Un-Jung Kim

Tetrabromobisphenol A and hexabromocyclododecane flame retardants in infant–mother paired serum samples, and their relationships with thyroid hormones and environmental factors

The concentrations of tetrabromobisphenol A (TBBPA) and hexabromocyclododecanes (HBCDs), and their correlations with thyroid hormones, were investigated in sera from 26 infants with congenital hypothyroidism, 12 healthy infants, and their mothers. The analyte concentrations were not significantly different in the two infant groups. Polybrominated diphenyl ethers (measured in a previous study) were the dominant brominated flame retardants, contributing 42-87% of the total, and HBCDs contributed 5-18%. TBBPA concentrations were 2-5 times higher in the infants than in the mothers. The TBBPA concentrations decreased dramatically with age for 2-3 months after birth, which might be caused by its relatively high maternal transfer rate, short half-life, and fast excretion. Significant correlations were found between mothers and infants in the TBBPA and HBCD concentrations, implying that maternal transfer was important. TBBPA correlated weakly with thyroid hormones, showing a positive relationship with FT4 but a negative relationship with T3.

Occurrence of synthetic musks in Korean sewage sludges.

Six polycyclic musks (PCMs) and five nitro musks (NMs) were analyzed in dewatered sludge samples from 13 municipal, 4 livestock and 1 pharmaceutical wastewater treatment plants (WWTPs) in South Korea. 1,3,4,6,7,8-Hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-(g)-2-benzopyran (HHCB; Galaxolide), Abbalide), and 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (AHTN; Tonalide, Fixolide) were the two predominant PCMs in the sludge samples, at concentrations ranging from 0.52 to 82.0mg/kg dry weight (dw) and 0.12 to 28.8mg/kg (dw), respectively, suggesting the extensive use of these two PCMs in South Korea. Hierarchical cluster analysis (HCA) revealed the different usage patterns of PCMs between livestock cultivating farm and household. The levels of HHCB and AHTN in the effluent discharged from the WWTPs were lower than the threshold effect levels derived for fish, suggesting low potential risks to aquatic organisms. Nevertheless, the calculated discharge of synthetic musks (SMs) from sludge in each target WWTP ranged from 36 to 10,961g/d. These results indicate the necessity of conducting monitoring studies in marine ecosystems due to ocean disposal of sludge, particularly focused on the two prevailing PCMs.

Distribution and seasonal occurrence of UV filters in rivers and wastewater treatment plants in Korea.

The occurrence and distribution of eight UV filters benzophenone (BP), benzophenone-3 (BP-3), ethylhexyl methoxy cinnamate (EHMC), 4-methylbenzylidene camphor (4-MBC), 2-ethylhexyl 4-dimethylaminobenzoate (OD-PABA), 2-ethylhexyl salicylate (EHS), isoamyl benzoate, and benzyl cinnamate in eleven sites among three rivers, five sewage treatment plants (STPs), and four wastewater treatment plants (WWTPs) located in different parts of Korea was investigated. The total concentrations of UV filters in the three sampled seasons were 62.9-412 ng L(-1) (river), 417-5055 ng L(-1) (STP influent), 108-2201 ng L(-1) (STP effluent), 122-4154 ng L(-1) (WWTP influent), and 120-849 ng L(-1) (WWTP effluent). The concentration of the target pollutants in the influent of the treatment systems was directly proportional to the resident population density. A seasonal increase of >27% was observed in the total concentration of the UV filters in the rivers and influents of the treatment plants (TPs) during summer. BP, BP-3, EHMC, 4-MBC, and EHS were the most dominant, showing a distinct distribution pattern that was dependent on the effectiveness of the treatment process and properties of each compound. The concentrations of the UV filters were higher in the TPs influents than in the rivers, and the most dominant UV filters in the rivers were those with low removal rate. Although biological treatment processes favored the removal of the UV filter compounds in the TPs, complete removal was not achieved before discharge into the rivers.

Monitoring of PBDEs concentration in umbilical cord blood and breast milk from Korean population and estimating the effects of various parameters on accumulation in humans.

