Suspect screening of pollutants in rivers around a chemical industrial park in China

Suspect screening of pollutants in rivers around a chemical industrial park in China | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Suspect screening of pollutants in rivers around a chemical industrial park in China Daoxu Zhong, Jiaming Li, Shui Wang, Lisen Bai, Guangbing Liu, and 3 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4651810/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Chinese chemical companies often cluster in specific regions, leading to concentrated emissions of various chemicals and pollutants, which poses significant risks to ecosystems and human health. Water samples were collected from the rivers near the chemical industrial park (CIP) in Jiangsu Province, China, and utilized suspect screening to identify pollutants. This study aimed to examine the correlation between these pollutants and those detected in the effluent from the companies or wastewater treatment plants (WWTPs) within the CIP, thereby providing a scientific basis for government management decisions. In the rivers surrounding the CIP, over 50 types of pollutants were found, with 26 identified near the river estuary, half of which were pesticides. Analysis indicated that sites closest to the WWTPs discharge outlets exhibited heightened pollutant levels, suggesting the release of challenging-to-treat pollutants into the environment. Additionally, compounds consistent with those used by the companies were detected in rivers without WWTP discharge, underscoring that pollutants originating from CIP enterprises are not solely attributed to wastewater treatment plant discharges. This information underscores the need for comprehensive and effective environmental management and monitoring strategies within chemical industrial parks. Earth and environmental sciences/Environmental sciences Earth and environmental sciences/Environmental sciences/Environmental chemistry suspect screening hazardous chemicals chemical industrial park rivers wastewater treatment plants Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 1. Introduction The chemical industries worldwide tend to develop in clusters, in purpose-built industrial areas (Ding et al. 2020 ; Lyu et al. 2020 ; Pines 2005 ). In China, the number of chemical industrial parks (CIPs) has increased significantly since their inception in the 1990s, experiencing rapid expansion, especially after 2000 (China Petroleum and Chemical Industry Federation. http://www.cpcia.org.cn/ ). The number of national key CIPs in China surged from 200 in 2009 to 676 by the end of 2018. This includes 57 national chemical parks (encompassing economic and technological development zones and high-tech zones), 351 provincial chemical parks, and 268 municipal chemical parks. This significant increase highlights the rapid development and strategic importance of CIPs in China’s industrial landscape. Clustering these enterprises together in CIPs has led to significant growth in the Chinese chemical industry, a pivotal national sector. This growth is attributed to several factors, including the efficient utilization of public infrastructure, collaboration among upstream and downstream enterprises within the industrial chain, and decreased transportation and operational costs. Additionally, this clustering model enables more effective governance and oversight by governmental and local authorities (Yang et al. 2018 ; Yune et al. 2016 ; Zheng et al. 2021 ). As a result, the proportion of enterprises exceeding the designated size entering these parks reached nearly 45%, underscoring the success and importance of this strategy. This demonstrates how strategic planning and focused investment can drive industrial growth and economic development in key sectors (China Petroleum and Chemical Industry Federation. http://www.cpcia.org.cn/ ; Yune et al. 2016 ). The concentration of chemical companies in industrial parks can indeed lead to significant environmental challenges, primarily due to the concentrated discharge of pollutants (He et al. 2018 ; Huang et al. 2011 ; Luo et al. 2020 ). Researchers have detected many kinds of pollutants in the atmosphere, water, and soil within or around CIPs, raising concerns about environmental and public health impacts (Pan et al. 2011 ; Zhang et al. 2021 ). Moreover, occasional pollution accidents caused by leaks in chemical parks harm the health of nearby residents (Hou et al. 2021 ). Although the Chinese government has mandated the construction of centralized wastewater treatment facilities in industrial parks, these facilities primarily focus on conventional pollutants like COD, ammonia nitrogen, SO 2 , and NO x (Hu et al. 2019 , Ding and Hua 2012 ; Hou et al. 2021 ; Hu et al. 2019 ; Luo et al. 2020 ). Consequently, emerging contaminants and less conventional pollutants remain a significant concern. This gap highlights the need for more comprehensive environmental regulations and advanced treatment technologies to address the complex pollution profiles associated with chemical industrial parks. It is worth noting that numerous compounds, including pharmaceuticals (Gao et al. 2016 ; Ratola et al. 2012 ), active pharmaceutical ingredients (Hey et al. 2012 ), persistent organic pollutants (POPs) (Bester 2005 ), and personal care products, are challenging to remove from wastewater (Guo et al. 2019 ; Perez-Cataluna et al. 2021 ; Rizzo et al. 2019 ). These compounds tend to adsorb onto suspended particles and settle into activated sludge during the treatment process. Some micropollutants may be released from activated sludge (Katsoyiannis and Samara 2005 ), and additional byproducts may be generated in the degradation process (Gao et al. 2016 ). These challenges underscore the complexity of managing wastewater from industrial parks and the importance of developing more effective treatment technologies to address emerging contaminants. As wastewater treatment technology continues to evolve, innovative solutions will be necessary to ensure the removal of these complex and persistent pollutants, safeguarding environmental and public health. The pollutants that remain after WWTP processes can be discharged into the environment through effluent. These pollutants usually have intricate compositions and low concentrations, making them challenging to detect using conventional methods. However, advancements in technology, such as non-target and suspect screening utilizing high-resolution mass spectrometry (HRMS) coupled with gas or liquid chromatography (Schymanski et al. 2015 ; Wu, Y. et al.2023), have provided new tools for identifying these pollutants. Non-target and suspect screening technologies have become a standard approach for detecting and analyzing unknown pollutants in wastewater, surface water, and other environmental media (Kang et al. 2020 ; Wang et al. 2020 ). These advanced analytical methods enable more comprehensive monitoring of environmental pollutants, facilitating the identification of emerging contaminants and enhancing our understanding of their behavior and impact in the environment. In a previous study conducted in chemical industrial parks (CIPs) in Jiangsu Province, researchers utilized suspect screening and liquid chromatography time-of-flight mass spectrometry (LC-QTOF-MS) to identify the types of pollutants present in different chemical enterprises and at various stages of wastewater treatment (Liu et al. 2020 ). This study aimed to investigate the pollutants in rivers near a CIP, tributaries in the downstream areas of these rivers, and locations near the river estuary at the coast. By screening pollutants in multiple small rivers flowing through the CIP, the study sought to uncover potential relationships between water pollutants and discharges from the industrial park. The comprehensive approach allowed for the detection of a wide range of pollutants, enhancing our understanding of the environmental impact of chemical discharges and highlighting the need for improved wastewater treatment and monitoring practices in industrial areas. 2. Materials and methods 2.1 Sample collection The study involved collecting 29 surface water samples from various rivers around the chemical industrial park (CIP) in Jiangsu Province, including the GH River, ZB River (which runs through the CIP), XY River, and the Yellow Sea coast. The samples were collected from different sites along each river, with specific sites denoted based on their location relative to the CIP and other landmarks. Samples were also collected from sites near the GH River estuary at the coast. ach sample collected was 1 liter in volume and underwent filtration through 1-µm glass fiber filter membranes and 0.45-µm nylon filter membranes to remove solid impurities. The filtered samples were then stored at 4°C and transported to the laboratory for further analysis. This meticulous sampling process was conducted to investigate the presence of pollutants in the rivers surrounding the CIP and to assess any potential relationships between water quality and industrial discharges. 2.2 Sample pretreatment The pollutants present in the water samples were extracted using solid phase extraction (SPE) (Liu et al. 2020 ). A preconditioned Oasis HLB cartridge (6 cc/500 mg, Waters, USA) was used for the extraction process. The extraction flow rate was maintained at 3–5 mL/min, and after extraction, elution was carried out using 10 mL of methanol followed by 10 mL of dichloromethane (Merck, Germany). The extracted sample was then evaporated using N 2 and dissolved in 1 mL of methanol. The resulting extract was filtered through a 0.2 µm polypropylene membrane syringe filter (Acrodisc® GHP, 13 mm, 0.2 µm, Waters, USA), collected in an amber vial, and stored at -20°C until further analysis. To prevent sample contamination, all equipment used in the extraction process was thoroughly pre-cleaned with hexane, dichloromethane, and methanol. This meticulous extraction process ensured the integrity of the collected water samples for subsequent analysis of pollutants. 2.3 LC-QTOF-MS analysis and mass spectrometry data analysis In this study, LC-QTOF-MS analysis method was used adhered to the identical workflow for mass spectrometry data analysis as demonstrated in our prior investigation (Liu et al. 2020 ). In Brief, the samples were analyzed using liquid chromatography (LC; Agilent Technologies, Waldbronn, Germany) coupled with a high-resolution hybrid quadrupole time-of-flight mass spectrometer (Triple TOF 5600, AB Sciex, Foster City, CA). A detailed description about the instrument parameter settings, quality assurance, and quality control are provided in the supplementary information (SI). We isolated the suspect peaks and identified the pollutants using standards and databases (details are provided in SI). And we referred to the reported methods and assigned a confidence level for each identified pollutant (Schymanski et al. 2014 ). The confidence level was 1 if the structure was confirmed by the authentic standards, or 2 for a probable structure, from either a library spectrum match (2a) or diagnostic evidence (2b). This study only considered substances with confidence levels of 1 and 2. 2.4 Data analysis tools The mass spectrometry data were analyzed with PeakView 2.2 software (AB SCIEX, USA). Principal component analysis (PCA) was performed using SPSS Statistics software version 24.0 (IBM, USA). The figures were drawn in SigmaPlot 12.5 (Systat, USA), Excel 2016 (Microsoft, USA), and Venny 2.1 ( https://bioinfogp.cnb.csic.es/tools/venny/index.html ). 