daily food ingestion rates. The mean and 95th percentile values for EDI were 1010 and 3040 ng/kg body weight (bw)/day for adult men and 1060 and 3170 ng/kg bw/day for adult women, respectively.     

DDTs in mothers' milk,placenta and hair,and health risk assessment for infants at two coastal and inland cities in China

This study is a one of the very few investigating the dichloro-diphenyl-trichloroethanes (DDTs) (summation of o,p′-DDE, p,p′-DDE, o,p′-DDD, p,p′-DDD, o,p′-DDT, and p,p′-DDT) in multiple human matrices in mothers' milk, placenta and hair collected from residents from two coastal cities: Guiyu (GY) and Taizhou (TZ) and one inland city: Lin'an (LA). TZ (milk: 360 ± 319 ng/g lipid wt.) showed significantly higher concentrations of DDTs than those from LA (milk: 190 ± 131 ng/g lipid wt.), whereas, concentrations of DDTs in GY (milk: 305 ± 109 ng/g lipid wt.) were in between TZ and LA. In addition, levels of DDTs in the human tissues from TZ (placenta: 122 ± 109 ng/g lipid wt.; hair: 79.9 ± 215 ng/g dry wt.) were significantly higher than those from Lin'an (placenta: 49.2 ± 30.2 ng/g lipid wt.; hair: 10.8 ± 7.09 ng/g dry wt.). The above concentrations of DDTs in milk exceeded the Codex Maximum Residue Limits/Extraneous Maximum Residue Limits for milk (20 ng/g lipid wt. whole milk), indicating that the human milk samples were grossly polluted. The present study revealed that human specimens collected from the coastal city (TZ) were more contaminated with inland one (LA), based on the levels of DDTs contained in samples which may be due to the higher dietary exposure to DDTs via consumption of contaminated seafood. The estimated daily intakes of DDTs by GY, TZ and LA infants were 1.69 ± 1.86, 1.48 ± 0.79, and 0.95 ± 0.73 μg/kg body wt./day, respectively which did not exceed 10 μg/kg body wt./day, the provisional tolerable daily intake proposed by the Food and Agriculture Organization/World Health Organization.     

Chlorinated biphenyls and pesticides in migrating and resident seabirds from East and West Antarctica

The unhatched eggs of the following seabirds were analyzed to quantify PCBs, hexachlorobenzene (HCB), α-, β-, γ-, δ-hexachlorocyclohexanes (HCHs), o,p′ and p,p′ isomers of DDT, DDD and DDE: resident Adèlie (Pygoscelis adèliae, ADPE) and Emperor (Aptenodytes forsteri, EMPE) penguins, migrating snow petrel (Pagodroma nivea, SNPT) and South Polar skua (Catharacta maccormicki, SPSK) from the Ross Sea (East Antarctica); and migrating Brown skua (Catharacta antartica, BRSK) and resident ADPE from the Brainsfield Strait (West Antarctica). The general aims were to evaluate the contaminant accumulation in eggs of migrating and resident species in the two study areas, and to compare levels in penguins and skuas nesting in East and West Antarctica. PCB congener and HCH and DDT isomer profiles were also assessed. Comparisons were evaluated using seven PCB congeners (IUPAC nos. 28, 52, 101, 118 + 149, 138, 153, and 180), p,p′-DDE, ΣDDTs, and ΣHCHs. Higher contaminant concentrations were detected in migrating seabirds (South polar skua and brown skua) > sub-Antarctic species (snow petrel) > Antarctic species (penguins) from both the sampling sites, suggesting contamination events at lower latitudes for those birds migrating northward. HCHs showed the lowest concentrations in all species (from 0.03 ± 0.03 ng/g wet wt in SPSK to 1.81 ± 1.23 ng/g wet wt in ADPE from West Antarctica), and PCBs were the most abundant contaminants (from 4.34 ± 2.15 ng/g wet wt. in EMPE to 53.41 ± 19.61 ng/g wet wt. in brown skua). Among pesticides, it is relevant the detection of p,p′-DDT in Adèlie penguin from West Antarctica and in both species of skua; the detection of this pesticide can confirm its actual use in certain malaria-endemic countries from where it is transferred through the long range transport to the polar regions. Contaminants did not show any significant temporal trend during a ten year time span, from 1994/95 to 2004/05, in organisms collected in East Antarctica and they did not indicate any latitudinal gradient along the Ross Sea coasts.     

