Next Article in Journal
Spatial Prediction of Total Nitrogen in Soil Surface Layer Based on Machine Learning
Previous Article in Journal
Energy Conservation for Indoor Attractions Based on NRBO-LightGBM
 
 
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Sustainable Proposal for Regulating Organophosphate Pesticides in Wastewater Treatment Plants in South Korea

Water Environment Research Department, National Institute of Environmental Research, Hwangyoungro 42, Seogu, Incheon 22689, Korea
*
Author to whom correspondence should be addressed.
Sustainability 2022, 14(19), 11979; https://doi.org/10.3390/su141911979
Submission received: 17 August 2022 / Revised: 11 September 2022 / Accepted: 19 September 2022 / Published: 22 September 2022
(This article belongs to the Section Pollution Prevention, Mitigation and Sustainability)

Abstract

:
Organophosphate pesticides (OPs) are highly toxic; their presence in surface waters is a matter of great concern. To the best of our knowledge, OPs in wastewater from agrochemical manufacturing facilities (AMFs) and influents and effluents from agrochemical wastewater treatment plants (AWWTPs) have not been previously investigated. Therefore, we investigated the presence of 8 OPs (5 of which are regulated under the Water Environment Conservation Act (WECA)) in 15 AMFs and 13 AWWTPs detected through surface water monitoring and proposed measures for effectively regulating these OPs in AWWTPs. Five OPs (chlorpyrifos, diazinon, dichlorvos, EPN, and fenitrothion) were detected in the AMF and AWWTP influents; three (methyldemeton, parathion, and phenthoate) were not. Of the five detected OPs, chlorpyrifos, dichlorvos, and fenitrothion are not currently regulated via effluent limitations for WWTPs under WECA; thus, additional regulations are required. The most effective process configuration for the removal of these OPs was biological treatment through activated sludge processes, followed by activated carbon adsorption. In the system, 100% OP removal from the AWWTP influents was observed. This treatment technology can be implemented in AWWTPs to minimize the presence of OPs in surface waters, thereby protecting human health and aquatic life.

1. Introduction

Numerous global studies have reported the detection of various agrochemicals in surface waters [1,2,3], with agricultural activities being cited as the primary source [1,4]. Different agrochemicals have also been detected in the effluent from wastewater treatment plants (WWTPs), which can be therefore considered pollution sources [5,6]. Among the various pesticides, highly toxic organophosphate pesticides (OPs) are the most common and account for 34% of global sales [7]. Accordingly, five OPs—diazinon, parathion, EPN, methyldemeton, and phenthoate—are regulated WWTP effluent in South Korea under the Water Environment Conservation Act (WECA).
However, it has not been clarified whether regulating only the aforementioned five OPs for WWTPs is optimal, and, to the best of our knowledge, few studies have focused on the type, concentration range, and frequency detection of OPs in wastewater from agrochemical manufacturing facilities (AMFs) and the influent and effluent of agrochemical wastewater treatment plants (AWWTPs). Since the ultimate goal of regulating OPs in WWTPs is to enhance sustainability and protect human health and aquatic life by minimizing the concentration of agrochemicals discharged into surface waters, a regulation strategy for OPs in AWWTPs based on those found in surface waters must be established. Although several previous studies identified OPs in the influents of WWTPs [8,9,10], to the best of our knowledge, practical solutions for treating OPs in AWWTPs have not been reported. Regarding OP removal, most studies have focused on individual unit processes, such as biological reactors, chemical oxidation (CO), and activated carbon (AC) adsorption, in laboratory-scale experiments using synthetic wastewater rather than real agrochemical wastewater (AW) [11,12,13,14]. Moreover, even in studies that apply the CO-activated sludge process (ASP), which has been recognized as a suitable process for treating wastewater containing toxic and refractory organic pollutants, such as AW, the removal of individual OPs has not been reported [15,16,17,18]. Therefore, proper treatment techniques must be developed for real AW in full-scale AWWTPs.
The present study examined eight OPs (chlorpyrifos, diazinon, dichlorvos, EPN, fenitrothion, methyldemeton, parathion, parathion, and phenthoate) that were identified from long-term (2007–2019) national monitoring sites (NMSs) in South Korean rivers [19,20] or regulated under the WECA for WWTP effluents. Furthermore, a technical method for effectively treating OPs to address this research gap and a sustainable management strategy for WWTPs are proposed.

2. Materials and Methods

2.1. Selection of Organophosphate Pesticides

Eight targeted OPs, five of which are regulated under the WECA, were surveyed in AMP wastewater and AWWTP influent and effluent (Table 1).

2.2. Agrochemical Wastewater Treatment Plants

Fifteen AMFs and thirteen AWWTPs were investigated to reveal the occurrence and removal characteristics of OPs (Table 2). Two of the fifteen AMFs treated AW directly in their own AWWTPs (W1 and W2 in Table 2), whereas the other thirteen AMFs directly subcontracted the treatment to eleven separate AWWTPs (W3–W13 in Table 2) that are also responsible for treating other types of wastewater mixed with AW. The main unit processes of the AWWTPs consisted of ASP, AC adsorption, and CO, while flocculation (FL), air floatation, and filtration were implemented as auxiliary processes to remove suspended solids (Table 2).

