Occurrence and ecological risk assessment for organophosphate esters in Luoma Lake

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The concentration, distribution and risk of OPEs has caused global concern in recent years. The Luoma Lake is one of drinking water source and four major freshwater in the Jiangsu provinces. The aim of this study is to investigate the pollution level of 11 OPEs in surface water and sediment of Luoma Lake within inflowing and outflowing river. The total concentration of 11 OPEs in the water and sediment were 1751–3967 ng/L and 288–513 µg/kg (ww), respectively. The concentration of 11 OPEs in Fangting River were higher than that in Yi River. Tris (2-chloroethyl) phosphate (TCEP) and triphenyl phosphate (TPhP) were the most abundant in the surface water. Tri-p-tolyl phosphate (TPTP) and Tris (1-chloro-2-propyl) phosphate (TCIPP) were the most abundant in the sediment. From the ecological risk, TPhP and TCIPP were the most significant contributors with moderate to high risk at all sampling sites, whereas most other OPEs posed low risk to the aquatic environment. organophosphate esters GC-MS/MS Luoma Lake surface water sediment risk assessment Figures Figure 1 Figure 2 Figure 3 Figure 4 1 Introductions Organophosphate esters (OPEs), a kind of synthetic additive flame retardant, has good flame retardance and plasticity, and is widely used in a variety of products, such as textiles, electronic products and so on, involving all aspects of people's life (Cai et al., 2008 ; Wang et al., 2020 ). Since the polybrominated diphenyl ethers (PBDEs) was banned, as the substitutes of PBDEs, OPEs has been increasingly produced and used (Xing et al., 2018 ). Until 2016, the global consumption of OPEs reached up to 405,000 tons (Lu et al., 2020 ; Wang et al., 2013 ). As the largest consumer of OPEs, China accounts for a quarter of global OPEs consumption each year (Lin et al., 2022 ). OPEs are added into products as additive material with a non-chemical bands, resulting in their easy release from the product into environment (Lin et al., 2022 ; Pantelaki and Voutsa, 2019 ). With the extensive use of OPEs, a large quantities of OPES are released into the environment during production, use and disposal (Lv et al., 2022 ). Resent years, OPEs are frequently detected in various environment matrices, such as water (Ding et al., 2015 ; Shi et al., 2020 ; Zhu et al., 2022 ), soil (You et al., 2022 ). Sediment (Liao et al., 2020 ; Ye et al., 2021 ), air (Cao et al., 2019 ), organisms (Greaves and Letcher, 2017 ; Guo et al., 2017 ), and so on. Additional, OPEs have been detected in wildlife tissues (Pantelaki and Voutsa, 2020 ) and human serum (Hu et al., 2021 ; Ma et al., 2017 ). Toxicological studies reported that OPEs have a variety of toxic, such as neurotoxicity, carcinogenicity, endocrine disruption, developmental and reproductive toxicity, and genetic toxicity (Li et al., 2019 ). Some halogenated OPEs are restricted in many countries and organizations due to their dangerous properties (ECHA, 2018 ). Therefore, it have been attracted extensive attention that the occurrence and potential ecological effects of OPEs in the environment. Luoma Lake is one of the four freshwater lake with the total water surface area of 260 km (Xing et al., 2018 ). It is located in the northern of the Jiangsu province, where belonging to the three economic belts (coastal economic belt, along the Yangtze River Economic Belt, Longhai Economic Belt) cross radiation area. Luoma Lake is also the centralized public drinking water source in Jiangsu province. Lake water quality is very important to local public drinking water safety and regional ecological environment safety. As it is surrounded by multiple villages and factories, a large amount of domestic and industrial sewage flows directly or indirectly into Luoma Lake each year through tributaries, which are potential sources of pollution for OPEs (Dan et al., 2017 ; Yan et al., 2017 ). However, there are few study focusing on occurrence and distribution of OPEs in Luoma Lake. Hence, the pollution and ecological risk of OPEs in freshwater lakes have received increasing attention. Studies have found that TCEP, TCPP, and TDCPP have potential carcinogenic. In the study, 11 OPEs containing the above 3 were selected for analysis in water and sediment of Luoma Lake. The objectives of this study were to: 1) investigate the concentration level and distribution characters Luoma Lake, 2) investigate the trend growth of OPEs, and 3) evaluate the ecological risk according to the risk quotient (RQ). 