Perfluoroalkyl acids in subarctic wild male mink (Neovison vison) in relation to age,season and geographical area

This study investigates the influence of biological and environmental factors on the concentrations of perfluoroalkyl acids (PFAAs) in a top predator; the American mink. Perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHxS), perfluorooctane sulfonate (PFOS) and perfluoroalkyl carboxylates (PFCAs) with C₈–C₁₃ perfluorinated carbon chains were analyzed in livers from wild male mink liver (n = 101) from four areas in Sweden representing two inland environments (rural and highly anthropogenic, respectively) and two different coastal environments. Mean PFOS concentrations were 1250 ng/g wet weight and some mink from the urban inland area had among the highest PFOS concentrations ever recorded in mink (up to 21 800 ng/g wet weight). PFBS was detected in 89% of the samples, but in low concentrations (mean 0.6 ng/g ww). There were significant differences in PFAA concentrations between the geographical areas (p < 0.001–0.01). Age, body condition and body weight did not influence the concentrations significantly, but there was a seasonal influence on the concentrations of perfluorodecanoic acid (PFDA) and perfluoroundecanoic acid (PFUnDA) (p < 0.01 and p < 0.05, respectively), with lower concentrations in autumn samples than in samples taken in the winter and spring. It is thus recommended to take possible seasonal differences into account when using mink exposure data. The overall results suggest that the mink is a suitable sentinel species for assessing and monitoring environmental levels of PFAAs.     

Hydroxylated PCB metabolites (OH-PCBs) in archived serum from 1950–60s California mothers: A pilot study

We are studying participants selected from the Child Health and Development Studies (CHDS), a longitudinal birth cohort of over 20,000 California pregnancies between 1959 and 1967, for associations between maternal body burden of organochlorine contaminants and thyroid function. We designed a pilot study using 30 samples selected among samples with high and low PCB concentrations to evaluate the feasibility of measuring OH-PCBs in the larger study population. GC-ECD and GC-NCI/MS were used to determine PCBs and OH-PCBs as methyl derivatives, respectively. Maternal serum levels of Σ₁₁PCBs and Σ₈OH-PCB metabolites varied from 0.74 to 7.99 ng/mL wet wt. with a median of 3.05 ng/mL, and from 0.12 to 0.98 ng/mL wet wt. with a median of 0.39 ng/mL, respectively. Average concentrations of Σ₈OH-PCB metabolites in the high PCB group were significantly higher than those in the low PCB group (p < 0.05). The levels of OH-PCB metabolites were dependent on PCB levels (r = 0.58, p < 0.05) but approximately an order of magnitude lower (p < 0.05). The average ratio of Σ₈OH-PCBs to Σ₁₁PCBs was 0.14 ± 0.08. The primary metabolite was 4-OH-CB187 followed by 4-OH-CB107. Both of these metabolites interfere with the thyroid system in in vitro, animal, and human studies. OH-PCBs were detectable in all archived sera analyzed, supporting the feasibility to measure OH-PCB metabolites in the entire cohort.     