2.3. Sample Collection

In the AMFs, samples were collected from the storage tank containing wastewater produced during the manufacturing of agrochemicals. At AWWTPs W1–W13, raw wastewater entering the AWWTPs was collected along with the effluent discharged after treatment. Sampling was performed three times (April 2021, June 2021, and August 2021) for each facility. For the evaluation of OP removal via FL, ASP, and AC adsorption, samples were collected before and after each unit process in 10 AWWTPs (all except for W3, W4, and W7 in which OPs were found in the influents). Sample collection for the evaluation of OP removal by CO was not carried out because the CO unit process in AWWTP W6 was not performed at the time of sampling.

2.4. Sample Analysis and Quality Control

The analysis method for four OPs—chlorpyrifos, diazinon, dichlorvos, and fenitrothion—was established using solid-phase extraction–liquid chromatography–tandem mass spectrometry (SPE–LC–MS/MS) based on the US EPA methodology [21,22]. The remaining four OPs—EPN, methyldemeton, parathion, and phenthoate—were analyzed using gas chromatography with a nitrogen phosphorus detector (GC-NPD) based on the Korea Standard Methods [23]. Sample pretreatment procedures and analysis conditions for the analysis of OPs using SPE–LC–MS/MS are shown in Figure S1 and Table S1, respectively. To ensure the reliability of the analysis results, quality control was performed according to the Korea Standard Methods [23], and the corresponding method detection limit, limit of quantification, precision, accuracy, calibration curve, regression coefficient, and recovery percentage were determined (Table S2).

3. Results and Discussion

3.1. Occurrence of Organophosphate Pesticides in Agrochemical Manufacturing Facilities and Agrochemical Wastewater Treatment Plants

OPs were detected in 11 of the 15 AMFs and in 10 of the 13 AWWTPs (all except W3, W4, and W7). Table 3 shows the concentration ranges and frequencies of detection for the eight OPs in the AMF wastewater and AWWTP influents/effluents. Of the eight OPs, methyldemeton, parathion, and phenthoate were not detected in the examined sources while chlorpyrifos, diazinon, dichlorvos, EPN, and fenitrothion were observed in the AMF wastewater and AWWTP influents. Only diazinon and dichlorvos were detected in the AWWTP effluents, with diazinon detected at the highest concentration in the AMF wastewater and AWWTP influents, with average concentrations of 7178 μg/L (standard deviation: 3809 μg/L) and 6.027 μg/L (standard deviation: 37.4 μg/L), respectively (Figure 1). Chlorpyrifos was detected most frequently in the AMF wastewater (at 57% of the sites); however, its average concentration (0.422 ± 1.795 μg/L) and frequency of detection (7%) were significantly lower in the AWWTP influents. Notably, chlorpyrifos was not detected at all in the AWWTP effluents, where only diazinon and dichlorvos were observed. These results are meaningful because data are not available on the types and concentration ranges of OPs in industrial AWWTPs.
The characteristics of OP occurrence in AMFs and AWWTPs can be summarized based on two main points: first, large standard deviations were observed around the average concentrations (Figure 1); second, the OP concentrations observed in AWWTP influent were substantially higher than those in sewage treatment plant (STP) influent according to previous studies. Stamatis et al. [8] reported that the maximum concentrations of chlorpyrifos, diazinon, and dichlorvos in STP influent were 0.292 μg/L, 1.486 μg/L, and 0.230 μg/L, respectively, while Tang et al. [6] found that the chlorpyrifos STP influent concentration was 0.0035 μg/L. In a study by Köck-Schulmeyer [9], the maximum concentration of diazinon in STP influent was 0.684 μg/L. These results suggest the importance of applying appropriate OP treatment technologies to treat AWs with high concentrations and load variations of OPs.

3.2. Organophosphate Pesticide Removal Characteristics in Agrochemical Wastewater Treatment Plants

Among the five OPs detected in the AWWTP influents, chlorpyrifos, fenitrothion, and EPN exhibited stable and high removal efficiencies (100%; Figure 2) while diazinon and dichlorvos exhibited lower values at 75% (standard deviation: 50%) and 85.7% (standard deviation: 37.8%), respectively, indicating their comparatively lower removal efficiency and treatment stability. The low average removal efficiency of diazinon was likely related to its 0% removal efficiency from W13, which is one of only two AWWTPs (W12 and W13) in which it was detected in the influent. Notably, the results indicate that diazinon was not removed because the AW was treated simply through FL (Table 2), a technique that has been previously reported to have low removal efficiency for diazinon (15.5%) [24]. Comparatively, an ASP was implemented as the main treatment technique in W12 (with FL as an auxiliary technique), and the complete removal (100%) of diazinon was observed; however, previous studies reported lower biological removal efficiencies of ASPs [8,9].
Dichlorvos was detected in the influent of six AWWTPs (W1, W5, W6, W8, W10, and W11); 100% removal efficiency was achieved in five AWWTPs while 0% efficiency was reported in one (W6). These results indicate that the CO and AC adsorption processes implemented at W6 did not work properly. Regarding the five other AWWTPs in which dichlorvos was detected in the influents, the removal efficiency was 100% for W1, W10, and W11, wherein AC unit processes are used. Further, previous research has also reported that dichlorvos is very effectively removed by CO and AC adsorption [25,26,27,28,29,30].
AW generally contains various types of OPs, and the removal characteristics of these OP types in AW should be better understood instead of focusing on individual OPs. Accordingly, the overall removal characteristics of six OPs (chlorpyrifos, diazinon, dichlorvos, EPN, fenitrothion, and parathion) were assessed for four of the most commonly implemented unit processes in AW treatment: FL, ASP biological treatment, CO, and AC adsorption. Notably, methyldemeton and phenthoate were excluded from this portion of the analysis because the removal efficiency of these OPs by the above four unit processes has not been previously reported and they were not detected in the 13 AWWTPs in the present study (Table 2). Among the four unit processes, AC adsorption demonstrated the highest efficiency (93.5%) of OP removal (Table 4), followed by CO (87.0%). AC adsorption also showed higher treatment stability (lower standard deviation) than CO (Table 4). Notably, the standard deviation of OP removal efficiency by AC adsorption (± 7.7%) was smaller than that of CO (± 16.8%). Stable treatment characteristics of AC adsorption and CO were also observed for individual OP removal. For the CO and AC adsorption processes, stable removal was observed and the OP type did not have a large impact (Figure 3c,d). However, the removal of individual OPs via FL and ASPs was significantly affected by the OP type (Figure 3a,b). The overall OP removal efficiencies by FL and ASP were 53.0% (standard deviation: 31.6%) and 48.5% (standard deviation: 37.6%), respectively, indicating their substantially lower removal efficiencies (Table 4). In particular, ASP, which is commonly employed in WWTPs given its economic efficiency [31,32,33], showed significant variability in the overall OP removal efficiency, implying that this process alone cannot effectively remove OPs from AW.