3. Results and Discussion 3.1 Pollutant identification From the suspect screening, 55 chemicals were identified in the GH River (detailed information is provided in Table S4). The total intensity and quantity of pollutants detected at each site are shown in Figure 1a. Significant variations in the total response intensity were observed, with sites G-3 to G-6 exhibiting notably higher values compared to sites G-1 and G-2. For instance, the total response intensity of the sample from G-6 was 10 times greater than that at G-2. The CIP was situated between sites G-4 and G-5, potentially contributing to the heightened response intensities at G-3 to G-6. Across all sites, the distribution patterns in both the number of pollutants detected and their respective response displayed similar trends from G-1 to G-10. The 55 chemical substances detected were classified based on their applications (Figure 2) and identified 8 bactericides, 3 plasticizers, 1 dye, 12 herbicides, 5 insecticides, 11 pharmaceuticals, 7 pharmaceutical or dye intermediates, 1 pesticide, and 7 chemicals with miscellaneous uses, with pesticides (bactericides, herbicides, insecticides, and plant growth regulators) comprising 47.3% of the total. Furthermore, among the detected chemicals, 13 substances were listed in the List of Hazardous Chemicals in China (Table S4). The presence of these hazardous chemicals highlights the potential risks to both the environment and public health. Continuous monitoring and effective management strategies are crucial to mitigate the impact of these pollutants on the river ecosystem and surrounding communities. Detailed analyses of the chemical profiles and their potential sources can provide valuable insights for developing targeted remediation efforts. The suspect screening results showed the presence of 55 chemical substances in the samples collected from the ZB River (Table S5). The total intensity of response peaks and quantity of pollutants detected at each site are illustrated in Figure 1b. Significantly higher total response intensity was observed at ZB-4 compared to other points, it was 13 times greater than that at ZB-6, possibly due to ZB-4 being situated within the CIP and experiencing a strong impact as a result. This elevated response intensity at ZB-4 highlights the need for further investigation into local sources of contamination and their potential impacts on the river's ecosystem. When classified according to their use, the 55 substances detected included 12 pharmaceuticals, 12 herbicides, 8 bactericides, 1 dye, 5 insecticides, 3 plasticizers, 8 pesticides, pharmaceutical, or dye intermediates; 1 plant growth regulator; and 5 chemicals with other uses (Figure 2). This diverse array of chemicals underscores the complexity of pollution sources affecting the river. Among these, 15 substances were listed on the List of Hazardous Chemicals in China (Table S5). The identification of these hazardous chemicals raises concerns about potential risks to aquatic life and human health, necessitating ongoing monitoring and intervention strategies. Detailed chemical profiling and source tracking are essential steps towards effective pollution control and ensuring the long-term health of the river and its surrounding environments. Collaboration between regulatory bodies, local industries, and the scientific community is crucial to address and mitigate the adverse effects of these pollutants. The upper section of the XY River, located above the confluence of the GH River, was divided into three segments - north, middle, and south - each equipped with a sluice. Sites within the sluices, namely XY-1, XY-3, and XY-5, were compared to sites outside the sluices, specifically XY-2, XY-4, and XY-6. The suspect screening analysis revealed 51 chemical substances present in the XY River samples (Table S6). The total intensity of response peaks and quantity of pollutants detected at each site are depicted in Figure 1c. Notably, the response intensity was lower inside the sluice compared to outside, indicated by XY-1 < XY-2, XY-3 < XY-4, and XY-5 < XY-6. The number of pollutants detected at each site aligned with the corresponding intensity ranking, suggesting that the river sluice had a beneficial effect on reducing the inflow of pollutants. This finding underscores the importance of sluice management in controlling pollutant distribution in river systems. Classification of the 51 detected substances by use showed that there were 9 bactericides, 9 pharmaceuticals, 12 herbicides, 6 insecticides, 3 plasticizers, 5 pesticides, pharmaceutical, or dye intermediates, 1 plant growth regulator, and 6 chemicals with other uses (Figure 2); of these, 54.9% were pesticides. The high percentage of pesticides highlights the extensive agricultural impact on the river’s chemical profile. A total of 14 substances were listed on the List of Hazardous Chemicals in China (Table S6), raising concerns about their potential environmental and health risks. Further analysis and continuous monitoring are essential to understand the sources and long-term effects of these chemicals on the river ecosystem. Effective regulatory measures and targeted pollution control strategies must be developed to protect the river and surrounding habitats. Additionally, collaboration with local agricultural sectors to promote sustainable practices could significantly reduce the input of hazardous chemicals into the river. Public awareness and education initiatives regarding the impact of chemical pollutants can also play a crucial role in fostering a more environmentally conscious community. The suspect screening conducted at the coast (YS) detected a total of 26 chemical substances (Table S7), with the intensity of response peaks and number of pollutants detected at each site depicted in Figure 1d. Notably, the response intensity was elevated at YS-5, a site distant from the river estuary, potentially influenced by water flow direction or discharges from other sources. YS-3 and YS-4 also exhibited higher response intensities compared to YS-1 and YS-2, likely due to seawater dilution effects. The elevated levels at YS-3 and YS-4 could also indicate localized contamination sources. YS-5 had the lowest number of substances detected, leading to a relatively high average response intensity per substance, indicating potential pollution sources unrelated to the CIP or GH river. The 26 identified substances were classified into 3 bactericides, 4 pharmaceuticals, 13 herbicides, 1 insecticide, 4 pesticides, pharmaceuticals, or dye intermediates, and 1 miscellaneous chemical, with pesticides representing 65.4% of the total. This high percentage of pesticides suggests significant agricultural runoff impacting the coastal water quality. Importantly, none of the substances identified at YS were listed as hazardous chemicals in China, distinguishing this site from others in the study. This finding highlights the variable nature of chemical pollution sources along the coast, which may differ significantly from inland river sources. Further investigations are warranted to identify the specific sources contributing to the elevated pollutant levels at YS-5 and to understand the broader impacts on coastal ecosystems. Regular monitoring and comprehensive assessments are necessary to track changes over time and evaluate the effectiveness of implemented pollution control measures. Additionally, engaging local communities and industries in pollution reduction efforts can enhance environmental protection and sustainability. Enhanced public awareness and educational programs about the importance of preserving coastal water quality can further support these initiatives, fostering a collaborative approach to mitigating chemical pollution. 3.2 Analysis of the frequently detected pollutants The suspect screening results revealed that across the GH River, ZB River, XY River, and YS sampling sites, 12, 13, 23, and 2 chemical substances were detected, respectively (Figure 3). Upon classification by use, it was determined that 75%, 61.5%, 69.6%, and 100% of the substances in the GH River, ZB River, XY River, and YS were pesticides, respectively. Notably, certain hazardous chemicals listed in China were found in specific rivers, such as 2-nitrophenol, 2,4-dichlorophenol, and tributylamine in the GH River; 2-nitrophenol, nonylphenol, and tributylamine in the ZB River; and 2,4-dichlorophenol, 2,4,6-trichlorophenol, nonylphenol, and 2-phenylphenol in the XY River. Phenolic derivatives, common organic water pollutants, have the potential for conversion into substitute compounds in sewage treatment and natural water environments (Abaide et al. 2019; Arasteh et al. 2010). These substances exhibit toxicity even at low environmental concentrations, with nonylphenol acting as an endocrine disruptor capable of interfering with biological hormone systems (Soares et al. 2008). A notable compound, tributylamine, a strong Lewis base, finds extensive use in catalysts, extractants, and pesticides (Tian et al. 2020; Wang et al. 2008). The analysis of substances detected frequently in the GH River (Figure 4) revealed varying response intensities at different sampling sites. Specifically, the response intensities were notably higher at sites G-3 to G-6, and relatively lower at G-1 and G-2 (Figure 4). Notably, the response intensities of pesticides and pesticide intermediates were significantly elevated at sampling points near the chemical park, indicating a strong influence of the Chemical Industrial Park (CIP) on the concentrations of these substances in the GH River. However, prometryne and tributylamine exhibited distinct patterns. Prometryne, a selective herbicide widely used in controlling annual grasses, exhibited the highest response intensity at G-10, with a noticeable increase at the site closest to the CIP compared to other locations. Prometryne is a selective herbicide of the striazine family that inhibits photosynthesis in plants and is commonly used to control annual grasses in developing countries including China (Chen et al. 2010; Jin et al. 2012; Tian et al. 2020). Prometryne poses challenges in terms of biodegradation and accumulates readily in aquatic organisms (such as fish, shrimp, and shellfish) (Chen et al. 2013 Saka et al. 2018; Yang et al. 2021;). On the other hand, tributylamine was consistently detected at all sampling sites, but with relatively low response intensity, showing no clear association with environmental exposure near the chemical parks. Additionally, 16 chemical substances, including nonylphenol, metribuzin, and pentachlorophenol, were not detected at G-1 and G-2 but were found at sites beyond G-3, suggesting a potential link to CIP emissions (Figure S1). 