Contamination characteristics of polycyclic aromatic hydrocarbons in river and coastal sediments collected from the multi-industrial city of Ulsan, South Korea.

River and coastal sediments were collected at 17 stations in Ulsan, the largest industrial city in South Korea, to evaluate the levels, profiles, emission sources, and spatial distribution of polycyclic aromatic hydrocarbons (PAHs). The mean concentration of Σ16 PAHs was 722 ng/g, and fluoranthene was a predominant compound. PAHs with 4-6 rings showed higher proportions than PAHs with 2-3 rings. The stations located near industrial complexes showed elevated levels of indicator compounds for petroleum, coal, coke, and fuel combustion. Therefore, petrochemical industries, coal pier, non-ferrous industries, and vehicles were identified as the emission sources. As industrialization and urbanization progressed, an increase in PAH levels and profile changes were observed as a result of the increasing industrial fuel consumption and the increasing number of vehicles. This is the first study that confirmed the change of PAHs in sediment caused by the change of emission sources over time in Ulsan.

Spatially high-resolved monitoring and risk assessment of polycyclic aromatic hydrocarbons in an industrial city.

Polycyclic aromatic hydrocarbons (PAHs) were monitored at 20 sites in semi-rural, urban, and industrial areas of Ulsan, the largest industrial city in South Korea, for one year. The target compounds were the 16 priority PAHs designated by the US Environmental Protection Agency except for naphthalene, acenaphthene, and acenaphthylene. Gaseous PAHs collected using polyurethane foam-based passive air samplers (PUF-PASs) and particulate PAHs predicted using gas/particle partitioning models were used to estimate the human health risks. The mean total cancer risk through inhalation intake and dermal absorption for all target age groups (children, adolescents, adults, and lifetime) ranged from 0.10 × 10-7 to 2.62 × 10-7, lower than the acceptable risk level (10-6), thus representing a safe level for residents. The cancer risk through dermal absorption and inhalation intake was predicted to be highest in winter, mostly due to the higher concentrations of PAHs, especially high-molecular-weight species with greater toxicity. Additionally, gaseous and particulate PAHs contributed more to dermal absorption and inhalation intake, respectively. As a consequence of local emissions and advection, the risks were higher in the industrial and semi-rural areas. This study suggests that human health risks can be cost-effectively mapped on a local scale using passive air sampling.

Abundance of diet-derived polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in the bodies and nests of the yellow-legged hornet Vespa velutina nigrithorax and risks to human health in South Korea.

Detecting polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in an organism's environment is ecologically significant. In particular, the detection of PCDD/Fs in organisms consumed as food suggests the possibility of human health risks. In South Korea, there is a unique custom in which social wasps, such as hornets, have been used as ingredients in traditional liquor. Thus, we investigated the concentrations and patterns of PCDD/Fs for the most common social wasps, the yellow-legged hornet (Vespa velutina nigrithorax), and estimated human health risks based on potential dietary exposure in traditional liquor made from the polluted wasps and their nests. The mean concentration of ∑17 PCDD/Fs in the wasps and nests of V. v. nigrithorax was 33.59 pg/g (median 25.31 pg/g), corresponding to 0.65 pg World Health Organization - Toxic equivalency factor (WHO-TEQ/g) (median 0.49 pg WHO-TEQ/g). The levels of ∑17 PCDD/Fs from the nests of V. v. nigrithorax were higher than those in the adults and larvae. As a result of this risk assessment, the daily intake of traditional liquor made with these wasps and their nests was found to be below safety levels; however, there could still be a possibility for health risks due to the detection of PCDD/Fs from organism. Therefore, continuous monitoring of environmental contaminants, including PCDD/Fs in wasps and nests, is required in order to evaluate human health risks associated with the consumption of traditional liquor made with these biological substances. In addition, the results of this study can be used to calculate dietary exposure to PCDD/Fs and the extent of risk to food in which the organism is consumed.

Spatial and temporal variations of volatile organic compounds using passive air samplers in the multi-industrial city of Ulsan, Korea.