3.3. Suggestions for Sustainable Organophosphate Pesticide Regulation in Wastewater Treatment Plants

Among the five OPs (diazinon, parathion, EPN, methyldemeton, and phenthoate) that are currently regulated by effluent limitations for WWTPs under the WECA in South Korea, methyldemeton, parathion, and phenthoate were not detected in the 15 AMFs or in the influents and effluents of the 13 AWWTPs (Table 3). Conversely, chlorpyrifos, dichlorvos, and fenitrothion, which are not currently regulated as effluent limitations, were detected in all 15 AMFs and 13 AWWTPs (Table 3). These results suggest the need for further regulation of chlorpyrifos, dichlorvos, and fenitrothion in South Korea. Notably, both chlorpyrifos and dichlorvos are regulated by the US EPA through effluent limitations for AWWTPs [51], and they are also controlled under the Environmental Quality Standards (EQS) for surface water in the European Union (EU) [52]. The long-term monitoring (2007–2019) results for chlorpyrifos and dichlorvos at the NMSs of South Korean rivers showed that their concentrations often exceeded the EU’s annual average value-environmental quality standards (AA-EQS) and maximum allowable concentration-environmental quality standards (MAC-EQS; Figure 4). These results imply the crucial need to reduce the concentrations of chlorpyrifos and dichlorvos in AWWTP effluents in South Korea to decrease their concentrations in rivers. Furthermore, additional regulations on chlorpyrifos, dichlorvos, and fenitrothion in AWWTPs based on their occurrence characteristics in rivers are desirable to improve the sustainable management of OPs in AWWTPs. Accordingly, the present study proposes an appropriate treatment method for OPs based on the observed removal efficiency of each unit process, as presented in Table 4; namely, an ASP with low operating costs (despite the low OP removal efficiency and treatment stability) should be implemented as the main treatment technology, and then followed by AC adsorption (with high removal efficiency and treatment stability) as a polishing treatment (Figure 5). Notably, when applying this process for treating AW containing OPs, the AC adsorption process should be applied after the ASP to minimize the decrease in adsorption efficiencies of OPs due to organic matter. The superiority of this configuration strategy is supported by previous studies in which the AC adsorption process was mainly applied to WWTP effluent [5,6,53]. Previous studies have reported that the application of AC adsorption as a tertiary treatment for WWTP effluent can effectively remove trace organic pollutants. To the best of our knowledge, the present study is the first to demonstrate the excellent potential of this process in the treatment of AW containing various OPs (Figure 5). Among the 10 of the 13 AWWTPs in which OPs were detected in the influents, the 3 that performed the same operating processes as shown in Figure 5 (W1, W10, and W11; Table 2) removed 100% of the OPs from the influents (Table 2). Importantly, this approach is expected to be more effective in terms of OP removal efficiency and treatment stability than that involving CO-biological treatment with an ASP, which is typically suggested for treating wastewater that contains large amounts of refractory organic matter and toxic substances (e.g., AW) [15,16,17,18,54,55]. In the configuration suggested in this study, the ASP with a settler could be replaced with a membrane biological reactor (MBR) to create solid-free effluent [56,57], and this configuration can enhance the AC adsorption column performance and extend the AC regeneration cycle, resulting in reduced economic costs associated with operating the AC adsorption column. Follow-up research should confirm the observed removal efficiencies to justify the operational costs across a more diverse array of OPs in addition to the eight investigated in this study.

4. Conclusions

This study aimed to reveal the occurrence and removal characteristics of 8 OPs (chlorpyrifos, diazinon, dichlorvos, EPN, fenitrothion, methyldemeton, parathion, parathion, and phenthoate) that are regulated in WWTP effluent under the WECA or detected at NMSs of South Korean rivers, in 15 AMFs and 13 AWWTPs. Furthermore, proper treatment technologies and sustainable management strategies for OPs in AWWTPs were suggested. Based on the results, the following conclusions can be drawn:
(1)
Five OPs (chlorpyrifos, diazinon, dichlorvos, EPN, and fenitrothion) were found at very high concentration levels in wastewaters generated from eleven AMFs and influents of ten AWWTPs.
(2)
Among the five OPs observed in the AWWTPs influents, chlorpyrifos, fenitrothion, and EPN were completely removed (100%). However, the average removal efficiencies of diazinon and dichlorvos were 75.0% and 85.7%, respectively, with high standard deviations of 50% and 37.8%, respectively, indicating their comparatively lower removal efficiency and treatment stability.
(3)
In the evaluation of four unit processes (FL, ASP, CO, and AC adsorption) for OP removal, the highest removal was observed for AC adsorption (93.4%), followed by CO (85%). In addition, AC adsorption showed higher treatment stability than CO while ASP showed a lower OP removal efficiency (48.5%).
(4)
For the sustainable management of OPs in AWWTPs, the additional regulation of chlorpyrifos, dichlorvos, and fenitrothion is required in South Korea. Additionally, the most effective basic process configuration for OP removal from AWWTPs includes ASP as the main treatment technology followed by AC adsorption as a polishing treatment.
(5)
The application of the process suggested in this study would lead to the effective control of OPs in AWWTPs, which would reduce the concentration and detection frequency of OPs in surface water.