3.3 Comparative analysis The analysis of pollutants detected in the GH River, ZB River, industrial wastewater, and WWTP effluents found that a total of 33 substances were consistently present across all these sources (Liu et al. 2020). Among these substances, pesticides accounted for 16, or 48.5%, of the detected pollutants (Figure 5). Three specific pollutants - Amitraz metabolite, Sulpiride, and Thiamethoxamn - were exclusively found in the GH River. Furthermore, the presence of Amitraz metabolite was detected at sites G-1, G-3, G-4, and G-5. Detection at site G-1 could be attributed to the use of Amitraz in cross-strait agricultural production, while the absence of detection at G-2 may be due to dilution from incoming tributaries. The presence of N’-(2,4-Dimethylphenyl)-N-methylformamidine at sites G-3, G-4, and G-5 may be linked to the metabolism of Amitraz under specific conditions, as identified in enterprise wastewater and WWTP effluent (Saito et al. 2008). Sole detection of Sulpiride occurred at G-6, while Thiamethoxam was exclusively found at three sites near the Chemical Industrial Park (CIP), indicating potential point source pollution. These pollutants found in the CIP water bodies were also detected in other surrounding water bodies, suggesting a spread of contaminants from the industrial area. Dinoctyl phthalate (DNOP) and Ranitidine were absent in the enterprises’ wastewater and WWTP effluent but were present in the river and surrounding water, raising concerns about non-industrial sources or transformation processes occurring in the environment. Phthalates, like DNOP, are commonly used as plasticizers in PVC production, where they are physically mixed with raw materials to form plastic without chemical bonding, leading to their widespread detection in soil, water, and the atmosphere (Kuang et al. 2010; Sarkar et al. 2013; Wu et al. 2010). Various phthalate compounds, such as N-octyl phthalate, Dibutyl phthalate, and Diethyl phthalate, were identified in the enterprises’ wastewater and WWTP effluent, indicating their pervasive use and release in industrial processes. Ranitidine, an H-2 receptor antagonist used to treat peptic ulcers, esophageal reflux, and Zollinger-Ellison syndrome, is generally well-tolerated. Ranitidine hydrochloride, which can be converted to Ranitidine under specific conditions (Bens et al. 2004; Isidori et al. 2009), was detected in the WWTP effluent and may be linked to the presence of Ranitidine in the irrigation river. This highlights the complexity of pollutant sources and the need for comprehensive monitoring to understand the full extent of chemical contamination. Further studies should focus on the pathways and transformations of these substances in the environment to develop effective mitigation strategies. Collaborative efforts between regulatory bodies, industries, and scientific communities are essential to address and reduce the impact of these pollutants on the ecosystem and human health. The XY River, a tributary of the GH River, exhibited similar pollutant profiles to the GH River (Figure 6), indicating comparable sources of contamination. This suggests that pollutants discharged on both banks of the XY River mirrored those released into the GH River, or that materials could have been transported between the two rivers due to tidal fluctuations, with sluices potentially failing to act as a barrier. The potential influence of tidal actions underscores the need for a comprehensive understanding of hydrodynamic conditions in the region to mitigate pollutant dispersion effectively. We further analyzed the 43 substances detected inside and outside the sluices, revealing three substances exclusively found outside (Barban, Amitraz metabolite, and Sulpiride) and five substances exclusively detected inside (Bifenthrin, Carbofuran, Pentachlorophenol, 4-Chloro-o-tolyloxyacetic acid, and Sulbactam acid). This differentiation in pollutant distribution highlights the partial effectiveness of the sluices in controlling pollutant flow and points to possible localized sources of contamination within the sluiced sections. Barban, Amitraz metabolite, and Sulpiride, found exclusively outside the sluices, suggest that these contaminants may have been introduced from external sources such as agricultural runoff or upstream industrial activities. Conversely, the presence of Bifenthrin, Carbofuran, Pentachlorophenol, 4-Chloro-o-tolyloxyacetic acid, and Sulbactam acid inside the sluices indicates internal sources, which could be due to localized usage or the presence of point source discharges within the sluiced areas. Further detailed investigations are required to pinpoint the exact origins of these substances and to understand the mechanisms driving their distribution. Monitoring programs should include more frequent sampling and advanced analytical techniques to capture the temporal and spatial variations of these pollutants. Additionally, collaborative efforts involving local authorities, industrial stakeholders, and agricultural sectors are crucial to implement effective pollution control measures. Public engagement and awareness campaigns can also play a vital role in reducing pollutant inputs by encouraging best practices in waste management and sustainable agricultural practices. Understanding the specific pathways and behaviors of these pollutants in the aquatic environment will aid in developing targeted strategies to minimize their impact. Continued research and policy development are essential to safeguard the water quality of the XY and GH Rivers, ensuring the protection of both ecological and human health in the region. Of the substances detected inside and outside the sluice of the XY River and GH River, two substances, Bifenthrin and Sulbactam acid, were exclusively found inside the sluice, while one substance, Barban, was solely detected outside the sluice. Additionally, Barban and Cyprodinil were found outside the sluice but not in the GH River. Barban is an herbicide, and Cyprodinil is an anilinopyrimidine plant bactericide (Karadag and Ozhan 2015; Schirra et al. 2009), which may affect the cardiac development of vertebrates through its interaction with the aromatic hydrocarbon receptor (AhR) (Medjakovic et al. 2014; Tang et al. 2020). The exclusive detection of these substances outside the sluice suggests that they may originate from agricultural activities in the surrounding areas, highlighting the need for improved agricultural practices to prevent runoff into water bodies. The presence of Bifenthrin and Sulbactam acid inside the sluice indicates potential localized contamination sources, such as specific agricultural applications or untreated wastewater discharges. Bifenthrin, a pyrethroid insecticide, is widely used for pest control and has been shown to persist in the environment, affecting aquatic life (Spurlock and Lee 2008). Sulbactam acid, a beta-lactamase inhibitor, is commonly used in combination with antibiotics to treat bacterial infections, and its presence in the water may be indicative of pharmaceutical residues entering the aquatic system. Further detailed investigations are required to pinpoint the exact origins of these substances and understand the mechanisms driving their distribution. Monitoring programs should include more frequent sampling and advanced analytical techniques to capture the temporal and spatial variations of these pollutants. Additionally, collaborative efforts involving local authorities, industrial stakeholders, and agricultural sectors are crucial to implement effective pollution control measures. Public engagement and awareness campaigns can also play a vital role in reducing pollutant inputs by encouraging best practices in waste management and sustainable agricultural practices. Understanding the specific pathways and behaviors of these pollutants in the aquatic environment will aid in developing targeted strategies to minimize their impact. Continued research and policy development are essential to safeguard the water quality of the XY and GH Rivers, ensuring the protection of both ecological and human health in the region. 3.4 Analysis of the sources of pollutants in the GH River and ZB River in the CIP 3.4.1 GH river Principal Component Analysis (PCA) was conducted to explore the potential sources of pollutants identified in all sampling sites along the GH River. Following varimax rotation, two main principal components, PC1 and PC2, were discerned, explaining 59.28% and 25.50% of the total variance, respectively (Figure 7). The first component (Figure 7a) was primarily influenced by anileridine, atrazine, azoxystrobin, isoprothiolane, metolachlor, paclobutrazol, triazophos, and tricyclazole, all of which are pesticides except anileridine, a pharmaceutical. These pesticides were predominantly detected at sites G-3 to G-6, exhibiting higher levels compared to other locations. This indicates a significant impact from agricultural activities and potential point sources near these sites. Figure 7b illustrated that pollutants detected at G-3 to G-6, both upstream and downstream of WWTPs, shared similar sources. The presence of anileridine and other compounds in WWTP effluents suggests influences from land-based sources, consistent with previous research (Liu et al. 2020). This finding underscores the role of WWTPs as conduits for both pharmaceutical and pesticide contaminants entering the river system. Sites G-1 and G-2, situated in the upper GH River far from industrial zones, primarily showed pesticide contamination possibly originating from agricultural activities on both sides of the river. The detection of these substances in such locations highlights the pervasive nature of agricultural runoff and its capacity to affect even remote sections of the river. Pollutants detected at sites G-7 to G-10 might have stemmed from effluents released by additional industrial and sewage treatment facilities downstream in the river. The variation in pollutant types and concentrations across these sites suggests diverse sources, including industrial discharges and urban runoff, contributing to the pollution load in the lower reaches of the GH River. The results of the PCA provide a clearer understanding of the spatial distribution and potential sources of pollutants along the GH River. This analysis underscores the need for targeted pollution control measures tailored to specific sections of the river. For instance, enhanced agricultural practices and runoff management could mitigate pesticide contamination in the upper river, while stricter regulation and improved treatment technologies at WWTPs and industrial facilities could address pollutant sources in the mid to lower river sections. Further studies should focus on identifying the exact pathways through which these contaminants enter the river system. This could involve a combination of field surveys, modeling studies, and advanced analytical techniques. Collaborative efforts between environmental agencies, agricultural stakeholders, and industrial operators are crucial to develop and implement effective strategies for reducing pollutant loads and improving water quality in the GH River. Understanding the specific pathways and behaviors of these pollutants in the aquatic environment will aid in developing targeted strategies to minimize their impact. Continued research and policy development are essential to safeguard the water quality of the XY and GH Rivers, ensuring the protection of both ecological and human health in the region. 3.4.2 ZB River Principal Component Analysis (PCA) was utilized to investigate the potential sources of pollutants exclusively detected in the ZB River. Following varimax rotation, three primary principal components (PC) were determined, explaining 53.71% (PC1), 24.24% (PC2), and 16.30% (PC3) of the total variance (Figure 8). In Figure 8a, PC1 was largely influenced by 2-nitrophenol, anileridine, carbendazim, dibutyl phthalate, diethyl phthalate, and tributylamine. All substances, except anileridine, were found in the chemical enterprise, with two-thirds detected in WWTP influents. The response intensity of these substances at site ZB-4 was significantly higher than at other sites, suggesting a specific source at this location. Figure 8b indicated that ZB-4 was distinct from other sampling sites, potentially representing a point source pollution, such as from WWTPs. The elevated levels of these pollutants at ZB-4 highlight the significant influence of a nearby WWTP or other industrial activities. The varied sources of pollutants at different sites, as well as the detection of pharmaceuticals and pesticides, could be linked to activities in the chemical industrial park, agricultural practices, and residential activities in the surrounding areas. The presence of 2-nitrophenol, dibutyl phthalate, and diethyl phthalate suggests contributions from industrial processes and possibly from the use of these compounds in various manufacturing activities. Carbendazim, a fungicide, points to agricultural runoff as a source of contamination. Tributylamine, used in various chemical syntheses, further supports the influence of industrial activities. The findings emphasize the importance of site-specific monitoring and pollution control measures. For instance, enhanced treatment processes at WWTPs and stringent regulation of industrial discharges could mitigate the impact of pollutants at ZB-4. Moreover, agricultural best practices should be promoted to reduce pesticide runoff into the river (Krier J, 2022). Understanding the specific pathways and behaviors of these pollutants in the aquatic environment will aid in developing targeted strategies to minimize their impact. Continued research and policy development are essential to safeguard the water quality of the ZB River, ensuring the protection of both ecological and human health in the region. Further studies should aim to identify the precise sources and pathways of these contaminants. This can be achieved through a combination of advanced analytical techniques, field surveys, and modeling studies. Collaborative efforts among environmental agencies, industrial stakeholders, and the agricultural community are crucial for developing and implementing effective pollution control strategies. Public engagement and awareness campaigns can also play a vital role in encouraging best practices and reducing pollutant inputs. 