The source-receptor relationship of volatile organic compounds (VOCs) is an important environmental concern, particularly in large industrial cities; however, only a few studies have identified VOC sources using high spatial resolution data. In this study, 28 VOCs were monitored in Ulsan, the biggest multi-industrial city in Korea. Passive air samplers were seasonally deployed at eight urban and six industrial sites. The target compounds were detected at all sites. No significant seasonal variations of VOCs were observed probably due to the continuous emissions from major industrial facilities. Benzene, toluene, ethylbenzene, xylenes, and styrene accounted for 66-86% of the concentration of Σ28 VOCs. The spatial distribution of the individual VOCs clearly indicated that petrochemical, automobile, non-ferrous, and shipbuilding industries were major VOC sources. Seasonal wind patterns were found to play a role in the spatial distribution of VOCs. Diagnostic ratios also confirmed that the industrial complexes were the dominant VOC sources. The results of principal component analysis and correlation analyses identified the influence of specific compounds from each industrial complex on individual sites. To the best of our knowledge, this is the first comprehensive report on the seasonal distribution of VOCs with high spatial resolution in a metropolitan industrial city in Korea.

Seasonal variation, phase distribution, and source identification of atmospheric polycyclic aromatic hydrocarbons at a semi-rural site in Ulsan, South Korea.

Polycyclic aromatic hydrocarbons (PAHs) in gaseous and particulate phases (n = 188) were collected in Ulsan, South Korea, over a period of one year (June 2013‒May 2014) to understand the seasonal variation and phase distribution of PAHs as well as to identify the seasonal PAH emission sources. The target compounds were the 16 US-EPA priority PAHs, with the exception of naphthalene, acenaphthylene, and acenaphthene. Winter and spring had the highest and lowest PAH concentrations, respectively. The mean of the Σ13 PAHs in the gaseous phase (4.11 ng/m3) was higher than that in the particulate phase (2.55 ng/m3). Fractions of the gaseous or 3- and 4-ring PAHs (i.e., Flu, Phe, and Ant) were high in summer, and those of the particulate or 5- and 6-ring PAHs (i.e., BkF, BaP, Ind, DahA, and BghiP) increased in winter. Gas/particle partitioning models also demonstrated the increased contributions of the particulate PAHs in spring and winter. Source identification of PAHs was undertaken using diagnostic ratios, principal component analysis, and positive matrix factorization. The results indicated that pyrogenic sources (e.g., coal combustion) were dominant in winter. Other types of pyrogenic (e.g., industrial fuel combustion) and petrogenic sources were the main PAH sources in summer and autumn. The influence of both sources, especially in summer, might be due to seasonal winds transporting PAHs from the industrial areas. Two types of pyrogenic sources, diesel and coal combustion, were identified as the main PAH sources in spring. This study clearly demonstrates a source-receptor relation of PAHs at a semi-rural site in a heavily industrialized city.

Updated national emission of perfluoroalkyl substances (PFASs) from wastewater treatment plants in South Korea.

A nationwide emission estimate of perfluoroalkyl substances (PFASs) from wastewater treatment plants (WWTPs) is required to understand the source-receptor relationship of PFASs and to manage major types of WWTPs. In this study, the concentrations of 13 PFASs (8 perfluorocarboxylic acids, 3 perfluoroalkane sulfonates, and 2 intermediates) in wastewater and sludge from 81 WWTPs in South Korea were collected. The emission pathways of PFASs were redefined, and then the national emission of PFASs from WWTPs was rigorously updated. In addition to the direct calculations, Monte Carlo simulations were also used to calculate the likely range of PFAS emissions. The total (Σ13PFAS) emission (wastewater + sludge) calculated from the direct calculation with mean concentrations was 4.03 ton/y. The emissions of perfluorooctanoic acid (PFOA, 1.19 ton/y) and perfluorooctane sulfonate (PFOS, 1.01 ton/y) were dominant. The Monte Carlo simulations suggested that the realistic national emission of Σ13PFASs is between 2 ton/y and 20 ton/y. Combined WWTPs treating municipal wastewater from residential and commercial areas were identified as a major emission source, contributing 65% to the total PFAS emissions. The Han and Nakdong Rivers were the primary contaminated rivers, receiving 89% of the total PFAS discharge from WWTPs. The results and methodologies in this study can be useful to establish a management policy for PFASs.

Leaching of polycyclic aromatic hydrocarbons (PAHs) from industrial wastewater sludge by ultrasonic treatment.