Route-specific daily uptake of organochlorine pesticides in food,dust, and air by Shanghai residents,China

Dichlorodiphenyltrichloroethane (DDT) and hexachlorocyclohexanes (HCHs) are widely detected in the environment, although they have been banned in China since 1980s. To better understand the route-specific daily uptake of the pesticides by humans, a total of 322 food, dust, and air samples were collected in Shanghai, China, during 2008–2011. The median concentrations were 0.2–126.6 and 0.03–1.6 ng/g wet weight for DDTs (DDT and its metabolites) and HCHs, respectively, in different types of foods. The values in dust (indoors and outdoors) were 5.7–29.8 and 1.3–5.4 ng/g, and 13.9 × 10^− 3 and 2.6 × 10^− 3 ng/m³ in air (gas + particle) for DDTs and HCHs, respectively. The daily uptake of a pesticide by humans was calculated via the pesticide intake multiplied by its uptake efficiency. The uptake efficiencies of DDTs and HCHs in food through human intestines were estimated using bioaccessibility measured via an in vitro method simulating the human gastrointestinal digestion process. The total daily uptakes of DDTs and HCHs through three routes (i.e., ingestion, inhalation, and dermal contact) were 79.4 and 4.9 ng/day, respectively, for children, and 131.1 and 8.0 ng/day, respectively, for adults. Ingestion via food and dust was the main route of human exposure to the pesticides, and the daily uptake of the pesticides via food consumption accounted for 95.0–99.2% of the total.     

Toxicokinetics of dioxins and other organochlorine compounds in Japanese people: Association with hepatic CYP1A2 expression levels

Concentrations of persistent organochlorine compounds (OCs) including polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) in the liver and adipose tissue of Japanese cadavers were measured, and their toxicokinetics were examined in association with hepatic cytochrome P450 (CYP) 1A protein expression levels. Total 2,3,7,8-tetrachlorodibenzo-p-dioxin toxic equivalents (TEQs) were 66 ± 74 and 65 ± 57 pg/g lipid weight (mean ± S.D.) in the liver and adipose tissue, respectively. Total PCBs (sum of 62 congeners targeted), p,p′-dichlorodiphenyl-dichloroethylene (p,p′-DDE) and β-hexachlorocyclohexane (β-HCH) were detected at concentrations over 1 μg/g lipid in both tissues of some specimens. For most of the dioxin-like congeners, total PCBs, p,p′-DDE, oxychlordane, α- and β-HCH, hexachlorobenzene (HCB), and tris(4-chlorophenyl)methane (TCPMe), age-dependent increases in concentrations were found in the adipose tissue of males. No such age-dependent trend was observed in the liver, suggesting that there are different mechanisms underlying the hepatic concentrations of OCs. Immunoblot analyses indicated detectable expression of hepatic CYP1A2 protein, whereas no CYP1A1 protein was detected. The CYP1A2 expression levels were positively correlated with concentrations (on wet weight basis) of 2,3,4,7,8-P₅CDF, the dominant TEQ-contributed congeners in the liver, indicating the induction of this CYP. Hepatic CYP1A2 protein levels were strongly correlated with the liver to adipose concentration (L/A) ratios of PCDD/F congeners with more than 5 chlorine atoms. Together with higher concentrations of the congeners in the liver than in the adipose tissue, the observation on L/A ratios of highly chlorinated PCDD/Fs suggests that induced hepatic CYP1A2 protein is involved in their sequestration in this human population, as observed in model animals (rodents). Nonetheless, the magnitude of hepatic sequestration (L/A ratio) of PCDD/Fs in this human population was lower than in other mammals and birds, reported previously. This study emphasizes the fact that toxicokinetics of some OCs can be affected at least partly by CYP1A2 protein levels in humans. For the extrapolation of their toxicokinetics from model animals to humans, knowledge on the induction and sequestration potencies of CYP1A is necessary.     