Supplementary Materials

The following supporting information can be downloaded at https://www.mdpi.com/article/10.3390/su141911979/s1: Table S1: Analytical conditions for LC–MS/MS; Table S2: Quality control results of eight organophosphate pesticides based on instrumental analysis method; and Figure S1: Pretreatment procedures for LC–MS/MS analysis.

Author Contributions

Conceptualization, H.-D.R.; methodology, H.-D.R. and H.H.; validation, H.-D.R. and J.-H.P.; formal analysis, H.-D.R. and H.H.; investigation, H.H.; data curation, H.-D.R. and H.H.; writing—original draft preparation, H.-D.R.; writing—review and editing, H.-D.R. and J.-H.P.; supervision, J.-H.P.; project administration, Y.S.K. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Not applicable.

Acknowledgments

This study was supported by the National Institute of Environmental Research, Republic of Korea (Project No. NIER-2021-01-01-115).

Conflicts of Interest

The authors declare no conflict of interest.

Abbreviations

AA-EQS, annual average value-environmental quality standards; AC, activated carbon; AF, air floatation; AMF, agrochemical manufacturing facility; ASP, activated sludge process; AW, agrochemical wastewater; AWWTP, agrochemical wastewater treatment plant; CO, chemical oxidation; EQS, environmental quality standards; EU, European Union; FL, flocculation; GC-NPD, gas chromatography with a nitrogen phosphorus detector; MAC-EQS, maximum allowable concentration-environmental quality standards; MBR, membrane biological reactor; NMS, national monitoring sites; OP, organophosphate pesticide; SPE–LC–MS/MS, solid-phase extraction–liquid chromatography–tandem mass spectrometry; STP, sewage treatment plant; WECA, water environment conservation act; WWTPs, wastewater treatment plants.