4. Conclusion In this study, the pollutants in the surrounding rivers of the chemical industrial park (CIP) and its estuary were identified through suspect screening, and the possible relationship between these pollutants and the effluent of the CIP enterprises and wastewater treatment plants (WWTPs) was analyzed. It was found that despite claims of meeting discharge standards by the WWTPs, a significant amount of pollutants in the rivers near the CIP may be attributed to the discharge from the CIP. This indicates that the WWTPs might not be effectively removing all contaminants, or that there are unregulated discharges occurring. The presence of pollutants within the CIP's rivers highlights a direct correlation with the pollutants discharged by the enterprises. This suggests that some enterprises in the CIP may be utilizing discharge pathways outside of the WWTPs, possibly through illegal or unregulated means. This finding necessitates enhanced supervision and stricter enforcement of environmental regulations for these enterprises. To address these issues, it is crucial and urgent to enhance the management of the sewage treatment plants. This could involve upgrading treatment technologies, implementing stricter monitoring and reporting protocols, and ensuring compliance with discharge standards. Additionally, targeted inspections and enforcement actions should be taken to prevent illegal discharges from enterprises within the CIP. Further research and continuous monitoring are essential to better understand the sources and behaviors of these pollutants. This would involve the use of advanced analytical techniques to track the origin and pathways of contaminants, coupled with field surveys to identify potential points of discharge. In summary, the findings underscore the need for comprehensive pollution control strategies that include: 1). Upgrading WWTP infrastructure and treatment processes. 2). Strengthening regulatory oversight and enforcement for both WWTPs and CIP enterprises. 3). Conducting regular monitoring and inspections to detect and prevent illegal discharges. 4). Promoting best practices and compliance among industrial stakeholders. 5). Engaging the public and raising awareness about the importance of protecting water quality. By implementing these measures, it will be possible to reduce pollutant loads and safeguard the ecological and human health of the rivers surrounding the CIP. Declarations Data availability The datasets generated during the current study are available from the corresponding author on reasonable request. Acknowledgements We thank Liwen Bianji (Edanz) (www.liwenbianji.cn/) for editing the English text of a draft of this manuscript. Funding This research was supported by Key Research and Development Program of Jiangsu Province (BE2021731), Independent Research Project of Jiangsu Key Lab of Environmental Engineering (ZZ2020002), Jiangsu Funding Program for Excellent postdoctoral Talent（JB0206016）. Ethics approval and consent to participate Not applicable Consent for publication Not applicable Competing interests The authors declare no competing interests. Authors' contributions Conceptualization: Wei Liu; methodology: Wei Liu, Zhong Daoxu, Jiaming Li; formal analysis: Jiaming Li; investigation: Wei Liu, Zhong Daoxu, Jiaming Li, and Lisen Bai; resources: Jiaming Li and Lisen Bai; visualization: Zhong Daoxu, Jiaming Li; project administration: Shui Wang and Guangbing Liu; funding acquisition: Wei Liu and Shui Wang; Writing–original draft: Jiaming Li; Writing–review & editing: Wei Liu, Jingzhong Tao. All authors have read and agreed to the published version of the manuscript. References Abaide ER, Dotto GL, Tres MV, Zabot GL, Mazutti MAJBt (2019) Adsorption of 2–nitrophenol using rice straw and rice husks hydrolyzed by subcritical water. Bioresource technology 284:25-35. https://doi.org/10.1016/j.biortech.2019.03.110 Arasteh R, Masoumi M, Rashidi A, Moradi L, Samimi V, Mostafavi SJASS (2010) Adsorption of 2-nitrophenol by multi-wall carbon nanotubes from aqueous solutions. 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Environmental Pollution 316:120557. https://doi.org/10.1016/j.envpol.2022.120557 Yang T, Ren Y, Shi L, Wang G (2018) The circular transformation of chemical industrial parks: An integrated evaluation framework and 20 cases in china. Journal of Cleaner Production 196:763-772. https://doi.org/10.1016/j.jclepro.2018.06.099 Yang Z, Huang S, Kong W, Chen L, Ekaterina P, Khatoon Z, Ashraf MN, Akram W (2021) Effects of fish feed addition scenarios with prometryn on microcystis aeruginosa growth and water qualities. Ecotoxicology and Environmental Safety 209. https://doi.org/10.1016/j.ecoenv.2020.111810 Yune JH, Tian J, Liu W, Chen L, Descamps-Large C (2016) Greening chinese chemical industrial park by implementing industrial ecology strategies: A case study. Resources Conservation and Recycling 112:54-64. https://doi.org/10.1016/j.resconrec.2016.05.002 Zhang T, Liu F, Yu X, Jiang X, Cui Y, Li M (2021) Risk assessment and ecotoxicological diagnosis of soil from a chemical industry park in nanjing, china. Ecotoxicology. https://doi.org/10.1007/s10646-020-02320-2 Zheng B, Liu W, Xu H, Li J, Jiang X (2021) Occurrence and distribution of antimicrobial resistance genes in the soil of an industrial park in china: A metagenomics survey. Environmental pollution (Barking, Essex : 1987) 273:116467-116467. https://doi.org/10.1016/j.envpol.2021.116467 Additional Declarations No competing interests reported. Supplementary Files Supplementaryinformation.docx Supplementary Information The following are provided in supplementary information: LC-QTOF-MS analysis, Figure S1: Sample sites of GH River, ZB River, XY River, and Yellow Sea coast; Table S1-S7. 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number of pollutants in the (a) GH River, (b) ZB River, (c) XY River, and (d) YS.\u003c/p\u003e","description":"","filename":"floatimage1.jpg","url":"https://assets-eu.researchsquare.com/files/rs-4651810/v1/2d465602c3f8a654520f4174.jpg"},{"id":60897271,"identity":"749c5d32-26c4-452c-bf9a-4b8b7f4ed09f","added_by":"auto","created_at":"2024-07-23 10:03:35","extension":"jpg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":117251,"visible":true,"origin":"","legend":"\u003cp\u003eClassification of pollutants identified by their use.\u003c/p\u003e","description":"","filename":"floatimage2.jpg","url":"https://assets-eu.researchsquare.com/files/rs-4651810/v1/36691546bcd58e01f29043fd.jpg"},{"id":60895466,"identity":"c6451f4d-6f68-4113-8348-c9f3a7fd5067","added_by":"auto","created_at":"2024-07-23 09:47:35","extension":"jpg","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":107375,"visible":true,"origin":"","legend":"\u003cp\u003eClassification of the frequently detected pollutants.\u003c/p\u003e","description":"","filename":"floatimage3.jpg","url":"https://assets-eu.researchsquare.com/files/rs-4651810/v1/2954e497c5996b1a15e9171e.jpg"},{"id":60896171,"identity":"48677dcd-aa66-49e9-90da-ef400c11779f","added_by":"auto","created_at":"2024-07-23 09:55:35","extension":"jpg","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":146521,"visible":true,"origin":"","legend":"\u003cp\u003ePollutants with a detection rate of 100% in the GH River.\u003c/p\u003e","description":"","filename":"floatimage4.jpg","url":"https://assets-eu.researchsquare.com/files/rs-4651810/v1/4f62e0a003f662588d3f93c2.jpg"},{"id":60895465,"identity":"f26c1f03-33c5-4216-9a13-fd40b57de016","added_by":"auto","created_at":"2024-07-23 09:47:35","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":206110,"visible":true,"origin":"","legend":"\u003cp\u003eVenn diagram showing the number of pollutants detected in the GH River, chemical enterprises, WWTP effluents, and ZB River.\u003c/p\u003e","description":"","filename":"floatimage5.png","url":"https://assets-eu.researchsquare.com/files/rs-4651810/v1/cac1f903adaff11cc6a72ee4.png"},{"id":60895470,"identity":"c35c4272-e7f2-4ca7-8a50-c8a9905ff521","added_by":"auto","created_at":"2024-07-23 09:47:35","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":202263,"visible":true,"origin":"","legend":"\u003cp\u003eVenn diagram of the number of pollutants detected inside/outside the sluice, GH River, and sea coast.\u003c/p\u003e","description":"","filename":"floatimage6.png","url":"https://assets-eu.researchsquare.com/files/rs-4651810/v1/bf504a67a1cf45f947ab8c53.png"},{"id":60896172,"identity":"767f107e-7e7f-4ec3-8f14-4c99cae2b9e6","added_by":"auto","created_at":"2024-07-23 09:55:35","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":45618,"visible":true,"origin":"","legend":"\u003cp\u003ePrincipal component (a) loading plot and (b) score plot after varimax rotation\u003c/p\u003e","description":"","filename":"floatimage7.png","url":"https://assets-eu.researchsquare.com/files/rs-4651810/v1/4304e642b2ffb35fc18dcfbf.png"},{"id":60897945,"identity":"9a1938b5-8ed0-4f9f-a7c8-acb991804bad","added_by":"auto","created_at":"2024-07-23 10:11:35","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":129773,"visible":true,"origin":"","legend":"\u003cp\u003ePrincipal component (a) loading plot and (b) score plot after varimax rotation.\u003c/p\u003e","description":"","filename":"floatimage8.png","url":"https://assets-eu.researchsquare.com/files/rs-4651810/v1/5c52e6e74329070f45659ee5.png"},{"id":72357895,"identity":"240c07fc-fb9e-4830-be93-cbfc8abe27f0","added_by":"auto","created_at":"2024-12-26 05:01:37","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1527637,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4651810/v1/f095f6b7-6a59-4138-bff7-96efa8d1e430.pdf"},{"id":60895473,"identity":"60617319-973c-4c65-b8d9-75eaa5c30f9c","added_by":"auto","created_at":"2024-07-23 09:47:35","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":2832140,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eSupplementary Information\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe following are provided in supplementary information: LC-QTOF-MS analysis, Figure S1: Sample sites of GH River, ZB River, XY River, and Yellow Sea coast; Table S1-S7.\u003c/p\u003e","description":"","filename":"Supplementaryinformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-4651810/v1/32f01947506c83c0209ed437.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Suspect screening of pollutants in rivers around a chemical industrial park in China","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eThe chemical industries worldwide tend to develop in clusters, in purpose-built industrial areas (Ding et al. \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e2020\u003c/span\u003e; Lyu et al. \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e2020\u003c/span\u003e; Pines \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e2005\u003c/span\u003e). In China, the number of chemical industrial parks (CIPs) has increased significantly since their inception in the 1990s, experiencing rapid expansion, especially after 2000 (China Petroleum and Chemical Industry Federation. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttp://www.cpcia.org.cn/\u003c/span\u003e\u003cspan address=\"http://www.cpcia.org.cn/\" targettype=\"URL\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e). The number of national key CIPs in China surged from 200 in 2009 to 676 by the end of 2018. This includes 57 national chemical parks (encompassing economic and technological development zones and high-tech zones), 351 provincial chemical parks, and 268 municipal chemical parks. This significant increase highlights the rapid development and strategic importance of CIPs in China\u0026rsquo;s industrial landscape.\u003c/p\u003e \u003cp\u003eClustering these enterprises together in CIPs has led to significant growth in the Chinese chemical industry, a pivotal national sector. This growth is attributed to several factors, including the efficient utilization of public infrastructure, collaboration among upstream and downstream enterprises within the industrial chain, and decreased transportation and operational costs. Additionally, this clustering model enables more effective governance and oversight by governmental and local authorities (Yang et al. \u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e2018\u003c/span\u003e; Yune et al. \u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e2016\u003c/span\u003e; Zheng et al. \u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). As a result, the proportion of enterprises exceeding the designated size entering these parks reached nearly 45%, underscoring the success and importance of this strategy. This demonstrates how strategic planning and focused investment can drive industrial growth and economic development in key sectors (China Petroleum and Chemical Industry Federation. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttp://www.cpcia.org.cn/\u003c/span\u003e\u003cspan address=\"http://www.cpcia.org.cn/\" targettype=\"URL\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e; Yune et al. \u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e2016\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eThe concentration of chemical companies in industrial parks can indeed lead to significant environmental challenges, primarily due to the concentrated discharge of pollutants (He et al. \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e2018\u003c/span\u003e; Huang et al. \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e2011\u003c/span\u003e; Luo et al. \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). Researchers have detected many kinds of pollutants in the atmosphere, water, and soil within or around CIPs, raising concerns about environmental and public health impacts (Pan et al. \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e2011\u003c/span\u003e; Zhang et al. \u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). Moreover, occasional pollution accidents caused by leaks in chemical parks harm the health of nearby residents (Hou et al. \u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). Although the Chinese government has mandated the construction of centralized wastewater treatment facilities in industrial parks, these facilities primarily focus on conventional pollutants like COD, ammonia nitrogen, SO\u003csub\u003e2\u003c/sub\u003e, and NO\u003csub\u003ex\u003c/sub\u003e (Hu et al. \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2019\u003c/span\u003e, Ding and Hua \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e2012\u003c/span\u003e; Hou et al. \u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e2021\u003c/span\u003e; Hu et al. \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2019\u003c/span\u003e; Luo et al. \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). Consequently, emerging contaminants and less conventional pollutants remain a significant concern. This gap highlights the need for more comprehensive environmental regulations and advanced treatment technologies to address the complex pollution profiles associated with chemical industrial parks.\u003c/p\u003e \u003cp\u003eIt is worth noting that numerous compounds, including pharmaceuticals (Gao et al. \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2016\u003c/span\u003e; Ratola et al. \u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e2012\u003c/span\u003e), active pharmaceutical ingredients (Hey et al. \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e2012\u003c/span\u003e), persistent organic pollutants (POPs) (Bester \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e2005\u003c/span\u003e), and personal care products, are challenging to remove from wastewater (Guo et al. \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e2019\u003c/span\u003e; Perez-Cataluna et al. \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e2021\u003c/span\u003e; Rizzo et al. \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). These compounds tend to adsorb onto suspended particles and settle into activated sludge during the treatment process. Some micropollutants may be released from activated sludge (Katsoyiannis and Samara \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e2005\u003c/span\u003e), and additional byproducts may be generated in the degradation process (Gao et al. \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2016\u003c/span\u003e). These challenges underscore the complexity of managing wastewater from industrial parks and the importance of developing more effective treatment technologies to address emerging contaminants. As wastewater treatment technology continues to evolve, innovative solutions will be necessary to ensure the removal of these complex and persistent pollutants, safeguarding environmental and public health.\u003c/p\u003e \u003cp\u003eThe pollutants that remain after WWTP processes can be discharged into the environment through effluent. These pollutants usually have intricate compositions and low concentrations, making them challenging to detect using conventional methods. However, advancements in technology, such as non-target and suspect screening utilizing high-resolution mass spectrometry (HRMS) coupled with gas or liquid chromatography (Schymanski et al. \u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e2015\u003c/span\u003e; Wu, Y. et al.2023), have provided new tools for identifying these pollutants. Non-target and suspect screening technologies have become a standard approach for detecting and analyzing unknown pollutants in wastewater, surface water, and other environmental media (Kang et al. \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e2020\u003c/span\u003e; Wang et al. \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). These advanced analytical methods enable more comprehensive monitoring of environmental pollutants, facilitating the identification of emerging contaminants and enhancing our understanding of their behavior and impact in the environment.\u003c/p\u003e \u003cp\u003eIn a previous study conducted in chemical industrial parks (CIPs) in Jiangsu Province, researchers utilized suspect screening and liquid chromatography time-of-flight mass spectrometry (LC-QTOF-MS) to identify the types of pollutants present in different chemical enterprises and at various stages of wastewater treatment (Liu et al. \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). This study aimed to investigate the pollutants in rivers near a CIP, tributaries in the downstream areas of these rivers, and locations near the river estuary at the coast. By screening pollutants in multiple small rivers flowing through the CIP, the study sought to uncover potential relationships between water pollutants and discharges from the industrial park. The comprehensive approach allowed for the detection of a wide range of pollutants, enhancing our understanding of the environmental impact of chemical discharges and highlighting the need for improved wastewater treatment and monitoring practices in industrial areas.\u003c/p\u003e"},{"header":"2. Materials and methods","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1 Sample collection\u003c/h2\u003e \u003cp\u003eThe study involved collecting 29 surface water samples from various rivers around the chemical industrial park (CIP) in Jiangsu Province, including the GH River, ZB River (which runs through the CIP), XY River, and the Yellow Sea coast. The samples were collected from different sites along each river, with specific sites denoted based on their location relative to the CIP and other landmarks. Samples were also collected from sites near the GH River estuary at the coast.\u003c/p\u003e \u003cp\u003each sample collected was 1 liter in volume and underwent filtration through 1-\u0026micro;m glass fiber filter membranes and 0.45-\u0026micro;m nylon filter membranes to remove solid impurities. The filtered samples were then stored at 4\u0026deg;C and transported to the laboratory for further analysis. This meticulous sampling process was conducted to investigate the presence of pollutants in the rivers surrounding the CIP and to assess any potential relationships between water quality and industrial discharges.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2 Sample pretreatment\u003c/h2\u003e \u003cp\u003eThe pollutants present in the water samples were extracted using solid phase extraction (SPE) (Liu et al. \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). A preconditioned Oasis HLB cartridge (6 cc/500 mg, Waters, USA) was used for the extraction process. The extraction flow rate was maintained at 3\u0026ndash;5 mL/min, and after extraction, elution was carried out using 10 mL of methanol followed by 10 mL of dichloromethane (Merck, Germany). The extracted sample was then evaporated using N\u003csub\u003e2\u003c/sub\u003e and dissolved in 1 mL of methanol. The resulting extract was filtered through a 0.2 \u0026micro;m polypropylene membrane syringe filter (Acrodisc\u0026reg; GHP, 13 mm, 0.2 \u0026micro;m, Waters, USA), collected in an amber vial, and stored at -20\u0026deg;C until further analysis.\u003c/p\u003e \u003cp\u003eTo prevent sample contamination, all equipment used in the extraction process was thoroughly pre-cleaned with hexane, dichloromethane, and methanol. This meticulous extraction process ensured the integrity of the collected water samples for subsequent analysis of pollutants.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3 LC-QTOF-MS analysis and mass spectrometry data analysis\u003c/h2\u003e \u003cp\u003eIn this study, LC-QTOF-MS analysis method was used adhered to the identical workflow for mass spectrometry data analysis as demonstrated in our prior investigation (Liu et al. \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). In Brief, the samples were analyzed using liquid chromatography (LC; Agilent Technologies, Waldbronn, Germany) coupled with a high-resolution hybrid quadrupole time-of-flight mass spectrometer (Triple TOF 5600, AB Sciex, Foster City, CA). A detailed description about the instrument parameter settings, quality assurance, and quality control are provided in the supplementary information (SI).\u003c/p\u003e \u003cp\u003eWe isolated the suspect peaks and identified the pollutants using standards and databases (details are provided in SI). And we referred to the reported methods and assigned a confidence level for each identified pollutant (Schymanski et al. \u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e2014\u003c/span\u003e). The confidence level was 1 if the structure was confirmed by the authentic standards, or 2 for a probable structure, from either a library spectrum match (2a) or diagnostic evidence (2b). This study only considered substances with confidence levels of 1 and 2.