Perfluoroalkyl substances in soft tissues and tail feathers of Belgian barn owls (Tyto alba) using statistical methods for left-censored data to handle non-detects

Perfluoroalkyl substances (PFASs) were investigated in tail feathers and soft tissues (liver, muscle, preen gland and adipose tissue) of barn owl (Tyto alba) road-kill victims (n = 15) collected in the province of Antwerp (Belgium). A major PFAS producing facility is located in the Antwerp area and levels of PFASs in biota from that region have been found to be very high in previous studies. We aimed to investigate for the first time the main sources of PFASs in feathers of a terrestrial bird species. Throughout this study, we have used statistical methods for left-censored data to cope with levels below the limit of detection (LOD), instead of traditional, potentially biased, substitution methods.Perfluorooctane sulfonate (PFOS) was detected in all tissues (range: 11 ng/g ww in muscle–1208 ng/g ww in preen oil) and in tail feathers (< 2.2–56.6 ng/g ww). Perfluorooctanoate (PFOA) was measured at high levels in feathers (< 14–670 ng/g ww), but not in tissues (more than 50% < LOD). Perfluorohexane sulfonate (PFHxS) could only be quantified in liver and preen oil, while other PFASs were sporadically detected in liver. PFOS levels in feathers and liver were highly correlated (r = 0.78, p < 0.01), in contrast to PFOA (r = − 0.11, p = 0.78). Combined with high PFOA levels in feathers this suggests that PFOA may be present on the external surface of feathers, due to external contamination originating from the air in the vicinity of point sources. Therefore the possibility of using feathers as a passive air sampler for high PFOA levels should be investigated in the future.     

Maternal and fetal exposure to parabens in a multiethnic urban U.S. population

Fetal exposure to five parabens was investigated due to their endocrine-disrupting potential and possible impact on fetal development. Body burdens occurring from real-world exposures were determined typically as total concentrations after conjugate hydrolysis in 181 maternal urine and 38 umbilical cord blood plasma samples from a multiethnic cohort of 185 predominantly-black, pregnant women recruited in Brooklyn, New York between 2007/9. For 33 participants, both sample types (maternal urine and cord blood) were available. Methyl- (MePB), ethyl- (EtPB), propyl- (PrPB), butyl- (BuPB), and benzylparaben (BePB) were detected in 100, 73.5, 100, 66.3 and 0.0% of the urine samples at median concentrations of 279, 1.44, 75.3, 0.39, and < 0.02 μg/L, respectively. Median concentrations of MePB and PrPB were, respectively 4.4- and 8.7-fold higher compared to those reported previously for the general U.S. population (NHANES, 2005/6). Listed in the order above, the five parabens were detected in 97.4, 94.7, 47.4, 47.4, and 44.7% of cord blood plasma samples at median total concentrations of 25.0, 0.36, < 0.27, < 0.09, and < 0.10 μg/L, respectively. Free MePB, EtPB, and PrPB were detected in a subset of cord blood plasma samples at, respectively, 3.9, 71.7, and 6.4% of their total concentrations, whereas free BuPB and BePB were not detected. Literature data and those reported here show the urban community studied here to rank highest in the world for MePB and PrPB exposure in pregnant women, whereas it ranks among the lowest for EtPB and BuPB. This study is the first to report the occurrence of parabens in human umbilical cord blood. Maternal exposure to parabens is widespread, and substantial differences were found to exist between communities and countries both in the spectrum and degree of paraben exposures.     

Concentrations of polybrominated diphenyl ethers (PBDEs) and 2,4,6-tribromophenol in human placental tissues