References

  1. Lima, J.A.M.; Labanowski, J.; Bastos, M.C.; Zanella, R.; Prestes, O.D.; Vargas, J.P.R.; Mondamert, L.; Granado, E.; Tiecher, T.; Zafar, M.; et al. “Modern agriculture” transfers many pesticides to watercourses: A case study of a representative rural catchment of southern Brazil. Environ. Sci. Pollut. Res. 2020, 27, 10581–10598. [Google Scholar] [CrossRef] [PubMed]
  2. Carena, L.; Comis, S.; Vione, D. Geographical and temporal assessment of the photochemical decontamination potential of river waters from agrochemicals: A first application to the Piedmont region (NW Italy). Chemosphere 2021, 263, 127921–127930. [Google Scholar] [CrossRef] [PubMed]
  3. Horak, I.; Horn, S.; Pieters, R. Agrochemicals in freshwater systems and their potential as endocrine disrupting chemicals: A South African context. Environ. Pollut. 2021, 268, 115718–115730. [Google Scholar] [CrossRef] [PubMed]
  4. Montes, A.M.; González-Farias, F.A.; Botello, A.V. Pollution by organochlorine pesticides in Navachiste-Macapule, Sinaloa, Mexico. Environ. Monit. Assess. 2012, 184, 1359–1369. [Google Scholar] [CrossRef]
  5. Mailler, R.; Gasperi, J.; Coquet, Y.; Buleté, A.; Vulliet, E.; Deshayes, S.; Zedek, S.; Mirande-Bret, C.; Eudes, V.; Bressy, A.; et al. Removal of a wide range of emerging pollutants from wastewater treatment plant discharges by micro-grain activated carbon in fluidized bed as tertiary treatment at large pilot scale. Sci. Total Environ. 2016, 542, 983–996. [Google Scholar] [CrossRef] [PubMed]
  6. Tang, L.; Ma, X.Y.; Wang, Y.; Zhang, S.; Zheng, K.; Wang, X.C.; Lin, Y. Removal of trace organic pollutants (pharmaceuticals and pesticides) and reduction of biological effects from secondary effluent by typical granular activated carbon. Sci. Total Environ. 2020, 749, 141611–141620. [Google Scholar] [CrossRef] [PubMed]
  7. Torres-Palma, R.A.; Serna-Galvis, E.A. Sonolysis. In Advanced Oxidation Processes for Waste Water Treatment: Emerging Green Chemical Technology; Ameta, S.C., Ameta, R., Eds.; Academic Press: London, UK, 2018; pp. 177–213. [Google Scholar]
  8. Stamatis, N.; Hela, D.; Konstantinou, I. Pesticide inputs from the sewage treatment plant of Agrinio to River Acheloos, western Greece: Occurrence and removal. Water Sci. Technol. 2010, 62, 1098–1105. [Google Scholar] [CrossRef]
  9. Köck-Schulmeyer, M.; Villagrasa, M.; de Alda, M.L.; Céspedes-Sánchez, R.; Ventura, F.; Barceló, D. Occurrence and behavior of pesticides in wastewater treatment plants and their environmental impact. Sci. Total Environ. 2013, 458–860, 466–476. [Google Scholar] [CrossRef]
  10. Golovko, O.; Örn, S.; Sörengård, M.; Frieberg, K.; Nassazzi, W.; Lai, F.Y.; Ahrens, L. Occurrence and removal of chemicals of emerging concern in wastewater treatment plants and their impact on receiving water systems. Sci. Total Environ. 2021, 754, 142122–142130. [Google Scholar] [CrossRef]
  11. Zheng, W.; Sun, Y.; Gu, Y. Assembly of UiO-66 onto Co-doped Fe3O4 nanoparticles to activate peroxymonosulfate for efficient degradation of fenitrothion and simultaneous in-situ adsorption of released phosphate. J. Hazard. Mater. 2022, 436, 129058–129068. [Google Scholar] [CrossRef]
  12. Yu, X.; Kamali, M.; Aken, P.V.; Appels, L.; Bruggen, B.V.; Dewil, R. Synergistic effects of the combined use of ozone and sodium percarbonate for the oxidative degradation of dichlorvos. J. Water Process Eng. 2021, 39, 101721–101728. [Google Scholar] [CrossRef]
  13. Amiri, N.A.; Amiri, F.A.; Faravardeh, L.; Eslami, A.; Ghasemi, A.; Rafiee, M. Enhancement of MBBR reactor efficiency using effective microorganism for treatment of wastewater containing diazinon by engineered Pseudomonas putida KT2440 with manganese peroxidase 2 gene. J. Environ. Manag. 2022, 316, 115293–115306. [Google Scholar] [CrossRef] [PubMed]
  14. Hamadeen, H.M.; Elkhatib, E.A. Nanostructured modified biochar for effective elimination of chlorpyrifos from wastewater: Enhancement, mechanisms and performance. J. Water Process Eng. 2022, 47, 102703–102712. [Google Scholar] [CrossRef]
  15. Pariente, M.I.; Siles, J.A.; Molina, R.; Botas, J.A.; Melero, J.A.; Martinez, F. Treatment of an agrochemical wastewater by integration of heterogeneous catalytic wet hydrogen peroxide oxidation and rotating biological contactors. Chem. Eng. J. 2013, 226, 409–415. [Google Scholar] [CrossRef]
  16. Guieysse, B.; Norvill, Z.N. Sequential chemical–biological processes for the treatment of industrial wastewaters: Review of recent progresses and critical assessment. J. Hazard. Mater. 2014, 267, 142–152. [Google Scholar] [CrossRef]
  17. Vasiliadou, I.A.; Pariente, M.I.; Martinez, F.; Melero, J.A.; Molina, R. Modeling the integrated heterogeneous catalytic fixed-bed reactor and rotating biological contactor system for the treatment of poorly biodegradable industrial agrochemical wastewater. J. Environ. Chem. Eng. 2016, 4, 2313–2321. [Google Scholar] [CrossRef]
  18. Cui, T.; Zhang, Y.; Han, W.; Li, J.; Sun, X.; Shen, J.; Wang, L. Advanced treatment of triazole fungicides discharged water in pilot scale by integrated system: Enhanced electrochemical oxidation, upflow biological aerated filter and electrodialysis. Chem. Eng. J. 2017, 315, 335–344. [Google Scholar] [CrossRef]
