This study identified the spatial distributions of PCDD/Fs and PCBs of two media, including soils and pine needles in Ulsan, Korea. From the total concentrations and spatial distributions for three areas, the industrial area had higher concentrations of PCDD/Fs, dl-PCBs, and indicator PCBs in soils than those from suburban and urban areas. Since Ulsan has the industrial complexes on a large scale, the concentrations of target compounds in soils were mainly influenced by the industrial processes. Soils in urban and suburban areas; however, had the similar levels of PCDD/Fs and PCBs, indicating that suburban area was affected to either from the local sources or from the urban and industrial areas. Pine needles in some industrial sites were primarily polluted, but other than that, those from three areas were not different owing to the atmospheric transport of PCDD/Fs and PCBs based on the physicochemical properties and meteorological conditions.
According to the results of average and individual profiles for sampling sites, the average composition of ∑7PCDDs accounted for about 77% of the normalized concentrations in soils. The industrial area had a different profile compared to those of the urban and suburban areas, contributing slightly higher
∑10PCDFs due to the industrial activities. Furan groups with higher chlorine atoms such as HxCDFs and HpCDFs were predominant about 82% of the normalized concentrations in pine needles. For dl- PCBs and indicator PCBs in soils, about 85%, 60% of penta- and hexa-CBs were accounted for the total normalized concentrations, respectively. In case of pine needles, on the other hand, about 87% of tetra- and penta-CBs, about 80% of tri- to penta-CBs were accounted for the normalized concentrations.
According to the results of Spearman correlation analysis, ∑17PCDD/Fs and ∑18PCBs were positively correlated with each other, representing that Ulsan has many pollution sources in common, such as incomplete combustions and usage of commercial products during the industrial processes. However, TOC and most PCDFs and heavy chlorinated PCBs (penta- to hepta-CBs) had positive correlations because of their strong binding tendency to the organic carbons in soil while PCDDs and light chlorinated PCBs (tri- to tetra-CBs) had no correlations, assuming that they are directly deposited on the soil layer regardless of its organic carbon content. With the respect of pine needles, the correlation between every PCDD/F and PCB congener was somewhat impossible due to the unstable state of deposition in pine needle for organic compounds owing to the various factors such as photodegradation and changes in temperature. Furthermore, the lipid content of pine needle and PCDD/F and PCB congeners had negative or no correlations, indicating that physicochemical factors of each congener such as Kow and Koa would be mainly affected the sorption of organic pollutants to the bioindicator.
Eventually, it is imperative to study both media to understand the entire pathways of organic pollutants in the environment.
52
REFERENCES
Alcock, R. E., Behnisch, P. A., Jones, K. C., & Hagenmaier, H. (1998). Dioxin-like PCBs in the environment - human exposure and the significance of sources. Chemosphere, 37(8), 1457- 1472.
Antunes, P., Viana, P., Vinhas, T., Rivera, J., & Gaspar, E. M. S. M. (2012). Emission profiles of polychlorinated dibenzodioxins, polychlorinated dibenzofurans (PCDD/Fs), dioxin-like PCBs and hexachlorobenzene (HCB) from secondary metallurgy industries in Portugal. Chemosphere, 88(11), 1332-1339.
Baráková, D., Klánová, J., Chropeňová, M., & Čupr, P. (2017). Towards improved comparability of studies addressing atmospheric concentrations of semivolatile organic compounds based on their sequestration in pine needles. Chemosphere, 185, 47-55.
Bochentin, I., Hanari, N., Orlikowska, A., Wyrzykowska, B., Horii, Y., Yamashita, N., & Falandysz, J.
(2007). Polychlorinated dibenzo-p-dioxins (PCDDs) and –furans (PCDFs) in pine needles of Poland. Journal of Environmental Science and Health, Part A, 42(13), 1969-1978.
Breivik, K., Alcock, R., Li, Y.-F., Bailey, R. E., Fiedler, H., & Pacyna, J. M. (2004). Primary sources of selected POPs: regional and global scale emission inventories. Environmental Pollution, 128(1), 3-16.
Chen, J., Zhao, H., Gao, L., Henkelmann, B., & Schramm, K.-W. (2006). Atmospheric PCDD/F and PCB levels implicated by pine (Cedrus deodara) needles at Dalian, China. Environmental Pollution, 144(2), 510-515.
Chen, P., Mei, J., Peng, P. a., Hu, J., & Chen, D. (2012). Atmospheric PCDD/F Concentrations in 38 Cities of China Monitored with Pine Needles, a Passive Biosampler. Environmental Science &
Technology, 46(24), 13334-13343.