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e2.4 Data analysis tools\u003c/h2\u003e \u003cp\u003eThe mass spectrometry data were analyzed with PeakView 2.2 software (AB SCIEX, USA). Principal component analysis (PCA) was performed using SPSS Statistics software version 24.0 (IBM, USA). The figures were drawn in SigmaPlot 12.5 (Systat, USA), Excel 2016 (Microsoft, USA), and Venny 2.1 (\u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://bioinfogp.cnb.csic.es/tools/venny/index.html\u003c/span\u003e\u003cspan address=\"https://bioinfogp.cnb.csic.es/tools/venny/index.html\" targettype=\"URL\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e).\u003c/p\u003e \u003c/div\u003e"},{"header":"3. Results and Discussion","content":"\u003cp\u003e\u003cstrong\u003e3.1 Pollutant identification\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eFrom the suspect screening, 55 chemicals were identified in the GH River (detailed information is provided in Table S4). The total intensity and quantity of pollutants detected at each site are shown in Figure 1a. Significant variations in the total response intensity were observed, with sites G-3 to G-6 exhibiting notably higher values compared to sites G-1 and G-2. For instance, the total response intensity of the sample from G-6 was 10 times greater than that at G-2. The CIP was situated between sites G-4 and G-5, potentially contributing to the heightened response intensities at G-3 to G-6. Across all sites, the distribution patterns in both the number of pollutants detected and their respective response displayed similar trends from G-1 to G-10. The 55 chemical substances detected were classified based on their applications (Figure 2) and identified 8 bactericides, 3 plasticizers, 1 dye, 12 herbicides, 5 insecticides, 11 pharmaceuticals, 7 pharmaceutical or dye intermediates, 1 pesticide, and 7 chemicals with miscellaneous uses, with pesticides (bactericides, herbicides, insecticides, and plant growth regulators) comprising 47.3% of the total. Furthermore, among the detected chemicals, 13 substances were listed in the List of Hazardous Chemicals in China (Table S4). The presence of these hazardous chemicals highlights the potential risks to both the environment and public health. Continuous monitoring and effective management strategies are crucial to mitigate the impact of these pollutants on the river ecosystem and surrounding communities. Detailed analyses of the chemical profiles and their potential sources can provide valuable insights for developing targeted remediation efforts.\u003c/p\u003e\n\u003cp\u003eThe suspect screening results showed the presence of 55 chemical substances in the samples collected from the ZB River (Table S5). The total intensity of response peaks and quantity of pollutants detected at each site are illustrated in Figure 1b. Significantly higher total response intensity was observed at ZB-4 compared to other points, it was 13 times greater than that at ZB-6, possibly due to ZB-4 being situated within the CIP and experiencing a strong impact as a result. This elevated response intensity at ZB-4 highlights the need for further investigation into local sources of contamination and their potential impacts on the river\u0026apos;s ecosystem. When classified according to their use, the 55 substances detected included 12 pharmaceuticals, 12 herbicides, 8 bactericides, 1 dye, 5 insecticides, 3 plasticizers, 8 pesticides, pharmaceutical, or dye intermediates; 1 plant growth regulator; and 5 chemicals with other uses (Figure 2). This diverse array of chemicals underscores the complexity of pollution sources affecting the river. Among these, 15 substances were listed on the List of Hazardous Chemicals in China (Table S5). The identification of these hazardous chemicals raises concerns about potential risks to aquatic life and human health, necessitating ongoing monitoring and intervention strategies. Detailed chemical profiling and source tracking are essential steps towards effective pollution control and ensuring the long-term health of the river and its surrounding environments. Collaboration between regulatory bodies, local industries, and the scientific community is crucial to address and mitigate the adverse effects of these pollutants.\u003c/p\u003e\n\u003cp\u003eThe upper section of the XY River, located above the confluence of the GH River, was divided into three segments - north, middle, and south - each equipped with a sluice. Sites within the sluices, namely XY-1, XY-3, and XY-5, were compared to sites outside the sluices, specifically XY-2, XY-4, and XY-6. The suspect screening analysis revealed 51 chemical substances present in the XY River samples (Table S6). The total intensity of response peaks and quantity of pollutants detected at each site are depicted in Figure 1c. Notably, the response intensity was lower inside the sluice compared to outside, indicated by XY-1 \u0026lt; XY-2, XY-3 \u0026lt; XY-4, and XY-5 \u0026lt; XY-6. The number of pollutants detected at each site aligned with the corresponding intensity ranking, suggesting that the river sluice had a beneficial effect on reducing the inflow of pollutants. This finding underscores the importance of sluice management in controlling pollutant distribution in river systems.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eClassification of the 51 detected substances by use showed that there were 9 bactericides, 9 pharmaceuticals, 12 herbicides, 6 insecticides, 3 plasticizers, 5 pesticides, pharmaceutical, or dye intermediates, 1 plant growth regulator, and 6 chemicals with other uses (Figure 2); of these, 54.9% were pesticides. The high percentage of pesticides highlights the extensive agricultural impact on the river\u0026rsquo;s chemical profile. A total of 14 substances were listed on the List of Hazardous Chemicals in China (Table S6), raising concerns about their potential environmental and health risks.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eFurther analysis and continuous monitoring are essential to understand the sources and long-term effects of these chemicals on the river ecosystem. Effective regulatory measures and targeted pollution control strategies must be developed to protect the river and surrounding habitats. Additionally, collaboration with local agricultural sectors to promote sustainable practices could significantly reduce the input of hazardous chemicals into the river. Public awareness and education initiatives regarding the impact of chemical pollutants can also play a crucial role in fostering a more environmentally conscious community.\u003c/p\u003e\n\u003cp\u003eThe suspect screening conducted at the coast (YS) detected a total of 26 chemical substances (Table S7), with the intensity of response peaks and number of pollutants detected at each site depicted in Figure 1d. Notably, the response intensity was elevated at YS-5, a site distant from the river estuary, potentially influenced by water flow direction or discharges from other sources. YS-3 and YS-4 also exhibited higher response intensities compared to YS-1 and YS-2, likely due to seawater dilution effects. The elevated levels at YS-3 and YS-4 could also indicate localized contamination sources. YS-5 had the lowest number of substances detected, leading to a relatively high average response intensity per substance, indicating potential pollution sources unrelated to the CIP or GH river.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe 26 identified substances were classified into 3 bactericides, 4 pharmaceuticals, 13 herbicides, 1 insecticide, 4 pesticides, pharmaceuticals, or dye intermediates, and 1 miscellaneous chemical, with pesticides representing 65.4% of the total. This high percentage of pesticides suggests significant agricultural runoff impacting the coastal water quality. Importantly, none of the substances identified at YS were listed as hazardous chemicals in China, distinguishing this site from others in the study. This finding highlights the variable nature of chemical pollution sources along the coast, which may differ significantly from inland river sources.\u003c/p\u003e\n\u003cp\u003eFurther investigations are warranted to identify the specific sources contributing to the elevated pollutant levels at YS-5 and to understand the broader impacts on coastal ecosystems. Regular monitoring and comprehensive assessments are necessary to track changes over time and evaluate the effectiveness of implemented pollution control measures. Additionally, engaging local communities and industries in pollution reduction efforts can enhance environmental protection and sustainability. Enhanced public awareness and educational programs about the importance of preserving coastal water quality can further support these initiatives, fostering a collaborative approach to mitigating chemical pollution.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e3.2 Analysis of the frequently detected pollutants\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe suspect screening results revealed that across the GH River, ZB River, XY River, and YS sampling sites, 12, 13, 23, and 2 chemical substances were detected, respectively (Figure 3). Upon classification by use, it was determined that 75%, 61.5%, 69.6%, and 100% of the substances in the GH River, ZB River, XY River, and YS were pesticides, respectively. Notably, certain hazardous chemicals listed in China were found in specific rivers, such as 2-nitrophenol, 2,4-dichlorophenol, and tributylamine in the GH River; 2-nitrophenol, nonylphenol, and tributylamine in the ZB River; and 2,4-dichlorophenol, 2,4,6-trichlorophenol, nonylphenol, and 2-phenylphenol in the XY River. Phenolic derivatives, common organic water pollutants, have the potential for conversion into substitute compounds in sewage treatment and natural water environments (Abaide et al. 2019; Arasteh et al. 2010). These substances exhibit toxicity even at low environmental concentrations, with nonylphenol acting as an endocrine disruptor capable of interfering with biological hormone systems (Soares et al. 2008). A notable compound, tributylamine, a strong Lewis base, finds extensive use in catalysts, extractants, and pesticides (Tian et al. 2020; Wang et al. 2008).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe analysis of substances detected frequently in the GH River (Figure 4) revealed varying response intensities at different sampling sites. Specifically, the response intensities were notably higher at sites G-3 to G-6, and relatively lower at G-1 and G-2 (Figure 4). Notably, the response intensities of pesticides and pesticide intermediates were significantly elevated at sampling points near the chemical park, indicating a strong influence of the Chemical Industrial Park (CIP) on the concentrations of these substances in the GH River. However, prometryne and tributylamine exhibited distinct patterns. Prometryne, a selective herbicide widely used in controlling annual grasses, exhibited the highest response intensity at G-10, with a noticeable increase at the site closest to the CIP compared to other locations. Prometryne is a selective herbicide of the striazine family that inhibits photosynthesis in plants and is commonly used to control annual grasses in developing countries including China (Chen et al. 2010;\u0026nbsp;Jin et al. 2012;\u0026nbsp;Tian et al. 2020). Prometryne poses challenges in terms of biodegradation and accumulates readily in aquatic organisms (such as fish, shrimp, and shellfish) (Chen et al. 2013\u0026nbsp;Saka et al. 2018;\u0026nbsp;Yang et al. 2021;). On the other hand, tributylamine was consistently detected at all sampling sites, but with relatively low response intensity, showing no clear association with environmental exposure near the chemical parks. Additionally, 16 chemical substances, including nonylphenol, metribuzin, and pentachlorophenol, were not detected at G-1 and G-2 but were found at sites beyond G-3, suggesting a potential link to CIP emissions (Figure S1).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e3.3 Comparative analysis\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe analysis of pollutants detected in the GH River, ZB River, industrial wastewater, and WWTP effluents found that a total of 33 substances were consistently present across all these sources (Liu et al. 2020). Among these substances, pesticides accounted for 16, or 48.5%, of the detected pollutants (Figure 5). Three specific pollutants - Amitraz metabolite, Sulpiride, and Thiamethoxamn - were exclusively found in the GH River. Furthermore, the presence of Amitraz metabolite was detected at sites G-1, G-3, G-4, and G-5. Detection at site G-1 could be attributed to the use of Amitraz in cross-strait agricultural production, while the absence of detection at G-2 may be due to dilution from incoming tributaries. The presence of N\u0026rsquo;-(2,4-Dimethylphenyl)-N-methylformamidine at sites G-3, G-4, and G-5 may be linked to the metabolism of Amitraz under specific conditions, as identified in enterprise wastewater and WWTP effluent (Saito et al. 2008).\u003c/p\u003e\n\u003cp\u003eSole detection of Sulpiride occurred at G-6, while Thiamethoxam was exclusively found at three sites near the Chemical Industrial Park (CIP), indicating potential point source pollution. These pollutants found in the CIP water bodies were also detected in other surrounding water bodies, suggesting a spread of contaminants from the industrial area. Dinoctyl phthalate (DNOP) and Ranitidine were absent in the enterprises\u0026rsquo; wastewater and WWTP effluent but were present in the river and surrounding water, raising concerns about non-industrial sources or transformation processes occurring in the environment. Phthalates, like DNOP, are commonly used as plasticizers in PVC production, where they are physically mixed with raw materials to form plastic without chemical bonding, leading to their widespread detection in soil, water, and the atmosphere (Kuang et al. 2010; Sarkar et al. 2013; Wu et al. 2010).\u003c/p\u003e\n\u003cp\u003eVarious phthalate compounds, such as N-octyl phthalate, Dibutyl phthalate, and Diethyl phthalate, were identified in the enterprises\u0026rsquo; wastewater and WWTP effluent, indicating their pervasive use and release in industrial processes. Ranitidine, an H-2 receptor antagonist used to treat peptic ulcers, esophageal reflux, and Zollinger-Ellison syndrome, is generally well-tolerated. Ranitidine hydrochloride, which can be converted to Ranitidine under specific conditions (Bens et al. 2004; Isidori et al. 2009), was detected in the WWTP effluent and may be linked to the presence of Ranitidine in the irrigation river. This highlights the complexity of pollutant sources and the need for comprehensive monitoring to understand the full extent of chemical contamination. Further studies should focus on the pathways and transformations of these substances in the environment to develop effective mitigation strategies. Collaborative efforts between regulatory bodies, industries, and scientific communities are essential to address and reduce the impact of these pollutants on the ecosystem and human health.\u003c/p\u003e\n\u003cp\u003eThe XY River, a tributary of the GH River, exhibited similar pollutant profiles to the GH River (Figure 6), indicating comparable sources of contamination. This suggests that pollutants discharged on both banks of the XY River mirrored those released into the GH River, or that materials could have been transported between the two rivers due to tidal fluctuations, with sluices potentially failing to act as a barrier. The potential influence of tidal actions underscores the need for a comprehensive understanding of hydrodynamic conditions in the region to mitigate pollutant dispersion effectively.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eWe further analyzed the 43 substances detected inside and outside the sluices, revealing three substances exclusively found outside (Barban, Amitraz metabolite, and Sulpiride) and five substances exclusively detected inside (Bifenthrin, Carbofuran, Pentachlorophenol, 4-Chloro-o-tolyloxyacetic acid, and Sulbactam acid). This differentiation in pollutant distribution highlights the partial effectiveness of the sluices in controlling pollutant flow and points to possible localized sources of contamination within the sluiced sections.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eBarban, Amitraz metabolite, and Sulpiride, found exclusively outside the sluices, suggest that these contaminants may have been introduced from external sources such as agricultural runoff or upstream industrial activities. Conversely, the presence of Bifenthrin, Carbofuran, Pentachlorophenol, 4-Chloro-o-tolyloxyacetic acid, and Sulbactam acid inside the sluices indicates internal sources, which could be due to localized usage or the presence of point source discharges within the sluiced areas.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eFurther detailed investigations are required to pinpoint the exact origins of these substances and to understand the mechanisms driving their distribution. Monitoring programs should include more frequent sampling and advanced analytical techniques to capture the temporal and spatial variations of these pollutants. Additionally, collaborative efforts involving local authorities, industrial stakeholders, and agricultural sectors are crucial to implement effective pollution control measures. Public engagement and awareness campaigns can also play a vital role in reducing pollutant inputs by encouraging best practices in waste management and sustainable agricultural practices.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eUnderstanding the specific pathways and behaviors of these pollutants in the aquatic environment will aid in developing targeted strategies to minimize their impact. Continued research and policy development are essential to safeguard the water quality of the XY and GH Rivers, ensuring the protection of both ecological and human health in the region. Of the substances detected inside and outside the sluice of the XY River and GH River, two substances, Bifenthrin and Sulbactam acid, were exclusively found inside the sluice, while one substance, Barban, was solely detected outside the sluice. Additionally, Barban and Cyprodinil were found outside the sluice but not in the GH River.\u003c/p\u003e\n\u003cp\u003eBarban is an herbicide, and Cyprodinil is an anilinopyrimidine plant bactericide (Karadag and Ozhan 2015; Schirra et al. 2009), which may affect the cardiac development of vertebrates through its interaction with the aromatic hydrocarbon receptor (AhR) (Medjakovic et al. 2014; Tang et al. 2020). The exclusive detection of these substances outside the sluice suggests that they may originate from agricultural activities in the surrounding areas, highlighting the need for improved agricultural practices to prevent runoff into water bodies.\u003c/p\u003e\n\u003cp\u003eThe presence of Bifenthrin and Sulbactam acid inside the sluice indicates potential localized contamination sources, such as specific agricultural applications or untreated wastewater discharges. Bifenthrin, a pyrethroid insecticide, is widely used for pest control and has been shown to persist in the environment, affecting aquatic life (Spurlock and Lee 2008). Sulbactam acid, a beta-lactamase inhibitor, is commonly used in combination with antibiotics to treat bacterial infections, and its presence in the water may be indicative of pharmaceutical residues entering the aquatic system.\u003c/p\u003e\n\u003cp\u003eFurther detailed investigations are required to pinpoint the exact origins of these substances and understand the mechanisms driving their distribution. Monitoring programs should include more frequent sampling and advanced analytical techniques to capture the temporal and spatial variations of these pollutants. Additionally, collaborative efforts involving local authorities, industrial stakeholders, and agricultural sectors are crucial to implement effective pollution control measures. Public engagement and awareness campaigns can also play a vital role in reducing pollutant inputs by encouraging best practices in waste management and sustainable agricultural practices.\u003c/p\u003e\n\u003cp\u003eUnderstanding the specific pathways and behaviors of these pollutants in the aquatic environment will aid in developing targeted strategies to minimize their impact. Continued research and policy development are essential to safeguard the water quality of the XY and GH Rivers, ensuring the protection of both ecological and human health in the region.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e3.4 Analysis of the sources of pollutants in the GH River and ZB River in the CIP\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e3.4.1 GH river\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003ePrincipal Component Analysis (PCA) was conducted to explore the potential sources of pollutants identified in all sampling sites along the GH River. Following varimax rotation, two main principal components, PC1 and PC2, were discerned, explaining 59.28% and 25.50% of the total variance, respectively (Figure 7). The first component (Figure 7a) was primarily influenced by anileridine, atrazine, azoxystrobin, isoprothiolane, metolachlor, paclobutrazol, triazophos, and tricyclazole, all of which are pesticides except anileridine, a pharmaceutical. These pesticides were predominantly detected at sites G-3 to G-6, exhibiting higher levels compared to other locations. This indicates a significant impact from agricultural activities and potential point sources near these sites.\u003c/p\u003e\n\u003cp\u003eFigure 7b illustrated that pollutants detected at G-3 to G-6, both upstream and downstream of WWTPs, shared similar sources. The presence of anileridine and other compounds in WWTP effluents suggests influences from land-based sources, consistent with previous research (Liu et al. 2020). This finding underscores the role of WWTPs as conduits for both pharmaceutical and pesticide contaminants entering the river system.\u003c/p\u003e\n\u003cp\u003eSites G-1 and G-2, situated in the upper GH River far from industrial zones, primarily showed pesticide contamination possibly originating from agricultural activities on both sides of the river. The detection of these substances in such locations highlights the pervasive nature of agricultural runoff and its capacity to affect even remote sections of the river.\u003c/p\u003e\n\u003cp\u003ePollutants detected at sites G-7 to G-10 might have stemmed from effluents released by additional industrial and sewage treatment facilities downstream in the river. The variation in pollutant types and concentrations across these sites suggests diverse sources, including industrial discharges and urban runoff, contributing to the pollution load in the lower reaches of the GH River.\u003c/p\u003e\n\u003cp\u003eThe results of the PCA provide a clearer understanding of the spatial distribution and potential sources of pollutants along the GH River. This analysis underscores the need for targeted pollution control measures tailored to specific sections of the river. For instance, enhanced agricultural practices and runoff management could mitigate pesticide contamination in the upper river, while stricter regulation and improved treatment technologies at WWTPs and industrial facilities could address pollutant sources in the mid to lower river sections.