  19. National Institute of Environmental Research. A Survey on the Monitoring of Potentially Hazardous Compounds and Contamination Routes in Tributary of Four Major Rivers; National Institute of Environmental Research: Incheon, Korea, 2018.
  20. Ministry of Environment. Study on the Investigation System Construction of Unregulated Water Pollutants; Ministry of Environment: Sejong, Korea, 2020.
  21. U.S. Environmental Protection Agency. Method 549.2: Determination of Diquat and Paraquat in Drinking Water by Liquid-Solid Extraction and High Performance Liquid Chromatography with Ultraviolet Detection, Revision 1.0; U.S. EPA: Cincinnati, OH, USA, 1997.
  22. U.S. Environmental Protection Agency. Method 540: Determination of Selected Organic Chemicals in Drinking Water by Solid Phase Extraction and Liquid Chromatography/Tandem Mass Spectrometry (LC/MS/MS), Version 1.0; U.S. EPA: Cincinnati, OH, USA, 2013.
  23. Ministry of Environment. Korea Standard Methods for the Examination of Water and Wastewater; National Institute of Environmental Research: Incheon, Korea, 2017.
  24. Pham, T.V.; Phuoc, V.M.; Nguyen, D.V.; Koyama, J. Treatment efficiency of a combination of alternative technologies in removing pollutants from pesticide containing wastewater. Environ. Eng. Res. 2021, 26, 200263–200271. [Google Scholar] [CrossRef]
  25. Golash, N.; Gogate, P.R. Degradation of dichlorvos containing wastewaters using sonochemical reactors. Ultrason. Sonochem. 2012, 19, 1051–1060. [Google Scholar] [CrossRef]
  26. Zhang, Y.; Zhang, W.; Pang, J.L.S.; Mishra, S.; Bhatt, P.; Zeng, D.; Chen, S. Emerging technologies for degradation of dichlorvos: A review. Int. J. Environ. Res. Public Health 2021, 18, 5789–5801. [Google Scholar] [CrossRef]
  27. Patil, P.N.; Gogate, P.R. Degradation of dichlorvos using hybrid advanced oxidation processes based on ultrasound. J. Water Process Eng. 2015, 8, e58–e65. [Google Scholar] [CrossRef]
  28. Aminu, A.S.; Gimba, C.E.; Kagbu, J.; Turoti, M.; Itodo, A.U.; Sariyya, A.I. Sorption efficiency study of pesticide adsorption on granulated activated carbon from groundnut shell using GC/MS. Electron. J. Environ. Agric. Food. Chem. 2010, 9, 1222–1231. [Google Scholar]
  29. Ogwuche, E.O.; Gimba, C.E.; Abechi, E.S. An evaluation of the adsorptive behaviour of activated carbon derived from Hyphaene thebaica nut shells for the removal of dichlorvos from wastewater. Int. J. Sci. Technol. 2015, 3, 274–285. [Google Scholar]
  30. Binh, Q.A.; Tungtakanpoung, D.; Kajitvichyanukul, P. Similarities and differences in adsorption mechanism of dichlorvos and pymetrozine insecticides with coconut fiber biowaste sorbent. J. Environ. Sci. Health B 2020, 55, 103–114. [Google Scholar] [CrossRef] [PubMed]
  31. Hernandez-Sancho, F.; Molinos-Senante, M.; Sala-Garrido, R. Cost modelling for wastewater treatment processes. Desalination 2011, 268, 1–5. [Google Scholar] [CrossRef]
  32. Rodriguez-Garcia, G.; Molinos-Senante, M.; Hospido, A.; Hernandez-Sancho, F.; Moreira, M.T.; Feijoo, G. Environmental and economic profile of six typologies of wastewater treatment plants. Water Res. 2011, 45, 5997–6010. [Google Scholar] [CrossRef]
  33. Lin, H.; Gao, W.; Meng, F.; Liao, B.Q.; Leung, K.T.; Zhao, L.; Chen, J.; Hong, H. Membrane bioreactors for industrial wastewater treatment: A critical review. Crit. Rev. Environ. Sci. Technol. 2012, 42, 677–740. [Google Scholar] [CrossRef]
  34. Ormad, M.P.; Miguel, N.; Claver, A.; Matesanz, J.M.; Ovelleiro, J.L. Pesticides removal in the process of drinking water production. Chemosphere 2008, 71, 97–106. [Google Scholar] [CrossRef]
  35. Leoni, V.; Cremisini, C.; Giovinazzo, R.; Puccetti, G.; Vitali, M. Activated sludge biodegradation test as a screening method to evaluate persistence of pesticides in soil. Sci. Total Environ. 1992, 123–124, 279–289. [Google Scholar] [CrossRef]
  36. Lee, Y.; Kim, Y.J.; Khan, M.S.I.; Na, Y.C. Identification and determination of by-products originating from ozonation of chlorpyrifos and diazinon in water by liquid chromatography–mass spectrometry. J. Sep. Sci. 2020, 43, 4047–4057. [Google Scholar] [CrossRef]
  37. Bourgeois, A.; Klinkhamer, E.; Price, J. Pesticide Removal from Water. Bachelor’s Thesis, Worcester Polytechnic Institute, Worcester, MA, USA, 2012. [Google Scholar]
  38. Badawy, M.I.; Ghaly, M.Y.; Gad-Allah, T.A. Advanced oxidation processes for the removal of organophosphorus pesticides from wastewater. Desalination 2006, 194, 166–175. [Google Scholar] [CrossRef]
  39. Real, F.J.; Benitez, F.J.; Acero, J.L.; Gonzalez, M. Removal of diazinon by various advanced oxidation processes. J. Chem. Technol. Biotechnol. 2007, 82, 566–574. [Google Scholar] [CrossRef]
  40. Toolabi, A.; Malakootian, M.; Ghaneian, M.T.; Esrafili, A.; Ehrampoush, M.H.; AskarShahi, M.; Tabatabaei, M.; Khatami, M. Optimizing the photocatalytic process of removing diazinon pesticide from aqueous solutions and effluent toxicity assessment via a response surface methodology approach. Rend. Lincei Sci. Fis. Nat. 2019, 30, 155–165. [Google Scholar] [CrossRef]