Cho, I.-G., Park, M.-K., Cho, H.-K., Jeon, J.-W., Lee, S.-E., & Choi, S.-D. (2019). Characteristics of metal contamination in paddy soils from three industrial cities in South Korea. Environmental Geochemistry and Health, 41(5), 1895-1907.
Choi, S.-D., Kwon, H.-O., Lee, Y.-S., Park, E.-J., & Oh, J.-Y. (2012). Improving the spatial resolution of atmospheric polycyclic aromatic hydrocarbons using passive air samplers in a multi- industrial city. Journal of Hazardous Materials, 241-242, 252-258.
Chun, M.-Y. (2009). Characteristics of PAHs Deposited on Pine Needles and Soil at Rural and Urban Area. Journal of Korean Society for Environmental Analysis, 12(1), 6-12.
Chun, M.-Y. (2013). Depositional Characteristics of Atmospheric PCBs in Several Media Used Passive Air Samplers. Journal of Environmental Health Science, 39(2), 151-158.
Chun, M.-Y. (2015). Estimation of PCDD/Fs Concentrations in Ambient Air Using Pine Needles as a Passive Air Sampler (PAS). Journal of Environmental Health Science, 41(2), 116-125.
53
Chung, D., Choi, J.-H., Lee, J.-H., Lee, S.-Y., Lee, H.-E., Park, K.-W., Lee, J.-C. (2018).
Physicochemical properties of deposited particles on surface of pine leaves as biomarker for air pollution. Analytical Science & Technology, 31(6), 247-258.
Dömötörová, M., Stachová Sejáková, Z., Kočan, A., Čonka, K., Chovancová, J., & Fabišiková, A.
(2012). PCDDs, PCDFs, dioxin-like PCBs and indicator PCBs in soil from five selected areas in Slovakia. Chemosphere, 89(4), 480-485.
Edge, M., Allen, N. S., Turner, D., Robinson, J., & Seal, K. (2001). The enhanced performance of biocidal additives in paints and coatings. Progress in Organic Coatings, 43(1), 10-17.
Frame, G. M., Cochran, J. W., & Bøwadt, S. S. (1996). Complete PCB congener distributions for 17 Aroclor mixtures determined by 3 HRGC systems optimized for comprehensive, quantitative, congener‐specific analysis. Journal of High Resolution Chromatography, 19(12), 657-668.
Fueno, H., Tanaka, K., & Sugawa, S. (2002). Theoretical study of the dechlorination reaction pathways of octachlorodibenzo-p-dioxin. Chemosphere, 48(8), 771-778.
Govers, H. A. J., & Krop, H. B. (1998). Partition constants of chlorinated dibenzofurans and dibenzo- p-dioxins. Chemosphere, 37(9), 2139-2152.
Hanari, N., Horii, Y., Okazawa, T., Falandysz, J., Bochentin, I., Orlikowska, A., Yamashita, N. (2004).
Dioxin-like compounds in pine needles around Tokyo Bay, Japan in 1999. Journal of Environmental Monitoring, 6(4), 305-312.
Hanedar, A., Güneş, E., Kaykioğlu, G., Çelik, S. Ö., & Cabi, E. (2019). Presence and distributions of POPS in soil, atmospheric deposition, and bioindicator samples in an industrial-agricultural area in Turkey. Environmental monitoring and assessment, 191(1), 42.
Holt, E., Kočan, A., Klánová, J., Assefa, A., & Wiberg, K. (2016). Spatiotemporal patterns and potential sources of polychlorinated biphenyl (PCB) contamination in Scots pine (Pinus sylvestris) needles from Europe. Environmental Science and Pollution Research, 23(19), 19602-19612.
Hong, S. H., Yim, U. H., Shim, W. J., & Oh, J. R. (2005). Congener-Specific Survey for Polychlorinated Biphenlys in Sediments of Industrialized Bays in Korea: Regional Characteristics and Pollution Sources. Environmental Science & Technology, 39(19), 7380-7388.
Kannan, N., Hong, S. H., Yim, U. H., & Shim, W. J. (2009). Biomonitoring background levels of PCBs and PBDEs in Seoul metropolitan atmosphere for possible health effects. Toxicology and Environmental Health Sciences, 1(2), 109-116.
Kim, B.-H., Lee, S.-J., Mun, S.-J., & Chang, Y.-S. (2005). A case study of dioxin monitoring in and around an industrial waste incinerator in Korea. Chemosphere, 58(11), 1589-1599.