2 Materials and methods 2.1 Chemical and reagents HPLC grade methanol, acetonitrile and ethyl acetate were purchased from Merck (Darmstadt, Germany). HPLC grade formic acid and ammonium hydroxide were purchased from Sigma Aldrich (St. Louis, MO, USA). Deionized water (18.2 MΩ) was prepared with Milli-Q unit (Millipore, USA). The SPE cartridges Oasis HLB 500 mg were acquired from Waters Technology co. LTD (Massachusetts, USA). Organophosphate esters standards: Tributyl phosphate (TBP, 99.0%), tris(1,3-dichloro-2-propyl)phosphate (TDCPP, 96.0%), triphenyl phosphate (TPhP, 98.0%), Tris(2-chloroethyl) phosphate (TCEP, 98.0%), Triethyl phosphate (TEP, 99.7%), trimethyl phosphate (TMP, 98.0%), tripropyl phosphate (TPrP, 99.0%), tri-iso-butyl phosphate (TiBP, 98.0%), tri-o-tolyl phosphate (ToTP, 99.0%) were purchased from AMPE Technology co. LTD (Jiangsu, China). Tri-m-tolyl phosphate (TmTP, 98.0%), tris (2-chloroisopropyl) phosphate (TCIPP, 99.0%), Tri-p-tolyl phosphate (TPTP, 98.0%) were purchased from J&K scientific (Beijing, China). The properties of 12 organophosphates were listed in Table S1 . 2.2 Sample collection The water and sediment samples from 21 sites around Luoma Lake were collected in August 2019(summer, wet season). As shown in Fig. 1 , 14 sites (LMH1-LMH14) were located at the Luoma Lake, 4 samples were obtained from Fangting River (F1, F2) and Yi River (Y1, Y2), two inflowing river, and 3 samples points were collected from outflowing river, Zhangshan Gate (X1) and the southern section of the Zhongyun River (Z1, Z2). Water samples were collected at an underwater depth of 0.5-1m, and stored in brown glass bottle. In addition, 6 sampling sites were chosen at LMH1, 3, 9, 10, 11 and 12 to collect sediment samples. The sediment samples were collected using a grab sampler at depth of 10 cm from the top, and stored in stainless steel boxes. All samples were taken back to laboratory in low-temperature (0–4℃) and dark conditions. The water samples were filtered through a glass fiber filters and stored at 4℃ before preparation. The sediment samples were air-dried at room temperature, then ground and sieved by a 60-mesh screen. 2.3 Sample preparation 500 mL water sample was measured accurately and conducted as the following method. The HLB cartridges were pre-activated with 5 mL of ethyl acetate, 5 mL of methanol and 5 mL of ultrapure water respectively. Then water samples passed through the cartridge at 3–5 mL/min. After sample loading, rinse the HLB cartridges with 10 mL of ultrapure water. Then the cartridges were dried at least 30 min under negative pressure. Finally, the analyses from the cartridges were eluted with 10mL of ethyl acetate. All eluents was collected, and dried with weak nitrogen concentrator. The residue was diluted and vortexed with 1.0 mL n-hexane. Then the extraction filtered through a 0.22 µm organic filter into amber vials, and stored at 4℃ until GC-MS/MS analysis. 5.0 g of air-dried sediments were extracted twice by ultrasonic extraction with 25 ml ethyl acetate for 30 min each time. Then, the samples were centrifuge at 6000 rpm for 5 min. the supernatant were collected into a flash. The extract was combined, and concentrated to dry. After which, the residue was redissolved to 1.0 mL n-hexane. Finally, the extraction filtered through a 0.22 µm organic filter into amber vials, and stored at 4℃ until GC-MS/MS analysis. 2.4 Instrumental analysis The GC-MS/MS system consisted of a Trace 1310 gas chromatograph coupled to a TSQ 9000 MS/MS triple quadrupole mass spectrometer (Thermo fisher) equipped with an electron impact ion source (EI). The separation of the analyte was mainly performed by a TG-5 capillary column (30m×0.25mm, 0.25µm, Thermo fisher, USA). The temperatures of sample inject, transfer line and ion source were 250℃, 280℃ and 300℃, respectively. The temperature program proceeded as followed: the GC oven was initially held at 50℃ for 2min, increased to 150℃ at a rate of 20℃/min and held 1 min, then to 250℃ at a rate of 25℃/min, and held 3 min, finally to 280℃ at a rate of 20℃/min, held for a final 3 min. Helium was the carrier gas with 1.2 ml/min flow rate. Quantitative analysis of 12 OPEs was performed by multiple reaction-monitoring mode (MRM), and the MS parameters are show in Table S1 . 