Legacy environmental contaminants such as polybrominated diphenyl ethers (PBDEs) are widely detected in human tissues. However, few studies have measured PBDEs in placental tissues, and there are no reported measurements of 2,4,6-tribromophenol (2,4,6-TBP) in placental tissues. Measurements of these contaminants are important for understanding potential fetal exposures, as these compounds have been shown to alter thyroid hormone regulation in vitro and in vivo. In this study, we measured a suite of PBDEs and 2,4,6-TBP in 102 human placental tissues collected between 2010 and 2011 in Durham County, North Carolina, USA. The most abundant PBDE congener detected was BDE-47, with a mean concentration of 5.09 ng/g lipid (range: 0.12–141 ng/g lipid; detection frequency 91%); however, 2,4,6-TBP was ubiquitously detected and present at higher concentrations with a mean concentration of 15.4 ng/g lipid (range:1.31–316 ng/g lipid; detection frequency 100%). BDE-209 was also detected in more than 50% of the samples, and was significantly associated with 2,4,6-TBP in placental tissues, suggesting they may have a similar source, or that 2,4,6-TBP may be a degradation product of BDE-209. Interestingly, BDE-209 and 2,4,6-TBP were negatively associated with age (r_s = − 0.16; p = 0.10 and r_s = − 0.17; p = 0.08, respectively). The results of this work indicate that PBDEs and 2,4,6-TBP bioaccumulate in human placenta tissue and likely contribute to prenatal exposures to these environmental contaminants. Future studies are needed to determine if these joint exposures are associated with any adverse health measures in infants and children.     

Selective transfer of persistent organic pollutants and their metabolites in grey seals during lactation

Twenty grey seal (Halichoerus grypus) mother–pup pairs from the colony of the Isle of May (Scotland) were sampled at early and late lactation in order to study the transfer of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and their metabolites (HO-PCBs and HO-PBDEs) as well as organochlorine pesticides (OCPs), such as DDT and metabolites (DDXs) and hexachlorobenzene (HCB). The transfer of the naturally produced MeO-PBDEs was also investigated. Generally, concentrations (on a lipid weight basis) of the sum of PCBs, PBDEs and DDXs tended to be higher in all tissues at late lactation (for maternal outer blubber ΣPCBs = 3860 ± 2091 ng/g, ΣPBDEs = 120 ± 74 ng/g and ΣDDXs = 559 ± 207 ng/g; for maternal inner blubber ΣPCBs = 4229 ± 3274 ng/g, ΣPBDEs = 148 ± 118 ng/g and ΣDDXs = 704 ± 353 ng/g; for maternal serum ΣPCBs = 1271 ± 796 ng/g, ΣPBDEs = 27 ± 16 ng/g and ΣDDXs = 242 ± 125 ng/g; for milk ΣPCBs = 1190 ± 747 ng/g, ΣPBDEs = 55 ± 36 ng/g and ΣDDXs = 357 ± 160 ng/g; for pup serum ΣPCBs = 1451 ± 901 ng/g, ΣPBDEs = 48 ± 31 ng/g and ΣDDXs = 395 ± 201 ng/g). In all tissues, ΣMeO-PBDEs were found at very low levels or even undetected and their concentrations appeared to increase at late lactation only in maternal inner blubber (2.7 ± 1.3 to 5.3 ± 2.9 ng/g for early and late lactation, respectively) and milk (0.6 ± 0.3 to 1.1 ± 0.5 ng/g for early and late lactation, respectively). The transfer from inner blubber to maternal serum was selective and strongly depended on the log K_ow value of the compounds, with less lipophilic compounds being more efficiently released. Only a limited amount of HO-PCBs was transferred during lactation as 4-HO-CB-107 was the only metabolite detected in milk (29 to 40 pg/g lw). On the contrary, most of HO-PCB metabolites found in maternal serum were also detected in pup serum. These findings suggest not only a transplacental transfer of HO-PCBs from mothers to pups but also the possibility of endogenous biotransformation in suckling pups or accumulation of undetectable low amounts from milk.     