Ultrasonic treatment for sludge reduction in wastewater treatment plants (WWTPs) can substantially affect the fate of trace pollutants. However, their fates in the different phases of sludge and mass balances have rarely been reported. In this study, wastewater sludge samples were ultrasonicated at 600W for 0-30min. Then, the leaching of the 16 priority polycyclic aromatic hydrocarbons (PAHs) from the sludge solids (sediment) to the liquid phase (supernatant) was investigated. The total concentration of PAHs (∑16 PAHs) in the sludge sediment (2.10µg/g) was comparable with those of previous worldwide studies. Among the 16 PAHs, naphthalene and acenaphthylene were dominant. The total concentrations of PAHs in the supernatant generally increased with sonication time, indicating that PAHs associated with sludge materials, such as microorganisms, were released into the supernatant. Lighter and more water soluble PAHs were released preferentially into the supernatant in dissolved form, whereas heavier and more hydrophobic PAHs were strongly bound to particles. According to mass balance calculations, 21% of the PAHs in the sludge sediment moved to the supernatant without discernible sonodegradation. An additional experiment for degradation of PAHs supported this interpretation, and several reasons for the no significant sonodegradation were discussed. This result suggests that leaching trace pollutants may significantly contaminate the sludge filtrate after ultrasonic treatment, and therefore their fates should be investigated.

Influence of non-detect data-handling on toxic equivalency quantities of PCDD/Fs and dioxin-like PCBs: A case study of major fish species purchased in Korea.

It has been known that substitution is not a suitable method to address non-detect (ND) data and can result in significant errors. However, reports of reliable statistical methods for handling ND data of polychlorinated dibenzo-p-dioxin/furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in fish are rare. This work examines US-EPA's recommended statistical methods and traditional substitution-based methods for handling ND data in PCDD/F and DL-PCB datasets obtained from 240 fish samples. The Kaplan-Meier (KM) method was confirmed as a suitable statistical approach for dealing with our fish datasets. The results of the KM and substitution methods were compared; a significant difference was found in TEQs derived from KM and substitution for PCDD/Fs, suggesting that the handling of ND data is a critical issue for PCDD/Fs. For example, the substitution by ½LOD resulted in 20-25% overestimation of PCDD/F TEQs for fish samples with ND data (60-70%). In conclusion, the use of KM method is preferable for average TEQs, and if the use of KM is not applicable, substitution by zero is preferred. Based on this conclusion, the characteristics of fish contamination by PCDD/Fs and DL-PCBs in Korea were investigated.

Arsenic speciation in water, suspended particles, and coastal organisms from the Taehwa River Estuary of South Korea.

Water, suspended particulate matter (SPM), and biota samples were collected from the Taehwa River Estuary to determine the distributions, partitioning, and bioaccumulation of arsenicals. Six forms of As were quantitated by the use of HPLC-ICP/MS. As was found mainly near urban and industrial areas, and inorganic As(V) was the predominant As form in both water and SPM. Particulate arsenicals were found at the greatest concentrations in coarse particles (>180µm), followed by medium (30-180µm) and fine (0.45-30µm) particles, in freshwater. Arsenical concentrations were similar across the three particle fractions in saltwater. Field-based distribution coefficient (Kd) values for As depended strongly on SPM, with a less robust dependence on salinity. Concentrations of As were greater in macroalgae than in marine animals, such as fishes, bivalves, crabs, shrimps, and gastropods. Overall, the results of the present study provide useful information on the behaviors and fate of arsenicals in an estuarine environment.

Watershed-scale modeling on the fate and transport of polycyclic aromatic hydrocarbons (PAHs).

PAHs are potentially carcinogenic substances that are persistent in the environment. Increasing concentrations of PAHs were observed due to rapid urbanization, thus; monitoring PAHs concentrations is necessary. However, it is expensive to conduct intensive monitoring activities of a large number of PAHs. This study addressed this issue by developing a multimedia model coupled with a hydrological model (i.e., Soil and Water Assessment Tool (SWAT)) for Taehwa River (TR) watershed in Ulsan, the industrial capital of South Korea. The hydrologic module of the SWAT was calibrated, and further used to simulate the fate and transport of PAHs in soil and waterbody. The model demonstrated that the temporal or seasonal variation of PAHs in soil and waterbody can be well reproduced. Meanwhile, the spatial distribution of PAHs showed that urban areas in TR watershed have the highest PAH loadings compared to rural areas. Sensitivity analyses of the PAH soil and PAH water parameters were also able to determine the critical processes in TR watershed: degradation, deposition, volatilization, and wash off mechanism. We hope that this model will be able to aid the stakeholders in: regulating PAH concentrations emitted by various sources; and also apply the model to other Persistent Organic Pollutants (POPs).

A national discharge load of perfluoroalkyl acids derived from industrial wastewater treatment plants in Korea.

Levels of 11 perfluoroalkyl acids (PFAAs), including perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), were measured in wastewater (influent and effluent) and sludge samples collected from 25 industrial wastewater treatment plants (I-WWTPs) in five industrial sectors (chemicals, electronics, metals, paper, and textiles) in South Korea. The highest ∑11PFAAs concentrations were detected in the influent and effluent from the paper (median: 411ng/L) and textile (median: 106ng/L) industries, and PFOA and PFOS were the predominant PFAAs (49-66%) in wastewater. Exceptionally high levels of PFAAs were detected in the sludge associated with the electronics (median: 91.0ng/g) and chemical (median: 81.5ng/g) industries with PFOS being the predominant PFAA. The discharge loads of 11 PFAAs from I-WWTP were calculated that total discharge loads for the five industries were 0.146ton/yr. The textile industry had the highest discharge load with 0.055ton/yr (PFOA: 0.039ton/yr, PFOS: 0.010ton/yr). Municipal wastewater contributed more to the overall discharge of PFAAs (0.489ton/yr) due to the very small industrial wastewater discharge compared to municipal wastewater discharge, but the contribution of PFAAs from I-WWTPs cannot be ignored.

Spatial distribution and source identification of indicator polychlorinated biphenyls in soil collected from the coastal multi-industrial city of Ulsan, South Korea for three consecutive years.

The concentrations, profiles, and source-receptor relationships of seven indicator polychlorinated biphenyls (PCBs) (#28, 52, 101, 118, 138, 153, and 180) found in soil at 25 rural, urban, and industrial sites in Ulsan, South Korea were investigated. For this study, 75 soil samples were collected, 25 each in January of 2011, 2012, and 2013. Principal component analysis was used to evaluate the influence of the emission sources on the soil samples. The concentrations of total seven PCBs (Σ7 PCBs) ranged between 0.034 ng/g and 143 ng/g (mean: 5.10 ng/g, median: 0.440 ng/g), which indicated slight or moderate contamination levels, respectively, compared to those in the other countries or other cities in Korea. The concentrations of Σ7 PCBs at the industrial and urban sites were significantly higher than those at the rural sites, due to the direct influence of emission sources related to industrial activities rather than urban emission sources. Generally, the profiles of PCBs were dominated by penta- and hexa-chlorinated biphenyls at all the study sites, suggesting common sources of PCBs in Ulsan. PCB source identification indicated that leakage from transformer oils in the major industrial complexes and PCB-containing paints used in the automobile and shipbuilding industrial complexes were possibly the main sources of indicator PCBs in the study areas.

Polycyclic aromatic hydrocarbons (PAHs) in soils from a multi-industrial city, South Korea.

We collected soil samples at 25 sites in Ulsan, Korea to investigate the levels, patterns, spatial distribution, and sources of polycyclic aromatic hydrocarbons (PAHs) in the summer 2010. The target compounds were the 16 US-EPA priority PAHs. For the source identification of PAHs, diagnostic ratios and the positive matrix factorization (PMF) model were used. The total concentrations of PAHs ranged from 65 ng/g to 12,000 ng/g (mean: 960 ng/g, median 330 ng/g). The levels and distribution of PAHs indicated that industrial areas were more polluted than rural and urban areas. The diagnostic ratios suggested that the soil samples were contaminated by pyrogenic sources and traffic emission. According to the result of PMF, four factors were identified: gasoline and heavy oil combustion (14%), diesel combustion (54%), coke oven (23%), and coal/biomass burning (9%). Therefore, it was concluded that vehicles and industrial complexes were major sources of PAHs in Ulsan.

Improving the spatial resolution of atmospheric polycyclic aromatic hydrocarbons using passive air samplers in a multi-industrial city.

The source-receptor relationship of polycyclic aromatic hydrocarbons (PAHs) in the industrial city has been generally investigated using active air samplers (AAS), but they only provide low spatial resolution data. In this study, the spatial resolution of PAHs was improved by the use of polyurethane foam based passive air samplers (PUF-PAS). We deployed 40 passive air samplers in duplicate at 20 sites in the largest industrial city of Ulsan, South Korea during winter (January 7-February 25, 2011). Among the 16 US-EPA priority PAHs, 13 compounds excluding naphthalene, acenaphthylene, and acenaphthene were selected for the calculation of air concentrations. The level of gaseous ∑(13)PAHs in Ulsan (mean: 43 ng/m(3)) was not as high as we expected due to prevailing winds which transported large amounts of PAHs to the East Sea. The spatial distribution of PAHs, principal component analysis, and diagnostic ratios suggested the influence of PAH emissions from industrial complexes to the surrounding areas. This study demonstrated that the source-receptor relationship of PAHs in the industrial area can be more clearly understood using passive air samplers.