2.5 Method validation In order to ensure accuracy, the glassware was selected to instead of plastic and rubber materials throughout the experiment. Before using, all glassware were heated at 450℃ for at least 4 h and then washed with acetone. A strict QA/QC protocol was used to guarantee quality of the data. The standard calibration curve contains six point calibration plots (10–500 µg/L), and the assessment was based on the obtained correlation coefficients (R 2 ༞0.990). The instrumental limits of detection (LOD) was defined as being three-fold of signal-to-noise (S/N), and the limit of quantification was ten- fold of signal-to-noise (S/N). The LODs rang of 12 OPEs was 0.0140-1.50 µg/L, and the LOQs ranges was 0.0462-4.59 µg/L. The recovery analysis was applied to determine the accuracy of the method. Recovery experiments were performed using black water and sediment as matrix spiked with 100 ng targets analyte. The spiked recoveries of 11 OPEs ranged from 62.9%-115% in water matrix, while only 54% recovery was achieved for TMP. The relative standard deviations (RSDs) in the spiked matrix samples ranged from 2.54%~8.71%. The spiked recoveries ranged from 42.6%-82.3% in sediment matrix, and the relative standard deviations (RSD) ranged from 3.65%~9.85% (Table S2). 3 Results and discussion 3.1 Distribution profile of OPE in Luoma Lake The concentrations of 12 OPEs detected in samples collected from Luoma Lake was shown in Fig. 2 . Except for TmTP not detected in any samples, 11 OPEs were identified in water and sediment samples to different degrees. Most of the OPEs appeared at all sampling sites. 8 target analysis were identified with detection frequencies 100% in water samples, excluding TMP (90.5%), ToTP (90.5%), and TPTP (42.9%). However, 11 OPEs were found in all sediment samples. The results are consistent with the previous studies (Cristale et al., 2013 ). The concentrations of 11 OPEs were higher in sediments than water samples, with mean concentrations of ∑ 11 OPEs of 2.76 µg/L and 36.8 µg/kg (dw) in water and sediment samples, respectively, which were consistent with their Log K ow values. The 11 OPEs was constituted by 4 alkyl-OPEs (TBP, TEP, TMP, TiBP, TPrP), 3 aryl-OPEs (TCEP, TCIPP, TDCPP) and 3 chlorinated OPEs (ToCP, TPCP, TPhP). The concentrations level of aryl-OPEs and chlorinated OPEs were higher than alkyl-OPEs in all samples (Fig. S1 ). 3.1.1 Concentration and distributions of OPEs in surfaces water sites The concentrations range, median, mean, detection frequencies (df) and ∑ 11 OPEs from surface water sites were shown in Table 1 . The concentration range of ∑ 11 OPEs from surface water was 1751–3967 ng/L, with an average value of 2764 ng/L. Low concentrations of TMP (average value of 24.6 ng/L) were detected in all surface water samples, which related to its variability. While TCEP (average value of 680 ng/L), TPhP (average value of 688 ng/L) and TCIPP (average value of 433 ng/L) were found to be of high concentration in most surface water samples. Similar results have been found in surface water in the Haihe River (Niu et al., 2019 ) and Pearl River (Shi et al., 2020 ), which demonstrated that human activity have a significant effect on the global environment. The TCEP and TPhP were detected as the most contamination species with maximum concentration of 1695ng/L and 1052 ng/L respectively, which was consistent with the previous studies (Xing et al., 2018 ). In this study, except for sites of LMH1, 4 and 13, the concentration of ∑ 11 OPEs in other sites was higher than 2000 ng/ L. However, the ∑ 11 OPEs concentration from 7 samples, including LMH2, 5, 7, 8, F1, F2 and Z1, exceeded 3000 ng/L, among the LMH8 concentration was as high as 3967 ng/L. the concentration of TMP, TEP, TCEP and TPhP were higher in this study than in previous that was detected in 2018, which needs to be further investigated Luoma Lake has two inflowing rivers, namely Fangting River and Yi River. The concentration of ∑ 11 OPEs detected at the Fangting River is higher than that in the Yi River, which indicated that Fangting River might contribute more contamination level then Yi River to the Luoma Lake. Similarly, considerably higher levels of ∑ 11 OPEs were detected in the west of Luoma River and Z1 than that in other areas. However, the ∑ 11 OPEs concentrations of samples near the outlet of Luoma River was generally low, which may be related to Log K ow value that OPEs were more easily enriched in sediment. 