Elsevier

Science of The Total Environment

Volume 659, 1 April 2019, Pages 168-176
Science of The Total Environment

Occurrence and distribution of pharmaceutical and personal care products, artificial sweeteners, and pesticides in groundwater from an agricultural area in Korea

https://doi.org/10.1016/j.scitotenv.2018.12.258Get rights and content

Highlights

  • ACE was detected most frequently in all groundwater.

  • CFE and CTM were frequently observed in all groundwater.

  • STZ, SMZ and OFZ were only observed in agricultural groundwater.

  • CBF widely used as insecticide was observed in agricultural groundwater.

Abstract

This study investigated the occurrence and distribution of 33 pharmaceutical and personal care products (PPCPs), five artificial sweeteners (ASs), and six pesticides in groundwater in rural agricultural and rural non-agricultural area in South Korea. A total of 31 target compounds (15 antibiotics, four anthelmintics, seven other PPCPs, four ASs, and one pesticide) were detected in agricultural groundwater at concentrations from not detected (ND) to 49.3 ng/L for PPCPs, ND to 1340 ng/L for ASs, and ND to 116 ng/L for pesticides. Four target compounds (two PPCPs and two ASs) were detected in rural non-agricultural groundwater in the range of 0.085–5.74 ng/L for PPCPs and 5.64–1330 ng/L for ASs. Among the target compounds, ASs, especially acesulfame (detection frequency 69% in rural agricultural areas and 100% in the rural non-agricultural area) were predominantly detected in both agricultural (mean: 32.9 ng/L) and non-agricultural (mean: 536 ng/L) groundwater, but different occurrence patterns were observed according to the sources of contamination. Known markers of sewage leakage were detected in both agricultural and non-agricultural groundwater samples (e.g., acesulfame (69% and 100%), caffeine (88% and 100%), and crotamiton (62% and 100%)), while compounds related to agricultural activities were only observed in agricultural groundwater (e.g., sulfathiazole (38%), sulfamethoxazole (31%), oxfendazole (69%), and carbofuran (42%)).

Introduction

Pollutants entering groundwater through anthropogenic activities, such as sewage leakages, livestock breeding, and leaching from agricultural activities, are a growing concern (Sui et al., 2015). However, groundwater pollution is relatively poorly understood compared to other freshwater bodies, although the long-term potential risk to groundwater resources is increasingly recognized (Lapworth et al., 2012; Stuart et al., 2012). Among such pollutants, the occurrence and potential risk of pharmaceutical and personal care products (PPCPs), which are regarded as emerging groundwater contaminants, have been recently reported by many researchers (Kolar and Finizio, 2017; Peng et al., 2014; Yao et al., 2017). Most studies of groundwater contamination have focused on locations near septic systems (James et al., 2016; Kolpin et al., 2002; Kuroda et al., 2012; Müller et al., 2012; Robertson et al., 2016, Robertson et al., 2013; Wolf et al., 2012; Yang et al., 2017) or close to the effluent discharge points of wastewater treatment plants (WWTPs) (Buerge et al., 2009; Clara et al., 2004; Kahle et al., 2009; Nakada et al., 2008). Various pharmaceuticals, life-style compounds, hormones, and food additives are frequently detected in groundwater. Some PPCPs, such as caffeine (Buerge et al., 2006; Nakada et al., 2006), crotamiton (Kahle et al., 2009; Kuroda et al., 2012), carbamazepine (Clara et al., 2004), and artificial sweeteners (ASs) (e.g., acesulfame and sucralose) (Buerge et al., 2009; Oppenheimer et al., 2011; Robertson et al., 2013; Soh et al., 2011) have been proposed as indicators of groundwater contamination from sewage leakage.