In this study, we investigated concentration, congener distribution pattern, and effects of potential environmental factors that affect PBDE accumulation. We also estimated correlation between PBDE concentration and health status or thyroid function by analyzing 90 cord blood and 21 breast milk samples obtained from Korean population. Seven from tri- to hepta-BDEs were analyzed by solid phase extraction-high-resolution gas chromatography/high-resolution mass spectrometry (SPE-HRGC/HRMS). The total concentration of 7 PBDEs in cord blood was 2.786-94.64 ng g(-1) lipid and that in breast milk was 1.076-8.664 ng g(-1) lipid. Tetra-BDE (#47) was the predominant type of PBDE and was present at concentrations of over 40% in both sample types. A weak correlation was observed between the concentration of BDE28 and 153 and thyroid hormone concentration only in the breast milk samples. In children, a weak negative correlation was observed between free thyroxine (FT4) concentration and BDE28 concentration (0.302, p<0.05), while in mothers, a weak positive correlation was observed between thyroid hormone concentration and BDE153 concentration (0.403, p<0.05). No significant correlations between PBDE concentration and work and residential environments were found in this study, but a weak correlation between BDE concentration in cord blood and potential PBDE sources was confirmed by investigating the frequency of oil paint usage (0.510, p<0.001). A weak correlation was also found between PBDE concentration in breast milk during pregnancy and dietary habits such as green tea drinking (0.541, p=0.025) and Trichiuridae intake (0.565, p=0.015).

Investigation of bioaccumulation and biotransformation of polybrominated diphenyl ethers, hydroxylated and methoxylated derivatives in varying trophic level freshwater fishes

The concentrations and distributions of polybrominated diphenyl ethers (PBDEs) and their hydroxylated and methoxylated derivatives (OH- and MeO-BDEs) were determined in seven representative fish species from a river in the Republic of Korea. The PBDEs and their derivatives were found to be accumulated in the internal organs of the fish to different extents. PBDEs were preferentially accumulated in the internal organs rather than muscle tissue, and especially, showed increasing accumulation tendencies with increasing bromination level in liver. The OH-BDEs and MeO-BDEs were preferentially accumulated in the liver and gastrointestinal tract, respectively. MeO-BDE concentrations were found to increase according to relative trophic level, suggesting that the PBDE derivatives can be biomagnified to a greater extent than the parent PBDEs in freshwater food webs. In a comparison with the dissolved analyte concentrations in the water that were measured by using semi-permeable membrane devices, the greater uptake of non-ortho substituted MeO-BDEs by fish was observed.

Brominated flame retardants in Korean river sediments, including changes in polybrominated diphenyl ether concentrations between 2006 and 2009

Brominated flame retardants were analyzed in sediment samples from the Nakdong River basin, Korea. The total concentrations of the 27 polybrominated diphenyl ethers (PBDEs), including decabrominated diphenyl ether (BDE 209), analyzed were 0.55-300 ng g(-1) dry weight (dw), the BDE 209 concentrations were 0.39-190 ng g(-1) dw, the tetrabromobisphenol A (TBBPA) concentrations were 0.05-150 ng g(-1) dw, and the total hexabromocyclododecane (sum of α-, β-, γ-HBCDs) concentrations were 0.11-19 ng g(-1) dw. The PBDE and HBCD concentrations were comparable to or lower than the concentrations found in sediments from other countries, whereas the TBBPA concentrations were comparable to or higher than the concentrations found in other countries. The TBBPA concentrations were similar to or lower than the PBDE concentrations, even though more than twice as much TBBPA as total PBDEs is consumed in Korea, and this phenomenon was probably caused by TBBPA and PBDEs being used differently during the manufacture of products, and their different half-lives in sediment and affinities for the particle phase in aquatic environments. Sediment samples from several sampling sites close to facilities where expandable polystyrene, epoxy, and polycarbonate resins are manufactured and handled had relatively high TBBPA and HBCD concentrations. Temporal changes in the PBDE concentration strongly correlated with temporal variations in the geochemical compositions such as total organic carbon content and grain size value of the sediment. The PBDE and HBCD distribution profiles in the sediment samples indicated that commercial PBDE and HBCD products were released locally.

Comprehensive monitoring of synthetic musk compounds from freshwater to coastal environments in Korea: with consideration of ecological concerns and bioaccumulation.

