In-Seok Lee

Occurrence and fate of synthetic musk compounds in water environment

Synthetic musk compounds (SMCs) occur widely in water environments. The aims of this paper were to investigate the occurrence and fate of SMCs in sewage treatment plants (STPs) and surface waters. Total SMC concentrations ranged from 3.69 to 7.33microg/L (influent) and from 0.96 to 2.69microg/L (effluent) in 10 STPs. The SMC concentrations varied with the input source and treatment volume of each STP. Biological treatment processes had a greater SMCs removal effect than chemical treatment, filtration and disinfection processes. The SMC concentrations in surface waters ranged from 0.15 to 16.72microg/L and exhibited similar SMCs occurrence patterns generally. The fate of SMCs in water environments depends on their physical-chemical properties and their concentrations can be predicted from other SMC concentrations due to their similar fates.

Distribution and formation of chlorophenols and bromophenols in marine and riverine environments

To understand the distribution and formation of chlorophenols (CPs) and bromophenols (BPs), we analyzed water and sediment samples collected from the riverine areas and the marine environments near a nuclear power plant (NPP) in Korea. In the seawater, only BPs (2,4-dibromophenol and 2,4,6-tribromophenol) were detected, while CPs and BPs (4-chlorophenol, 2,6-dichlorophenol, 2,4,6-trichlorophenol and 2,4,6-tribromophenol) were detected in the riverine water. 2,4-DBP (0.531-32.7 ng/L) in the seawater was detected in sites near the NPP and 2,4,6-TBP (0.378-20.2 ng/L) was found in most of the seawater. In the riverine water, the sample near the industrial complex (118 ng/L) showed a greater total concentration than others (0.510-7.64 ng/L). In the marine sediments, BPs (99.0-553 ng/g dry weight) showed higher concentrations than CPs (0.145-16.1 ng/g dry weight). The BPs levels (1.01-8.55 ng/g dry weight) in the riverine sediments were much lower (10-500 times) than those in the marine sediments. The distribution patterns of CPs and BPs between the marine and riverine environments differed, with relatively high levels of BPs appearing in the marine environments due to natural formation except for anthropogenic sources. The chlorination process of the NPP also seems to form BPs (2-bromophenol, 2,4-dibromophenol and 2,4,6-tribromophenol). However, the effluents had an influence on the seawater near the NPP (about 2 km). In the riverine environments, CPs were dominant, which are related to the industrial complex. Thus, CPs and BPs in the marine and riverine environments are generated via various routes such as anthropogenic formation and biosynthesis.

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.

Assessment of characteristic distribution of PCDD/Fs and BFRs in sludge generated at municipal and industrial wastewater treatment plants

The presence of polychlorinated dibenzo-p-dioxins and furan (PCDD/Fs) and brominated flame retardants (BFRs) in sludge generated at municipal wastewater treatment plants (MWTPs) and industrial wastewater treatment plants (IWTPs) was investigated. The concentrations of these pollutants were in the following ranges: 5.38-7947ngkg(-1)dw (0.02-49.9ngWHO-TEQkg(-1) dw) for 17 PCDD/Fs, 17.5-66761μgkg(-1)dw for 27 polybrominated diphenyl ethers (PBDEs), 1.55-29604μgkg(-1)dw for hexabromocyclododecanes (HBCDs) (α-, β-, and γ-diastereomers), and 4.01-618μgkg(-1)dw for tetrabromobisphenol A (TBBPA). Generally, the levels of each compound in the sewage-sludge samples were higher than those in the industrial-sludge samples with some exceptions. The characteristic distribution profiles of target compounds were observed for different types of sludge and different sources of wastewater. High-chlorinated PCDD/Fs were dominant in all samples except those from the textile industry. The distribution of the BFRs in industrial-sludge samples varied, whereas that of the BFRs in sewage-sludge samples was consistent. The proportion of penta-BDEs in sewage sludge was higher than that in industrial sludge, even though BDE-209 was the most dominant congener in all the samples. For HBCDs, the distribution of diastereomers (α-, β-, and γ-HBCD) was similar across sludge samples that had the same source of wastewater and treatment processes.

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.

Rapid determination of organochlorine pesticides in fish using selective pressurized liquid extraction and gas chromatography–mass spectrometry

A rapid automated extraction and cleanup method using selective pressurized liquid extraction was developed and validated for 14 organochlorine pesticides in fish. The lipid-removal efficiencies achieved by adding alumina, Florisil, acid-treated silica gel, and silica gel to the extraction cell were determined and optimized. In the optimized method, fish (2-3g) was placed above alumina (30 g) in the extraction cell, then the sample was extracted using a 7:3 mixture of hexane and dichloromethane. The method was validated using certified reference materials (NIST SRM 1946 and 1974c), spiked fish, and four lipid-rich fish samples. The mean low- and high-concentration spike recoveries were 91% and 93% with RSD<20%, respectively. Measured concentrations of target OCPs showed good agreement with the certified concentrations in certified reference materials. It suggests the good accuracy and precision of the SPLE method. The proposed method met the most important requirements of an extraction and cleanup procedure, including having a short preparation (cleanup and concentration) time and minimal sample contamination and being able to be automated.

Evaluation of mono- to deca-brominated diphenyl ethers in riverine sediment of Korea with special reference to the debromination of DeBDE209.

The measured concentrations of polybrominated diphenyl ethers (PBDEs) in inland sediments, from mono- to deca-BDE congeners, ranged from 0.46 to 1760 ng/g dry weight (dw) with mean and median values of 55±230 ng/g dw and 12 ng/g dw, respectively. These concentrations were comparable to or lower than those reported in other countries. The large contributions of the nona- and octa-BDE congeners (14.6±5.0% of total PBDEs) in the present study highlight the necessity of examining these congeners. A high population density and wastewater discharge around the sampling sites are related to the high PBDE concentration. The most predominant congener was DeBDE209 (average proportion, 70.9±12.4%), which is in good agreement with the large amounts of commercial deca-BDE products used in Korea. Statistical analyses also confirmed the ubiquity of DeBDE209 in river sediment from the use of commercial deca-BDE products, such as Saytex-102E and DE-83R. On the other hand, the relatively large contributions of tri- to hepta-BDE congeners compared to the small quantities of commercial penta- and octa-BDE products used in Korea indicate the debromination potential for highly brominated congeners.