However, studies of groundwater contamination from agriculture (Hu et al., 2010; Spielmeyer et al., 2017; Watanabe et al., 2010, Watanabe et al., 2008), livestock waste (Bartelt-Hunt et al., 2011), or confined animal feeding operations (CAFOs) (Batt et al., 2006) are relatively limited, although there is the potential for groundwater contamination in agricultural areas due to fertilization with manure and sewage leaks (Bartelt-Hunt et al., 2011; Hu et al., 2010; Spielmeyer et al., 2017; Watanabe et al., 2010, Watanabe et al., 2008). In addition, pesticides and veterinary drugs are used widely for agricultural purposes, resulting in groundwater contamination (Capece et al., 2009; Sarmah et al., 2006; Sukul and Spiteller, 2006). The irrigation with contaminated agricultural groundwater can contaminate crops and might contribute to human exposure through the ingestion of contaminated crops or groundwater.

In Korea, studies of emerging pollutants in groundwater are rare, with most research focusing on WWTPs and rivers (Kim et al., 2009, Kim et al., 2007; Yoon et al., 2010). However, in 2003, the use of veterinary pharmaceuticals in meat production (0.72 kg/t meat production) in Korea was higher than in the United States (0.24 kg/t), Japan (0.36 kg/t), Denmark (0.04 kg/t), and Sweden (0.03 kg/t) (MAFRA, 2010). About 76% of all veterinary pharmaceuticals used in Korea in 2016 were consumed in animal husbandry (MAFRA, 2017). In addition, in 2009, pesticide usage per unit agricultural area (10.3 kg/ha) in Korea was higher than for other OECD countries, except Japan (13.2 kg/ha) and Israel (12.7 kg/ha) (OECD, 2013). Therefore, agricultural groundwater contamination by PPCPs, including veterinary pharmaceuticals and pesticides, in Korean groundwater is a growing concern.

In this study, 33 PPCPs including antibiotics and anthelmintics were selected based on their concentration and detection frequencies in previous Korean studies on PPCPs in WWTPs and water environment (Kim et al., 2017; Sim et al., 2013, Sim et al., 2011). Additionally, five artificial sweeteners as known markers of sewage leakage and six pesticides widely used in Korea (KCPA, 2012; Kim et al., 2016) were selected to determine the contamination status of groundwater in Korea. In addition, the characteristic patterns of occurrence of these chemicals in groundwater due to agricultural activities were investigated by comparing groundwater samples from the rural agricultural and rural non-agricultural areas. This enabled an assessment of the effect of the proximity to sources on the levels of these compounds in groundwater. This is the first study to determine the residual levels of PPCPs in Korean groundwater.

Section snippets

Chemicals and materials

In this study, the levels of 33 PPCPs, five ASs, and six pesticides were measured in groundwater. Table 1 presents specific information on the target compounds according to the groups and these compounds selected by the usage, the species that have maximum residue limits (MRLs) in food (Livestock) and potential effects of groundwater contamination based on the previous studies (Kim et al., 2016, Kim et al., 2017; Sim et al., 2013; Subedi et al., 2014). Acetaminophen-d3, atenolol-d7, BPA-d16,

Occurrence of target chemicals in groundwater

As shown in Table 1, the 44 compounds analyzed in this study were categorized into six groups: antibiotics, anthelmintics, β-blockers, other PPCPs, pesticides, and ASs. A total of 31 compounds (15 antibiotics, four anthelmintics, two β-blockers, five other PPCPs, one pesticide, and four ASs) were detected in groundwater samples, while 13 compounds (three antibiotics, three anthelmintics, one β-blocker, five pesticides, and one AS) were not detected. The concentrations of PPCPs, ASs, and

Conclusion

This study determined the occurrence and distribution of PPCPs, ASs, and pesticides in groundwater in South Korea for the first time. The groundwater concentration distributions of target compounds differed between rural agricultural and rural non-agricultural areas, which was attributed to the presence of different contamination sources. Carbofuran, sulfathiazole, sulfamethoxazole, and oxfendazole were frequently observed in agricultural groundwater samples, but not in non-agricultural

Acknowledgment

This work was supported by a grant from the National Institute of Environment Research (NIER), funded by the Ministry of Environment (MOE) of the Republic of Korea (NIER-SP2016-333) and Korea Environment Industry & Technology Institute (KEITI) through “The Chemical Accident Prevention Technology Development Project” funded by Korea Ministry of Environment (MOE) (A1180019708020000000000000).

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