Three decades (1983–2010) of contaminant trends in East Greenland polar bears (Ursus maritimus). Part 1: Legacy organochlorine contaminants

Legacy organochlorine contaminants were determined in adipose tissues from 294 polar bears (Ursus maritimus) sampled in East Greenland in 23 of the 28 years between 1983 and 2010. Of 19 major legacy contaminants and congeners (ΣPCB, 4 PCB congeners (CB153, 180, 170/190), ΣDDT, p,p′-DDE, p,p′ -DDD and p,p′-DDT, α- and β-hexachlorocyclohexane (HCH), HCB, octachlorostyrene, dieldrin, oxychlordane, cis- and trans-chlordane, cis- and trans-nonachlor, heptachlor epoxide and BB-153), 18 showed statistically significant average yearly declines of − 4.4% (range: − 2.0 to − 10.8%/year) among subadult polar bears (i.e. females < 5 years, males < 6 years). For example, the ∑ PCB concentrations declined 2.7 fold from 22 730 ng/g lw (95% C.I.: 12 470–32 990 ng/g lw) in 1983–1986 to 8473 ng/g lw (95% C.I.: 6369–9776 ng/g lw) in 2006–2010. Similar but fewer statistically significant trends were found for adult females and adult males likely due to smaller sample size and years. Despite declines as a result of international regulations, relatively high levels of these historic pollutants persist in East Greenland polar bear tissues.     

Occurrence,removal and bioaccumulation of steroid estrogens in Dianchi Lake catchment,China

The occurrence, removal and bioaccumulation of steroid estrogens such as the natural estrone (E1), 17β-estradiol (E2) and estriol (E3), as well as the synthetic 17α-ethynylestradiol (EE2) were investigated in Dianchi Lake catchment, China. The results show that traditional secondary treatment processes in eight sewage treatment plants (STPs) of Kunming were not efficient enough to completely remove steroid estrogens, but ultraviolet (UV) photodegradation in advanced treatment displayed more effectively for the removal of the residual compounds. The amount of total steroid estrogens (∑ SEs) discharged to Dianchi Lake catchment by the eight STPs was 35.8 g/day, in which STP-3 was the dominant source, accounting for 50.8%. Because of the pollution input from treated and untreated sewages, estrogens were widely detected in surface water and sediment samples collected from 21 inflow rivers of Dianchi Lake, 10 National Surface Water Quality Monitoring Sites of the lake itself and its unique outflow river, with the mean concentration of ∑ SEs in the range of 5.3–798.2 ng/L (water) and 3.7–202.4 ng/g (dry weight, sediment), 1.5–39.2 ng/L (water) and 2.7–20.9 ng/g (sediment), and 4.2 ng/L (water) and 6.6 ng/g (sediment), respectively. Due to the continuous input of estrogens to Dianchi Lake from STPs and inflow rivers, present estrogen levels in various tissues of wild fish species sampled from the lake (2013) were higher than the values detected in the previous years (2009 and 2010). The bioaccumulation of steroid estrogens in wild fish species from different sampling sites was in the order of STP-5 > Dianchi Lake (2013) > Dianchi Lake (2010) ≈ Dianchi Lake (2009) ≫ field control > laboratory control, which is mainly affected by exposure concentrations. By employing risk quotient (RQ), it is found that eco-toxicological risk of steroid estrogens in Dianchi Lake catchment was in a sequence of 22 rivers > effluents of eight STPs > Dianchi Lake (2013) > Dianchi Lake (2010), and high RQs were found in EE2, which should be controlled preferentially in this catchment.     

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.     

Measurement and health risk assessment of PM2.5, flame retardants,carbonyls and black carbon in indoor and outdoor air in kindergartens in Hong Kong