  41. Mahmoodi, N.M.; Arami, M.; Gharanjig, K.; Nourmohammadian, F.; Bidokhti, A.Y. Purification of water containing agricultural organophosphorus pollutant using titania nanophotocatalysis: Laboratory studies and numerical modeling. Desalination 2008, 230, 183–192. [Google Scholar] [CrossRef]
  42. Barbusiński, K.; Filipek, K. Use of Fenton’s reagent for removal of pesticides from industrial wastewater. Pol. J. Environ. Stud. 2001, 10, 207–212. [Google Scholar]
  43. Goodwin, L.; Carra, I.; Campo, P.; Soares, A. Treatment options for reclaiming wastewater produced by the pesticide industry. Int. J. Water Wastewater Treat. 2017, 4, 1–15. [Google Scholar] [CrossRef]
  44. Beduk, F.; Aydin, M.E.; Ozcan, S. Degradation of malathion and parathion by ozonation, photolytic ozonation, and heterogeneous catalytic ozonation processes. Clean—Soil Air Water 2012, 40, 179–187. [Google Scholar] [CrossRef]
  45. Alalm, M.G.; Tawfik, A.; Ookawara, S. Combined solar advanced oxidation and PAC adsorption for removal of pesticides from industrial wastewater. J. Mater. Environ. Sci. 2015, 6, 800–809. [Google Scholar]
  46. Moussavi, G.; Hosseini, H.; Alahabadi, A. The investigation of diazinon pesticide removal from contaminated water by adsorption onto NH4Cl-induced activated carbon. Chem. Eng. J. 2013, 214, 172–179. [Google Scholar] [CrossRef]
  47. Akbarlou, Z.; Alipour, V.; Heidari, M.; Dindarloo, K. Adsorption of diazinon from aqueous solutions onto an activated carbon sample produced in Iran. Environ. Health Eng. Manag. J. 2017, 4, 93–99. [Google Scholar] [CrossRef]
  48. Pirsaheb, M.; Dargahi, A.; Hazrati, S.; Fazlzadehdavil, M. Removal of diazinon and 2,4-dichlorophenoxyacetic acid (2,4-D) from aqueous solutions by granular-activated carbon. Desalination Water Treat. 2014, 52, 4350–4355. [Google Scholar] [CrossRef]
  49. Lee, D.I.; Chun, S.U.; Joo, Y.K. Sorption and leaching studies of fenitrothion and tebuconazole in granular activated carbon and charcoal. Asian J. Turfgrass Sci. 2006, 20, 47–55. [Google Scholar]
  50. Sigworth, E.A. Identification and removal of herbicides and pesticides. J. Am. Water Works Assoc. 1965, 57, 1016–1022. [Google Scholar] [CrossRef]
  51. Effluent Limitations Guidelines and Standards (ELG) Database. Available online: https://owapps.epa.gov/elg/ (accessed on 4 July 2022).
  52. Crane, M.; Babut, M. Environmental quality standards for water framework directive priority substances: Challenges and opportunities. Integr. Environ. Assess. Manag. 2007, 3, 290–296. [Google Scholar] [CrossRef]
  53. Guillossou, R.; Roux, J.L.; Mailler, R.; Vulliet, E.; Morlay, C.; Nauleau, F.; Gasperi, J.; Rocher, V. Organic micropollutants in a large wastewater treatment plant: What are the benefits of an advanced treatment by activated carbon adsorption in comparison to conventional treatment? Chemosphere 2019, 218, 1050–1060. [Google Scholar] [CrossRef]
  54. Han, T.; Zheng, J.; Han, Y.; Xu, X.; Li, M.; Schwarz, C.; Zhu, L. Comprehensive insights into core microbial assemblages in activated sludge exposed to textile-dyeing wastewater stress. Sci. Total Environ. 2021, 791, 148145–148155. [Google Scholar] [CrossRef]
  55. Manna, M.; Sen, S. Advanced oxidation process: A sustainable technology for treating refractory organic compounds present in industrial wastewater. Environ. Sci. Pollut. Res. 2022, 14, 1–29. [Google Scholar] [CrossRef]
  56. Al-Khafaji, S.A.; Al-Rekabi, W.S.; mawat, M.J. Apply membrane biological reactor (MBR) in industrial wastewater treatment: A mini review. Eurasian J. Eng. Technol. 2022, 7, 98–106. [Google Scholar]
  57. Al-Asheh, S.; Bagheri, M.; Aidan, A. Membrane bioreactor for wastewater treatment: A review. Case Stud. Chem. Environ. Eng. 2021, 4, 100109–100123. [Google Scholar] [CrossRef]
Figure 1. Average organophosphate pesticide (OP) concentrations in (a) agrochemical manufacturing facility (AMF) wastewater, (b) agrochemical wastewater treatment plant (AWWTP) influent, and (c) AWWTP effluent. Error bars indicate the standard deviation.
Figure 1. Average organophosphate pesticide (OP) concentrations in (a) agrochemical manufacturing facility (AMF) wastewater, (b) agrochemical wastewater treatment plant (AWWTP) influent, and (c) AWWTP effluent. Error bars indicate the standard deviation.
Sustainability 14 11979 g001
Figure 2. Average removal of organophosphate pesticides (OPs) observed in the agrochemical wastewater treatment plant (AWWTP) influents. Error bars indicate standard deviation.
Figure 2. Average removal of organophosphate pesticides (OPs) observed in the agrochemical wastewater treatment plant (AWWTP) influents. Error bars indicate standard deviation.
Sustainability 14 11979 g002
Figure 3. Removal of six individual organophosphate pesticides (OPs) (chlorpyrifos, diazinon, dichlorvos, EPN, fenitrothion, and parathion) using four unit processes. The literature cited for each unit process is as follows: (a) flocculation [24,31], (b) biological removal [8,9,35], (c) chemical oxidation [25,27,34,36,37,38,39,40,41,42,43,44], and (d) activated carbon adsorption [6,28,29,30,31,32,33,34,45,46,47,48,49,50].