Kim, K.-., S., Hong, K.-H., Ko, Y.-H., Yoon, K.-D., & Kim, M.-G. (2003). Emission characteristics of PCDD/Fs in diesel engine with variable load rate. Chemosphere, 53(6), 601-607.
Kirchner, M., Henkelmann, B., Jakobi, G., Kotalik, J., Fischer, N., Oxynos, K., & Schramm, K.-W.
(2006). Concentration measurements of PCDD/F in air and spruce needles in the Bavarian Forest and Bohemian Forest (Sumava): First results. Ecotoxicology and Environmental Safety, 63(1), 68-74.
54
Kurokawa, Y., Matsueda, T., Nakamura, M., Takada, S., & Fukamachi, K. (1996). Characterization of non-ortho coplanar PCBs, polychlorinated dibenzo-p-dioxins and dibenzofurans in the atmosphere. Chemosphere, 32(3), 491-500.
Li, X., Chen, J., Zhang, L., Qiao, X., & Huang, L. (2006). The Fragment Constant Method for Predicting Octanol–Air Partition Coefficients of Persistent Organic Pollutants at Different Temperatures.
Journal of Physical and Chemical Reference Data, 35(3), 1365-1384.
Liu, C., Wei, B. K., Bao, J. S., Wang, Y., Hu, J. C., Tang, Y. E., Jin, J. (2020). Polychlorinated biphenyls in the soil–crop–atmosphere system in e-waste dismantling areas in Taizhou: Concentrations, congener profiles, uptake, and translocation. Environmental Pollution, 257, 113622.
Liu, G., Zheng, M., Cai, M., Nie, Z., Zhang, B., Liu, W., Xiao, K. (2013). Atmospheric emission of polychlorinated biphenyls from multiple industrial thermal processes. Chemosphere, 90(9), 2453-2460.
Liu, J., & Liu, W. (2009). Distribution of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/Fs) and dioxin-like polychlorinated biphenyls (dioxin-like PCBs) in the soil in a typical area of eastern China. Journal of Hazardous Materials, 163(2), 959-966.
Loganathan, B. G., Kumar, K. S., Seaford, K. D., Sajwan, K. S., Hanari, N., & Yamashita, N. (2008).
Distribution of persistent organohalogen compounds in pine needles from selected locations in Kentucky and Georgia, USA. Arch Environ Contam Toxicol, 54(3), 422-439.
Lohmann, R., & Jones, K. C. (1998). Dioxins and furans in air and deposition: A review of levels, behaviour and processes. Science of The Total Environment, 219(1), 53-81.
Lopez Garcia, A., Den Boer, A. C., & De Jong, A. P. J. M. (1996). Determination of Non- and Mono- ortho-Polychlorinated Biphenyls in Background Ambient Air. Environmental Science &
Technology, 30(3), 1032-1037.
Masunaga, S., Takasuga, T., & Nakanishi, J. (2001). Dioxin and dioxin-like PCB impurities in some Japanese agrochemical formulations. Chemosphere, 44(4), 873-885.
Mei, J., & Chen, P. (2016). PCDD/Fs accumulation in pine needles: variation with species and pine needle age. Environmental Science and Pollution Research, 23(1), 563-570.
Moon, H.-B., Choi, M., Choi, H.-G., & Kannan, K. (2012). Severe pollution of PCDD/Fs and dioxin- like PCBs in sediments from Lake Shihwa, Korea: tracking the source. Marine pollution bulletin, 64(11), 2357-2363.
Moussaoui, Y., Tuduri, L., Kerchich, Y., Meklati, B. Y., & Eppe, G. (2012). Atmospheric concentrations of PCDD/Fs, dl-PCBs and some pesticides in northern Algeria using passive air sampling.
Chemosphere, 88(3), 270-277.
Nam, J. J., Gustafsson, O., Kurt-Karakus, P., Breivik, K., Steinnes, E., & Jones, K. C. (2008).
Relationships between organic matter, black carbon and persistent organic pollutants in European background soils: Implications for sources and environmental fate. Environmental Pollution, 156(3), 809-817.
Nguyen, T. N. T., Kwon, H.-O., Lee, Y.-S., Kim, L., Lee, S.-E., & Choi, S.-D. (2016). 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.
Chemosphere, 163, 184-191.
55
Nieuwoudt, C., Quinn, L. P., Pieters, R., Jordaan, I., Visser, M., Kylin, H., Bouwman, H. (2009). Dioxin- like chemicals in soil and sediment from residential and industrial areas in central South Africa.
Chemosphere, 76(6), 774-783.
Niu, J., Chen, J., Henkelmann, B., Quan, X., Yang, F., Kettrup, A., & Schramm, K. W. (2003).
Photodegradation of PCDD/Fs adsorbed on spruce (Picea abies (L.) Karst.) needles under sunlight irradiation. Chemosphere, 50(9), 1217-1225.
Odabasi, M., Ozgunerge Falay, E., Tuna, G., Altiok, H., Kara, M., Dumanoglu, Y., Elbir, T. (2015).
Biomonitoring the Spatial and Historical Variations of Persistent Organic Pollutants (POPs) in an Industrial Region. Environmental Science & Technology, 49(4), 2105-2114.
Ok, G., Ji, S.-H., Kim, S.-J., Kim, Y.-K., Park, J.-H., Kim, Y.-S., & Han, Y.-H. (2002). Monitoring of air pollution by polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans of pine needles in Korea. Chemosphere, 46(9), 1351-1357.
Paasivirta, J., & Sinkkonen, S. I. (2009). Environmentally Relevant Properties of All 209 Polychlorinated Biphenyl Congeners for Modeling Their Fate in Different Natural and Climatic Conditions. Journal of Chemical & Engineering Data, 54(4), 1189-1213.
Pereira, M. d. S. (2004). Polychlorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF) and polychlorinated biphenyls (PCB): main sources, environmental behaviour and risk to man and biota. Química Nova, 27, 934-943.
Pham, M. T. N., Anh, H. Q., Nghiem, X. T., Tu, B. M., Dao, T. N., & Nguyen, M. H. (2019).
Characterization of PCDD/Fs and dioxin-like PCBs in flue gas from thermal industrial processes in Vietnam: A comprehensive investigation on emission profiles and levels.
Chemosphere, 225, 238-246.
Rainer, M. (1998). Update of PCDD/PCDF-Intake from food in Germany. Chemosphere, 37(9), 1687- 1698.
Rappolder, M., Schröter-Kermani, C., Schädel, S., Waller, U., & Körner, W. (2007). Temporal trends and spatial distribution of PCDD, PCDF, and PCB in pine and spruce shoots. Chemosphere, 67(9), 1887-1896.
Romanić, S. H., & Krauthacker, B. (2006). Distribution of persistent organochlorine compounds in one- year and two-year-old pine needles. Bulletin of environmental contamination and toxicology, 77(1), 143-148.
Sakai, S.-I., Hayakawa, K., Takatsuki, H., & Kawakami, I. (2001). Dioxin-like PCBs Released from Waste Incineration and Their Deposition Flux. Environmental Science & Technology, 35(18), 3601-3607.
Schrenk, D., & Chopra, M. (2013). Dioxins and polychlorinated biphenyls (PCBs) in foods In M. Rose, A. Fernandes, T. F. a. E. R. Agency, & S. Hutton (Eds.), Persistent organic pollutants and toxic metals in foods (pp. 1-485). Woodhead Publishing Limited.
Schuhmacher, M., Nadal, M., & Domingo, J. L. (2004). Levels of PCDD/Fs, PCBs, and PCNs in Soils and Vegetation in an Area with Chemical and Petrochemical Industries. Environmental Science
& Technology, 38(7), 1960-1969.
56
Seo, H.-J., Kim, C.-G., & Bae, C.-H. (2011). Characteristics of PCDD/Fs Pollution and Relations to Sources in the Industrial Complexes in Korea. Journal of Korean Society for Environmental Analysis, 14(2), 100-109.
Shen, C., Chen, Y., Huang, S., Wang, Z., Yu, C., Qiao, M., . . . Lin, Q. (2009). Dioxin-like compounds in agricultural soils near e-waste recycling sites from Taizhou area, China: Chemical and bioanalytical characterization. Environment International, 35(1), 50-55.
Simonich, S. L., & Hites, R. A. (1995). Organic pollutant accumulation in vegetation. Environmental Science & Technology, 29(12), 2905-2914.
Srogi, K. (2008). Levels and congener distributions of PCDDs, PCDFs and dioxin-like PCBs in environmental and human samples: a review. Environmental Chemistry Letters, 6(1), 1-28.
Tang, X., Zeng, B., Hashmi, M. Z., Long, D., Yu, B., Ullah, N., Chen, Y. (2014). PBDEs and PCDD/Fs in surface soil taken from the Taizhou e-waste recycling area, China. Chemistry and Ecology, 30(3), 245-251.