Indoor air pollution is closely related to children's health. Polybrominated diphenyl ethers (PBDEs) and dechlorane plus (DP) transmitted through indoor PM_2.5 and dust, along with carbonyl compounds and black carbon (BC) aerosol were analysed in five Hong Kong kindergartens. The results showed that 60% of the median PM_2.5 levels (1.3 × 10¹ to 2.9 × 10¹ μg/m³ for indoor; 9.5 to 8.8 × 10¹ μg/m³ for outdoor) in the five kindergartens were higher than the guidelines set by the World Health Organization (2.5 × 10¹ μg/m³). Indoor PM_2.5 mass concentrations were correlated with outdoor PM_2.5 in four of the kindergartens. The PBDEs (0.10–0.64 ng/m³ in PM_2.5; 0.30–2.0 × 10² ng/g in dust) and DP (0.05–0.10 ng/m³ in PM_2.5; 1.3–8.7 ng/g in dust) were detected in 100% of the PM_2.5 and dust samples. Fire retardant levels in the air were not correlated with the levels of dust in this study. The median BC concentrations varied by > 7-fold from 8.8 × 10² ng/m^− 3 to 6.7 × 10³ ng/m^− 3 and cooking events might have caused BC concentrations to rise both indoors and outdoors. The total concentrations of 16 carbonyls ranged from 4.7 × 10¹ μg/m³ to 9.3 × 10¹ μg/m³ indoors and from 1.9 × 10¹ μg/m³ to 4.3 × 10¹ μg/m³ outdoors, whilst formaldehyde was the most abundant air carbonyl. Indoor carbonyl concentrations were correlated with outdoor carbonyls in three kindergartens. The health risk assessment showed that hazard indexes (HIs) HIs of non-cancer risks from PBDEs and DPs were all lower than 0.08, whilst non-cancer HIs of carbonyl compounds ranged from 0.77 to 1.85 indoors and from 0.50 to 0.97 outdoors. The human intake of PBDEs and DP through inhalation of PM_2.5 accounted for 78% to 92% of the total intake. The cancer hazard quotients (HQs) of formaldehyde ranged from 4.5E − 05 to 2.1E − 04 indoors and from 1.9E − 05 to 6.2E − 05 outdoors. In general, the indoor air pollution in the five Hong Kong kindergartens might present adverse effects to children, although different schools showed distinct pollution levels, so indoor air quality might be improved through artificial measures. The data will be useful to developing a feasible management protocol for indoor environments.     

Persistent organic pollutants in the Scheldt estuary: Environmental distribution and bioaccumulation

Levels of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and organochlorine pesticides (OCPs) were determined in the sediment and several species (European flounder, Platichthys flesus; common sole, Solea solea; Chinese mitten crab, Eriocheir sinensis; shore crab, Carcinus maenas; brown shrimp, Crangon crangon; blue mussel, Mytilus edulis and bristle worms, Polychaeta) from 7 locations in the Scheldt estuary (SE, the Netherlands–Belgium). Overall POP levels in the sediment were low. The average PCB and PBDE concentrations were respectively 31.5 and 115 ng/g dry weight (dw). Highest sediment loads were measured in the vicinity of Antwerp (368 ng PCBs/g dw), a location with intense harbor and industrial activities. Pollution concentrations in the tissues of biota were species-specific. Blue mussels contained the highest lipid concentrations (2.74 ± 0.55%) and reached the highest contamination levels (from 287 to 1688 ng PCBs/g ww, from 2.09 to 12.4 ng PBDEs/g ww). Lowest tissue loads were measured in brown shrimp (from 3.27 to 39.9 ng PCBs/g ww, from 0.05 to 0.47 ng PBDEs/g ww). The PCB congener profile in most of the species was similar with the pattern found in the sediment. PCB 153 was the most abundant congener (16.5–25.7% in biota, 10.4% in sediment). In the sediment, the total amount of PBDEs consisted for more than 99% of BDE 209. Congener BDE 47 had the highest concentrations in all sampled species (38.5–70.1%). Sediment POP loadings and tissue concentrations were poorly correlated, indicating that a simple linear or non-linear relationship is insufficient to describe this relationship, possible caused by the complexity of the bioaccumulation processes and the variability in exposure. Because of the high PCB levels, regular consumption of fish and seafood, especially mussels, from the Scheldt estuary should be avoided.     

Emission of artificial sweeteners,select pharmaceuticals,and personal care products through sewage sludge from wastewater treatment plants in Korea

Concern over the occurrence of artificial sweeteners (ASWs) as well as pharmaceuticals and personal care products (PPCPs) in the environment is growing, due to their high use and potential adverse effects on non-target organisms. The data for this study are drawn from a nationwide survey of ASWs in sewage sludge from 40 representative wastewater treatment plants (WWTPs) that receive domestic (WWTP_D), industrial (WWTP_I), or mixed (domestic plus industrial; WWTP_M) wastewaters in Korea. Five ASWs (concentrations ranged from 7.08 to 5220 ng/g dry weight [dw]) and ten PPCPs (4.95–6930 ng/g dw) were determined in sludge. Aspartame (concentrations ranged from 28.4 to 5220 ng/g dw) was determined for the first time in sewage sludge. The median concentrations of ASWs and PPCPs in sludge from domestic WWTPs were 0.8–2.5 and 1.0–3.4 times, respectively, the concentrations found in WWTPs that receive combined domestic and industrial wastewaters. Among the five ASWs analyzed, the median environmental emission rates of aspartame through domestic WWTPs (both sludge and effluent discharges combined) were calculated to be 417 μg/capita/day, followed by sucralose (117 μg/capita/day), acesulfame (90 μg/capita/day), and saccharin (66 μg/capita/day). The per-capita emission rates of select PPCPs, such as antimicrobials (triclocarban: 158 μg/capita/day) and analgesics (acetaminophen: 59 μg/capita/day), were an order of magnitude higher than those calculated for antimycotic (miconazole) and anthelmintic (thiabendazole) drugs analyzed in this study. Multiple linear regression analysis of measured concentrations of ASWs and PPCPs in sludge revealed that several WWTP parameters, such as treatment capacity, population-served, sludge production rate, and hydraulic retention time could influence the concentrations found in sludge.     

Human dietary intake of organohalogen contaminants at e-waste recycling sites in Eastern China

This study reports concentrations and human dietary intake of hexabromocyclododecanes (HBCDs), polychlorinated biphenyls (PCBs) as well as selected “novel” brominated flame retardants (NBFRs) and organochlorine pesticides, in ten staple food categories. Samples were sourced from areas in Taizhou City, eastern China, where rudimentary recycling and disposal of e-waste is commonplace, as well as from nearby non-e-waste impacted control areas. In most instances, concentrations in foods from e-waste recycling areas exceeded those from control locations. Concentrations of 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB) and bis-(2-ethylhexyl)-3,4,5,6-tetrabromophthalate (BEH-TBP) in samples from e-waste sites were 3.09–62.2 ng/g and 0.81–16.3 ng/g lipid weight (lw), respectively; exceeding consistently those in foods acquired from control sites by an order of magnitude in many cases. In contrast, while concentrations of HBCD in some foods from e-waste impacted areas exceed those from control locations; concentrations in pork, shrimp, and duck liver are higher in control samples. This highlights the potential significance of non-e-waste sources of HBCD (e.g. building insulation foam) in our study areas. While concentrations of DDT in all foods examined except pork were higher in e-waste impacted samples than controls; our exposure estimates were well below the provisional tolerable daily intake of 0.01 mg/kg bw/day derived by the Joint FAO/WHO Meeting on Pesticide Residues. Concentrations of ΣPCBs resulted in exposures (650 and 2340 ng/kg bw/day for adults and children respectively) that exceed substantially the Minimal Risk Levels (MRLs) for ΣPCBs of 20 ng/kg bw/day derived by the Agency for Toxic Substances & Disease Registry. Moreover, when expressed in terms of dioxin-like toxicity equivalency based on the four dioxin-like PCBs monitored in this study (DL-PCBs) (PCB-105, 118, 156, and 167); concentrations in e-waste impacted foods exceed limits set by the European Union in 6 of the 8 food groups studied and result in dietary exposures for children (10.2 pg TEQ/kg bw/day) that exceed the WHO tolerable daily intake of 1–4 pg TEQ/kg bw/day.