\u003c/p\u003e\n\u003cp\u003eFurther studies should focus on identifying the exact pathways through which these contaminants enter the river system. This could involve a combination of field surveys, modeling studies, and advanced analytical techniques. Collaborative efforts between environmental agencies, agricultural stakeholders, and industrial operators are crucial to develop and implement effective strategies for reducing pollutant loads and improving water quality in the GH River.\u003c/p\u003e\n\u003cp\u003eUnderstanding the specific pathways and behaviors of these pollutants in the aquatic environment will aid in developing targeted strategies to minimize their impact. Continued research and policy development are essential to safeguard the water quality of the XY and GH Rivers, ensuring the protection of both ecological and human health in the region.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e3.4.2 ZB River\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003ePrincipal Component Analysis (PCA) was utilized to investigate the potential sources of pollutants exclusively detected in the ZB River. Following varimax rotation, three primary principal components (PC) were determined, explaining 53.71% (PC1), 24.24% (PC2), and 16.30% (PC3) of the total variance (Figure 8).\u003c/p\u003e\n\u003cp\u003eIn Figure 8a, PC1 was largely influenced by 2-nitrophenol, anileridine, carbendazim, dibutyl phthalate, diethyl phthalate, and tributylamine. All substances, except anileridine, were found in the chemical enterprise, with two-thirds detected in WWTP influents. The response intensity of these substances at site ZB-4 was significantly higher than at other sites, suggesting a specific source at this location.\u003c/p\u003e\n\u003cp\u003eFigure 8b indicated that ZB-4 was distinct from other sampling sites, potentially representing a point source pollution, such as from WWTPs. The elevated levels of these pollutants at ZB-4 highlight the significant influence of a nearby WWTP or other industrial activities.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe varied sources of pollutants at different sites, as well as the detection of pharmaceuticals and pesticides, could be linked to activities in the chemical industrial park, agricultural practices, and residential activities in the surrounding areas. The presence of 2-nitrophenol, dibutyl phthalate, and diethyl phthalate suggests contributions from industrial processes and possibly from the use of these compounds in various manufacturing activities. Carbendazim, a fungicide, points to agricultural runoff as a source of contamination. Tributylamine, used in various chemical syntheses, further supports the influence of industrial activities.\u003c/p\u003e\n\u003cp\u003eThe findings emphasize the importance of site-specific monitoring and pollution control measures. For instance, enhanced treatment processes at WWTPs and stringent regulation of industrial discharges could mitigate the impact of pollutants at ZB-4. Moreover, agricultural best practices should be promoted to reduce pesticide runoff into the river (Krier J, 2022).\u003c/p\u003e\n\u003cp\u003eUnderstanding the specific pathways and behaviors of these pollutants in the aquatic environment will aid in developing targeted strategies to minimize their impact. Continued research and policy development are essential to safeguard the water quality of the ZB River, ensuring the protection of both ecological and human health in the region.\u003c/p\u003e\n\u003cp\u003eFurther studies should aim to identify the precise sources and pathways of these contaminants. This can be achieved through a combination of advanced analytical techniques, field surveys, and modeling studies. Collaborative efforts among environmental agencies, industrial stakeholders, and the agricultural community are crucial for developing and implementing effective pollution control strategies. Public engagement and awareness campaigns can also play a vital role in encouraging best practices and reducing pollutant inputs.\u003c/p\u003e"},{"header":"4. Conclusion","content":"\u003cp\u003eIn this study, the pollutants in the surrounding rivers of the chemical industrial park (CIP) and its estuary were identified through suspect screening, and the possible relationship between these pollutants and the effluent of the CIP enterprises and wastewater treatment plants (WWTPs) was analyzed. It was found that despite claims of meeting discharge standards by the WWTPs, a significant amount of pollutants in the rivers near the CIP may be attributed to the discharge from the CIP. This indicates that the WWTPs might not be effectively removing all contaminants, or that there are unregulated discharges occurring.\u003c/p\u003e\n\u003cp\u003eThe presence of pollutants within the CIP\u0026apos;s rivers highlights a direct correlation with the pollutants discharged by the enterprises. This suggests that some enterprises in the CIP may be utilizing discharge pathways outside of the WWTPs, possibly through illegal or unregulated means. This finding necessitates enhanced supervision and stricter enforcement of environmental regulations for these enterprises.\u003c/p\u003e\n\u003cp\u003eTo address these issues, it is crucial and urgent to enhance the management of the sewage treatment plants. This could involve upgrading treatment technologies, implementing stricter monitoring and reporting protocols, and ensuring compliance with discharge standards. Additionally, targeted inspections and enforcement actions should be taken to prevent illegal discharges from enterprises within the CIP.\u003c/p\u003e\n\u003cp\u003eFurther research and continuous monitoring are essential to better understand the sources and behaviors of these pollutants. This would involve the use of advanced analytical techniques to track the origin and pathways of contaminants, coupled with field surveys to identify potential points of discharge.\u003c/p\u003e\n\u003cp\u003eIn summary, the findings underscore the need for comprehensive pollution control strategies that include:\u003c/p\u003e\n\u003cp\u003e1). Upgrading WWTP infrastructure and treatment processes.\u003c/p\u003e\n\u003cp\u003e2). Strengthening regulatory oversight and enforcement for both WWTPs and CIP enterprises.\u003c/p\u003e\n\u003cp\u003e3). Conducting regular monitoring and inspections to detect and prevent illegal discharges.\u003c/p\u003e\n\u003cp\u003e4). Promoting best practices and compliance among industrial stakeholders.\u003c/p\u003e\n\u003cp\u003e5). Engaging the public and raising awareness about the importance of protecting water quality.\u003c/p\u003e\n\u003cp\u003eBy implementing these measures, it will be possible to reduce pollutant loads and safeguard the ecological and human health of the rivers surrounding the CIP.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eData availability\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe datasets generated during the current study are available from the corresponding author on reasonable request.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eWe thank Liwen Bianji (Edanz) (www.liwenbianji.cn/) for editing the English text of a draft of this manuscript.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis research was supported by Key Research and Development Program of Jiangsu Province (BE2021731), Independent Research Project of Jiangsu Key Lab of Environmental Engineering (ZZ2020002), Jiangsu Funding Program for Excellent postdoctoral Talent（JB0206016）.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eEthics approval and consent to participate\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eNot applicable\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConsent for publication\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eNot applicable\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting interests\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthors\u0026apos; contributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eConceptualization: Wei Liu; methodology: Wei Liu, Zhong Daoxu, Jiaming Li; formal analysis: Jiaming Li; investigation: Wei Liu, Zhong Daoxu, Jiaming Li, and Lisen Bai; resources: Jiaming Li and Lisen Bai; visualization: Zhong Daoxu, Jiaming Li; project administration: Shui Wang and Guangbing Liu; funding acquisition: Wei Liu and Shui Wang; Writing\u0026ndash;original draft: Jiaming Li; Writing\u0026ndash;review \u0026amp; editing: Wei Liu, Jingzhong Tao. All authors have read and agreed to the published version of the manuscript.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eAbaide ER, Dotto GL, Tres MV, Zabot GL, Mazutti MAJBt (2019) Adsorption of 2\u0026ndash;nitrophenol using rice straw and rice husks hydrolyzed by subcritical water. Bioresource technology 284:25-35. https://doi.org/10.1016/j.biortech.2019.03.110\u003c/li\u003e\n\u003cli\u003eArasteh R, Masoumi M, Rashidi A, Moradi L, Samimi V, Mostafavi SJASS (2010) Adsorption of 2-nitrophenol by multi-wall carbon nanotubes from aqueous solutions. Applied Surface Science 256:4447-4455. https://doi.org/10.1016/j.apsusc.2010.01.057\u003c/li\u003e\n\u003cli\u003eBens G, Herrmann M, Hubner U, Reichrath J, Herrmann W, Tilgen W, Koch P (2004) Immediate-type hypersensitivity to ranitidine. 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Environmental pollution (Barking, Essex : 1987) 273:116467-116467. https://doi.org/10.1016/j.envpol.2021.116467\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"suspect screening, hazardous chemicals, chemical industrial park, rivers, wastewater treatment plants","lastPublishedDoi":"10.21203/rs.3.rs-4651810/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4651810/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eChinese chemical companies often cluster in specific regions, leading to concentrated emissions of various chemicals and pollutants, which poses significant risks to ecosystems and human health. Water samples were collected from the rivers near the chemical industrial park (CIP) in Jiangsu Province, China, and utilized suspect screening to identify pollutants. This study aimed to examine the correlation between these pollutants and those detected in the effluent from the companies or wastewater treatment plants (WWTPs) within the CIP, thereby providing a scientific basis for government management decisions. In the rivers surrounding the CIP, over 50 types of pollutants were found, with 26 identified near the river estuary, half of which were pesticides. Analysis indicated that sites closest to the WWTPs discharge outlets exhibited heightened pollutant levels, suggesting the release of challenging-to-treat pollutants into the environment. Additionally, compounds consistent with those used by the companies were detected in rivers without WWTP discharge, underscoring that pollutants originating from CIP enterprises are not solely attributed to wastewater treatment plant discharges. This information underscores the need for comprehensive and effective environmental management and monitoring strategies within chemical industrial parks.\u003c/p\u003e","manuscriptTitle":"Suspect screening of pollutants in rivers around a chemical industrial park in China","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-07-23 09:47:30","doi":"10.21203/rs.3.rs-4651810/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"411dd8fc-5f55-4186-a8cc-3b165f376630","owner":[],"postedDate":"July 23rd, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[{"id":34835519,"name":"Earth and environmental sciences/Environmental sciences"},{"id":34835520,"name":"Earth and environmental sciences/Environmental sciences/Environmental chemistry"}],"tags":[],"updatedAt":"2024-12-26T04:53:24+00:00","versionOfRecord":[],"versionCreatedAt":"2024-07-23 09:47:30","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-4651810","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4651810","identity":"rs-4651810","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}