This study investigated the concentration levels of synthetic musk compounds (SMCs), including HHCB (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-(g)-2-benzopyran), AHTN (7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene), MK (Musk ketone), and MX (Musk xylene), in freshwater, freshwater and coastal sediments, and coastal bivalves from freshwater to coastal environments. The levels in freshwater close to sewage treatment plants (STPs) showed higher contamination and suggested a medium to high ecological risk, especially posed by MK making more than 65% contribution to the combined risk by the total SMCs. STP effluent discharge points showed higher SMC concentrations in freshwater and coastal sediments. Predominant HHCB contributions regardless of sample types such as abiota and biota were consistent with the greater usage of HHCB than AHTN and MK in Korea. However, the higher contributions of AHTN than those predicted from AHTN consumption in Korea indicate the need for further research on the characteristic properties of individual SMCs, including partitioning, biomagnification, degradation, and metabolism for a realistic risk characterization. With respect to the highest HHCB levels in coastal bivalves reported, we determined the biota-sediment accumulation factor (BSAF) to understand the bioaccumulation of SMCs between coastal sediment and bivalves. The calculated BSAF values suggested that SMCs in bivalves were not biomagnified via the food chain but mostly partitioned from sediment. To our knowledge, this is the first study to measure BSAF values of SMCs, especially HHCB, AHTN, and MK, in coastal bivalve samples.

Correction to Hydroxylated, Methoxylated, and Parent Polybrominated Diphenyl Ethers (PBDEs) in the Inland Environment, Korea and Potential OH- and MeO-BDE Source.

vegetation (pg/g) MEAN 24 2.8 6.7 0.67 27 110 MIN < LOQ < LOQ < LOQ < LOQ 11 57 MAX 89 5.6 16 1.5 130 220 SD 24 1.9 3.5 0.73 33 47 DF 12/12 12/12 12/12 4/12 12/12 12/12 MEAN = arithmetic mean. SD = standard deviation. DF = detection frequency. ∑18BDEs = total trito hepta-bromodiphenyl ether concentration; ∑27BDEs = total monoto deca-bromodiphenyl ether concentration; = limit of detection; see text for the PBDE, OHand MeO-BDE congeners analyzed Addition/Correction

Using SPMDs for monitoring hydrophobic organic compounds in urban river water in Korea compared with using conventional water grab samples.

We aimed to verify the effectiveness of semi-permeable membrane devices (SPMDs) for monitoring hydrophobic organic compounds, such as polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs), that are not easy to detect using conventional grab samples (because of their low concentrations), in water. We used SPMDs and grab samples to monitor PCBs and PBDEs upstream and downstream of a sewage treatment plant (STP) in the Suyeong River in Busan, Korea. Concentrations in three different phases (freely dissolved, apparently dissolved, and particulate) were measured, to investigate the aquatic fate of PCBs and PBDEs. The freely dissolved (SPMD) concentrations were 2-3 times higher than the apparently dissolved and particulate phase (grab sample) concentrations. No meaningful relationships were found between the total PCB and PBDE concentrations of the grab sample and SPMD sample because of the different partitioning behaviors and detection frequencies of the individual chemicals. However, the summed concentrations of specific PCB and PBDE congeners (that were abundant in all samples) in the grab and SPMD samples correlated well (r(2)=0.7451 for PCBs 28+52+153, r(2)=0.9987 for PBDEs 28+47+99). The PBDE concentrations measured using SPMDs decreased with increasing distance from the STP, but no apparent dilution effect was found in the grab samples. Our results show that SPMDs could be used to support grab sampling for specific chemicals, or to trace chemical sources (such as STPs) to the aquatic environment.

Occurrence, removal and release characteristics of dissolved brominated flame retardants and their potential metabolites in various kinds of wastewater

The dissolved phase compound and congener specific distribution characteristics of three widely used brominated flame retardants (BFRs) comprising 27 polybrominated diphenyl ethers (PBDEs), 12 hydroxylated and methoxylated metabolites (OH- and MeO-BDEs), 3 hexabromocyclododecanes (HBCDs) and tetrabromobisphenol A (TBBPA) were investigated in influents and effluents of various kinds of wastewater treatment plants (WWTPs), with varying source of wastewater and type of treatment, and nearby rivers in Korea. The concentration of total BFRs were the highest in industrial WWTPs nearby large industrial complexes specialized in heavy chemicals. The distribution of BFRs was differed according to composition of wastewater, with predominance of TBBPA in WWTPs with higher portion of inflowing industrial wastewater. Among HBCD diastereomers, γ-HBCD was dominant in industrial wastewater as consistent to the previous reports, however, similar contribution of α- and γ-HBCD was found in sewage and human wastewater. Through treatment process, PBDEs were the most effectively removed with a mean removal efficiency of 68.3%. HBCDs and TBBPA had removal efficiencies of 41.3% and 48.7%, respectively. The lowest removal efficiency (10.3%) was observed for PBDE metabolites and their concentration in effluent of human wastewater was even increased at maximum 1.9 fold compared with influent, implying the possibility of transformation during treatment. The estimated dissolved phase daily load of PBDEs was highest in sewage while that of TBBPA was highest in industrial wastewater.