Figure 3. Removal of six individual organophosphate pesticides (OPs) (chlorpyrifos, diazinon, dichlorvos, EPN, fenitrothion, and parathion) using four unit processes. The literature cited for each unit process is as follows: (a) flocculation [24,31], (b) biological removal [8,9,35], (c) chemical oxidation [25,27,34,36,37,38,39,40,41,42,43,44], and (d) activated carbon adsorption [6,28,29,30,31,32,33,34,45,46,47,48,49,50].
Sustainability 14 11979 g003
Figure 4. Concentrations of: (a) chlorpyrifos and (b) dichlorvos in national monitoring sites (NMSs) of South Korean rivers. AA-EQS and MAC-EQS indicate environmental quality standards in the EU, expressed as an annual average and maximum allowable concentration, respectively.
Figure 4. Concentrations of: (a) chlorpyrifos and (b) dichlorvos in national monitoring sites (NMSs) of South Korean rivers. AA-EQS and MAC-EQS indicate environmental quality standards in the EU, expressed as an annual average and maximum allowable concentration, respectively.
Sustainability 14 11979 g004
Figure 5. Application concept schematics of an agrochemical wastewater treatment plant (AWWTP) for treating organophosphate pesticide (OP)-containing wastewater. (1) Activated sludge reactor, (2) settler, and (3) activated carbon adsorption column.
Figure 5. Application concept schematics of an agrochemical wastewater treatment plant (AWWTP) for treating organophosphate pesticide (OP)-containing wastewater. (1) Activated sludge reactor, (2) settler, and (3) activated carbon adsorption column.
Sustainability 14 11979 g005
Table 1. Eight organophosphate pesticides (OPs) selected in this study.
Table 1. Eight organophosphate pesticides (OPs) selected in this study.
OPPercent Frequency of NMS detection in South Korean Rivers 1
Chlorpyrifos4 (68/1733) 2
Diazinon2 (25/1378)
Dichlorvos 4 (39/954)
EPN6 (66/1050)
Fenitrothion0.2 (1/414)
Methyldemetonn.a.
Parathionn.a.
Phenthoate5 (40/858)
1 Frequency of detection data are cited from National Institute of Environmental Research (2018) [19] and Ministry of Environment (2020) [20]; 2 values in parentheses indicate the number of sample.
Table 2. Agrochemical wastewater treatment plants.
Table 2. Agrochemical wastewater treatment plants.
AWWTPsMain Treatment ProcessesQuantity of Effluent
(m3/d)
W1In → FL 1 → ASP 2 → AC 3 → Out18
W2In → FL → ASP → FL → Out149
W3In → FL → AC → AF 4 → ASP → Out36
W4In → FL → ASP → AC → Out254
W5In → ASP → Out173
W6In → CO 5 (NaOCl) → FL → Filtration → AC → Out367
W7In → ASP → CO (Fenton) → Out537
W8In → ASP → FL → Out4000
W9In → FL → ASP → FL → Out200
W10In → FL → ASP → FL → AC → Out200
W11In → FL → ASP → Filtration → AC → Out270
W12In → FL → ASP → Out169
W13In → FL → Out60
1 Flocculation; 2 activated sludge process; 3 activated carbon; 4 air floatation; and 5 chemical oxidation.
Table 3. Concentration and detection frequency of organophosphate pesticides (OPs) in agrochemical manufacturing facility (AMF) wastewater and agrochemical wastewater treatment plant (AWWTP) influent and effluent.
Table 3. Concentration and detection frequency of organophosphate pesticides (OPs) in agrochemical manufacturing facility (AMF) wastewater and agrochemical wastewater treatment plant (AWWTP) influent and effluent.
OPAMF WastewaterAWWTPs
InfluentEffluent
Min.
(μg/L)
Max.
(μg/L)
Freq.
(%)
Min.
(μg/L)
Max.
(μg/L)
Freq.
(%)
Min.
(μg/L)
Max.
(μg/L)
Freq.
(%)
Chlorpyrifosn.d.24,68051.7n.d.10.047.7n.d.n.d.0
Diazinonn.d.205,20013.8n.d.233.610.3n.d.2.792.6
Dichlorvos n.d.378.617.2n.d.15.2917.9n.d.19.562.6
EPNn.d.3.913.4n.d.2.272.6n.d.n.d.0
Fenitrothionn.d.24.83.4n.d.3.257.7n.d.n.d.0
Methyldemetonn.d.n.d.0n.d.n.d.0n.d.n.d.0
Parathionn.d.n.d.0n.d.n.d.0n.d.n.d.0
Phenthoaten.d.n.d.0n.d.n.d.0n.d.n.d.0
Table 4. Overall removal of six organophosphate pesticides (OPs) (chlorpyrifos, diazinon, dichlorvos, EPN, fenitrothion, and parathion) using four unit processes.
Table 4. Overall removal of six organophosphate pesticides (OPs) (chlorpyrifos, diazinon, dichlorvos, EPN, fenitrothion, and parathion) using four unit processes.
Unit ProcessAverage Removal (%)
This StudyLiteratureOverall
Flocculation87.241.6 (±26.9 1) [24,34]53.0 (±31.6)
Biological removal with activated sludge30.752.1 (±40.9) [8,9,35]48.5 (±37.6)
Chemical oxidationn.a.87.0 (±16.8) [25,27,34,36,37,38,39,40,41,42,43,44]87.0 (±16.8)
Activated carbon adsorption10092.9 (±7.8) [6,28,29,30,31,32,33,34,45,46,47,48,49,50]93.5 (±7.7)
1 The numbers in parentheses indicate the standard deviation.
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Share and Cite

MDPI and ACS Style

Ryu, H.-D.; Han, H.; Park, J.-H.; Kim, Y.S. Sustainable Proposal for Regulating Organophosphate Pesticides in Wastewater Treatment Plants in South Korea. Sustainability 2022, 14, 11979. https://doi.org/10.3390/su141911979

AMA Style

Ryu H-D, Han H, Park J-H, Kim YS. Sustainable Proposal for Regulating Organophosphate Pesticides in Wastewater Treatment Plants in South Korea. Sustainability. 2022; 14(19):11979. https://doi.org/10.3390/su141911979

Chicago/Turabian Style

Ryu, Hong-Duck, Hyeyeol Han, Ji-Hyoung Park, and Yong Seok Kim. 2022. "Sustainable Proposal for Regulating Organophosphate Pesticides in Wastewater Treatment Plants in South Korea" Sustainability 14, no. 19: 11979. https://doi.org/10.3390/su141911979

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop