Nationwide assessment of atmospheric organochlorine pesticides over a decade during 2008-2017 in South Korea.

Long-term nationwide atmospheric monitoring of organochlorine pesticides (OCPs) was performed in South Korea during 2008-2017. Their occurrences, seasonal and temporal variability, sources, and effect of ambient temperature were investigated. The OCPs are pronounced with a mean concentration of total OCPs ranging from 5.2 to 256 pg/Sm3. However, a decrease of 54 % was observed in the mean concentration of total OCPs from 2008 to 2017 associated with regulatory actions. OCP concentrations did not show any variations between the different site types, and OCPs were ubiquitously present at all site types. The mean concentration of total OCPs in summer was two-fold higher than in winter. The concentrations of DRINs, DDTs, ENDOs, and HCHs were significantly higher in summer, but the concentrations of chlordane and heptachlor were higher in winter. The diagnostic ratios identified major sources as ongoing sources, past use, and atmospheric transport. Clausius Clapeyron plots strongly suggested the re-emission of α-endosulfan, ß-endosulfan, α-HCH, and ß-HCH, and ΔHsa (enthalpy of surface air exchange) values suggested the influence of the transport and/or new sources on aldrin, dieldrin, and chlordane. The occurrence of OCPs due to re-emissions, ongoing sources, and long-range atmospheric transport could be a challenge towards the complete phase-out of OCPs in South Korea.

Organochlorine pesticides in the urban, suburban, agricultural, and industrial soil in South Korea after three decades of ban: Spatial distribution, sources, time trend, and implicated risks.

Organochlorine pesticides in soil samples across urban, suburban, agricultural, and industrial sites were analyzed every year between 2013 and 2016 in South Korea. The study aims to understand the residual status, diminution of occurrence from the South Korean environment, and its risk to humans after three decades of the ban. A general decreasing trend of OCPs has been observed over the years. The OCP concentrations were below the guideline values prescribed for soil pollution. Metabolites like p,p'-DDD and endosulfan sulfate contributed a major portion to the total OCP concentration over the years. The agricultural sites showed higher OCP levels than other site types. Compositional profile and diagnostic ratios suggested that the occurrence of DDT and endosulfan residues were due to historical inputs, but those of HCH and chlordane reflect recent usage in some pockets. The calculated incremental lifetime cancer risk was within the safety limit for all age groups across the genders in the majority of the sites. It is evident that the OCP load on soil is decreasing since the ban on usage. However, regular monitoring with a special focus on metabolites can be an effective control measure to regulate and eliminate the contamination of OCPs.

Long-term nationwide assessment of polychlorinated dibenzo-p-dioxins/dibenzofurans and dioxin-like polychlorinated biphenyls ambient air concentrations for ten years in South Korea.

In this study, seasonal/regional variations of Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/DFs) and dioxin like-polychlorinated biphenyls in the ambient air were monitored for ten years (2008-2017) using a high volume air sampler. As a result of strict regulation enforced by Korea Ministry of Environment in 2008, PCDD/DFs concentrations in the ambient air decreased from 0.051 pg I-TEQ Sm-3 in 2009 to 0.014 pg I-TEQ Sm-3 in 2017 which was comparably associated with cut-down of their emission sources from 880.2 g I-TEQ Sm-3 in 2001 to 24.2 g I-TEQ Sm-3 in 2015; revealing that it was only 2.7% against that of 2001. In 2017, mean TEQ concentration level of PCDD/DFs in the air of South Korea was quite low in comparison to its ambient environmental standards of 0.6 pg I-TEQ Sm-3 for PCDD/DFs. Particularly, the sum of PCDD/DFs in the background revealed the lowest level, however, the fraction of octachlorodibenzodioxin among other isomers exposed at the highest level in this study, suggesting that the ambient air quality in the background being studied was severely and persistently impaired by inflowing unknown sources of any possible anthropogenic transboundary migratory air pollutants. Moreover, this study conducted the scientific analysis of the long-term variations in the ambient air and emission sources using principal component analysis. From this of 10 years long-term nationwide assessments for the PCDD/DFs and dl-PCBs in the ambient air, it is possible to prove that South Korean environmental policy to manage POPs has been successfully conducted for the last ten years.

Spatial distribution, source identification, and anthropogenic effects of brominated flame retardants in nationwide soil collected from South Korea.

Soil samples were collected at 61 sites of the national monitoring network for persistent organic pollutants (POPs) in South Korea. The target compounds were brominated flame retardants (BFRs), including polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs), hexabromocyclododecanes (HBCDDs), and tetrabromobisphenol A (TBBPA). The mean concentrations of Σ27 PBDEs, Σ3 HBCDDs, and TBBPA in soil were 222, 17.2, and 4.4 ng/g, respectively, but PBBs were not detected. Industrial sites had statistically higher BFR concentrations than suburban sites but no significant difference compared with urban sites. The commercial deca-BDE mixtures were the most likely source of PBDE contamination in the soil samples, with the minor influence of commercial penta-BDE and octa-BDE mixtures. The profiles of HBCDDs in most soil samples differed from those in the powder types of technical HBCDD mixtures, indicating that they are affected by the HBCDDs contained in commercial products and the conversion of HBCDD diastereoisomers (γ-HBCDD to α-HBCDD) in the environment. The concentrations of Σ27 PBDEs, Σ3 HBCDDs, and TBBPA were significantly correlated with population density, gross domestic product, and the number of companies (p < 0.01), indicating a direct impact of anthropogenic activities. Significant correlations among BFRs were determined (0.63 < r < 0.74, p < 0.01), suggesting that these pollutants had similar sources. Relatively good correlations (0.44 < r < 0.98, p < 0.01) between BDE-209 and other light BDEs (except for BDE-71, -77, -126, -156, and -205) might result from the degradation of heavy BDEs under anaerobic and natural sunlight conditions. To the best of our knowledge, this study provides the most comprehensive soil monitoring data for various BFRs in South Korea. Furthermore, it is the first report on soil contamination by deca-BDE, HBCDDs, and TBBPA in South Korea.

Nationwide levels and distribution of endosulfan in air, soil, water, and sediment in South Korea.

We investigated the levels and distribution patterns of α- and ß-endosulfan and endosulfan sulfate in air, soil, water, and sediment samples collected from the South Korean persistent organic pollutants (POPs) monitoring networks. In the air samples, the highest concentrations of the total (Σ3) endosulfan (50.3-611 pg/m3, mean: 274 pg/m3) were observed during summer. Spearman analysis revealed a good correlation between agricultural land area and atmospheric concentrations of Σ3 endosulfan except during winter. Regardless of the season, the ratio of the two isomers (α/ß) was 3.6-4.9 in the air samples, higher than that observed in technical mixtures (2.0-2.3), possibly due to the higher volatility of α-endosulfan, compared to ß-endosulfan. Concentrations of Σ3 endosulfan in the soil samples (n.d.-13.4 ng/g, mean: 0.8 ng/g) were not significantly different except at some stations adjacent to large areas of farmland. The average levels of Σ3 endosulfan in the water and sediment samples were 2.1 ng/L and 0.1 ng/g dw, respectively. In analyzing the four largest rivers, it was observed that a few water stations during spring and fall and sediment stations in fall had high concentrations of the two isomers and endosulfan sulfate, particularly around the Yeoungsan and Nakdong Rivers near large areas of agricultural land. Endosulfan sulfate was dominant at most water and sediment sampling stations. This study demonstrates that the endosulfan found in most environmental compartments most probably derives from agricultural areas despite its ban as a pesticide. On the other hand, given that it was also detected in industrial and urban areas, in which pesticide application does not occur, it can be conjectured that endosulfan is aerially transported at higher temperatures and continuously circulates within the environment.

Nationwide monitoring of atmospheric PCDD/Fs and dioxin-like PCBs in South Korea.

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) were measured in ambient air samples collected from different parts of South Korea in 2008, and the measured levels were used for assessing the spatial and temporal distribution of atmospheric PCDDFs and DL-PCBs in South Korea. The average concentrations of atmospheric PCDD/Fs and DL-PCBs among the 37 sites were 28 fg I-TEQ m(-3) (ND~617) and 1 fg WHO-TEQ m(-3) (ND~0.016). Elevated atmospheric levels of PCDD/Fs and DL-PCBs observed at residential/industrial sites and in the north-west of Korea, indicated a potential contribution and impacts of anthropogenic sources of PCDD/Fs and DL-PCBs. These levels were similar or lower than those previously reported in other ambient air surveys. Average concentrations of PCDD/Fs showed small seasonal variations (ANOVA analysis, p=0.144). The highest concentrations of PCDD/Fs were observed during winter, followed by spring, autumn and summer. Atmospheric PCDD/Fs and DL-PCBs in South Korea rapidly decreased during the last 10 years (1998-2008), demonstrating the efficiency of stricter regulations and the application of best available technologies/best environmental practices at emission sources. Comparison of the congener profiles and principal component analysis showed that current atmospheric PCDD/Fs are mostly influenced by industrial sources and PCBs from old commercial PCB uses. Nationwide POPs monitoring will continue and allows an effective evaluation of the implementation of the Stockholm Convention on POPs.