Tian, F., Chen, J., Qiao, X., Cai, X., Yang, P., Wang, Z., & Wang, D. (2008). Source identification of PCDD/Fs and PCBs in pine (Cedrus deodara) needles: A case study in Dalian, China.
Atmospheric Environment, 42(19), 4769-4777.
Tiernan, T. O., Taylor, M., Garrett, J., VanNess, G., Solch, J., Deis, D., & Wagel, D. (1983).
Chlorodibenzodioxins, chlorodibenzofurans and related compounds in the effluents from combustion processes. Chemosphere, 12(4-5), 595-606.
Tomashuk, T. A., Truong, T. M., Mantha, M., & McGowin, A. E. (2012). Atmospheric polycyclic aromatic hydrocarbon profiles and sources in pine needles and particulate matter in Dayton, Ohio, USA. Atmospheric Environment, 51, 196-202.
Ullah, R., Asghar, R., Baqar, M., Mahmood, A., Alamdar, A., Qadir, A., . . . Eqani, S. A. M. A. S. (2020).
Assessment of polychlorinated biphenyls (PCBs) in the Himalayan Riverine Network of Azad Jammu and Kashmir. Chemosphere, 240, 124762.
UMTA. (1984). Polychlorinated Biphenyls (PCBs) in Transit System Electrical Equipment. Urban Mass Transportation Administration
UNEP. (2017). Stockholm convention on persistent organic pollutants (POPs). United Nations Environmental Programme
Wang, D.-G., Yang, M., Jia, H.-L., Zhou, L., & Li, Y.-F. (2008). Levels, distributions and profiles of polychlorinated biphenyls in surface soils of Dalian, China. Chemosphere, 73(1), 38-42.
Watanabe, S., Kitamura, K., & Nagahashi, M. (1999). Effects of Dioxins on Human Health : A Review.
Journal of Epidemiology, 9(1), 1-13.
Wu, J., Hu, J., Wang, S., Jin, J., Wang, R., Wang, Y., & Jin, J. (2018). Levels, sources, and potential human health risks of PCNs, PCDD/Fs, and PCBs in an industrial area of Shandong Province, China. Chemosphere, 199, 382-389.
Yeo, H.-G., Choi, M., Chun, M.-Y., Kim, T.-W., Cho, K.-C., & Sunwoo, Y. (2004). Concentration characteristics of atmospheric PCBs for urban and rural area, Korea. Science of the Total Environment, 324(1-3), 261-270.
57
Yu, B.-W., Jin, G.-Z., Moon, Y.-H., Kim, M.-K., Kyoung, J.-D., & Chang, Y.-S. (2006). Emission of PCDD/Fs and dioxin-like PCBs from metallurgy industries in S. Korea. Chemosphere, 62(3), 494-501.
Zhang, S., Huang, W., Li, X., & Zhang, G. (2009). PCDD/PCDF pollution in soils and sediments from the Pearl River Delta of China. Chemosphere, 75(9), 1186-1195.
Zheng, M.-H., Bao, Z.-C., Zhang, B., & Xu, X.-B. (2001). Polychlorinated dibenzo-p-dioxins and dibenzofurans in paper making from a pulp mill in China. Chemosphere, 44(6), 1335-1337.
58
SUPPLEMENTARY INFORMATION
Figure S1. Chromatogram of PCDD/F standard.
59 Figure S2. Chromatogram of PCDD/Fs in sample.
60 Figure S3. Chromatogram of dl-PCB standard.
61 Figure S4. Chromatogram of dl -PCBs in sample.
62 Figure S5. Chromatogram of indicator PCB standard.
63 Figure S6. Chromatogram of indicator PCBs in sample.
64
Figure S7. TOC-normalized concentrations of PCDD/Fs in soil samples.
Figure S8. TOC-normalized concentrations of PCBs in soil samples.
0 0.06 0.12 0.18 0.24 0.3
S1 S2 S3 S4 S5 S6 S7 S8 S9 S10 S11 S12 S13 U1 U2 U3 U4 U5 U6 U7 I1 I2 I3 I4 I5 I6 I7 I8 I9 I10
ng/g dw ng/g dw TOC
Concentration (ng/g dw)
Suburban Urban Industrial
0 0.9 1.8 2.7 3.6 4.5
S1 S2 S3 S4 S5 S6 S7 S8 S9 S10 S11 S12 S13 U1 U2 U3 U4 U5 U6 U7 I1 I2 I3 I4 I5 I6 I7 I8 I9 I10
ng/g dw ng/g dw TOC
Concentration (ng/g dw)
Suburban Urban Industrial