3.1.2 Concentration and distributions of OPEs in sediment 6 sediment samples were collected at sites LMH1, LMH3, LMH9, LMH10, LMH11 and LMH12 of Luoma River. Table 1 summarizes the concentrations range, median, mean, detection frequencies (df) and ∑ 11 OPEs from sediment. Within 12 OPEs targets, 11 OPEs were detected in all sediment samples. The concentrations of ∑ 11 OPEs in sediment ranged from 288 µg/kg to 513 µg/kg (dw), with the mean of 365 µg/kg (dw). It was noted in Fig. 3 that TPTP and TCIPP were identified as the dominant species with average value of 92.3 µg/kg and 79.3 µg/kg, respectively. However, researches showed that the dominant species and concentration of OPEs in sediment varied with sampling and regional feature. It was notable that the concentrations of TMP in sediment were low, consistent with the observation in surface water. The concentrations of ∑ 11 OPEs ranges from 288 µg/kg to 513 µg/kg, Compared with other available investigations on OPEs that in Luoma Lake, the results of the present study were slightly higher, that may be related to the differences in sampling time and depth. Among, the maximum concentrations of ∑ 11 OPEs was S10 with 513 µg/kg, followed by the S3 at inflowing river of Fangting River. It was similarly that 11 OPEs detected in S1 and S12. The lowest levels were found in S9 with 288 µg/kg (dw). The concentration of OPEs was comparable to the levels observed the River Arga (292 ng/g) and Pearl River Estuary (322 ng/L) (Pintado-Herrera et al., 2017 ). 3.2 Ecological risk assessment More and more attention has been paid to their effects on ecosystem due to the accumulation and potential toxicity in the environment. The RQ (risk quotient) value is a commonly used index for evaluating chemical potential risks (Shi et al., 2016 ; Yan et al., 2017 ). In this study, the ecological risk assessment to aquatic organisms was performed in 8 OPEs, except for TOCP, TPCP and TPrP due to their relevant toxicological missing data. And the ecological risk of 8 OPEs in Luoma Lake water were characterized by RQ value. The calculation formula is as follow: RQ = MEC/PNEC, where MEC is the measured environmental concentration, PNEC is the predicted no effect concentration (Xing et al., 2018 ). According to the default classification standard, it is generally considered that low risk with RQ < 0.1, moderate risk with 0.1 < RQ 1 (Dan et al., 2017 ; Yan et al., 2017 ). By collecting the median lethal (effect) concentration of different aquatic organisms at three trophic levels, the most sensitive biological toxicity data was selected and divided by assessment factors (AF) to obtain the corresponding PNEC, as shown in Table 2 . Figure 4 show the RQ range of target OPEs in Luoma Lake. The related toxicity data were obtained from the European Chemicals Agency database ( https://echa.europa.eu/brief-profile/-/briefprofile/100.003.744 ) and the USEPA ECOTOX database ( http://cfpob.epa.-gov/ecotox ). The RQ values of 6 OPEs (TCEP, TiBP, TBP, TCIPP, TMP, TPrP) were below 0.1, indicating no/low risk to aquatic organisms in Luoma Lake. However, the concentration of TPhP and TDCPP reveal a moderate risk to high risk for aquatic organisms at all sampling sites. The TPhP show a high potential effect on aquatic organisms at sampling sites LMH2-3, 5–10, and 10–14, X1, Y1-2, Z1, and moderate risk at sampling sites LMH1, 4, 11 and Z2. The concentration of TDCPP indicates high risk for aquatic organisms at sampling sites LMH3 and 8, and moderate risk to other sites. On the whole, it is further indicted that TPhP and TCIPP are the dominant pollution in Luoma Lake. 4 Conclusions This study investigated the concentration, distribution, and ecological risk of OPEs in Luoma Lake, Fangting River, Yi River, Zhangshan Gate and Xi River. All 11 OPEs were detested in surface water and sediment with total concentration varied from 1751 ng/L to 3967 ng/L in surface water, and from 288 µg/kg to 513 µg/kg (ww) in sediment. It was found that TCEP and TPhP were the dominated pollution in surface water, as well as TPTP and TCIPP were the most abundant OPEs in sediment. The contamination level was higher in the west of Luoma Lake. For the ecology risk assessment, it indicated most OPEs posed low risk to the aquatic environment, whereas the TPhP and TCIPP posed a potential medium to high risk threat to the aquatic environment of Luoma Lake. Hence, it is necessary to conduct regular monitoring of OPEs in Luoma Lake. Declarations Acknowledgements This study was financially supported by the Central Scientific Research Projects for Public Welfare Research Institutes (ZX2023QT003) and Provincial Ecological Environment Science Program of Jiangsu (2022015). Competing interests Non-financial interests to disclose Author contribution All authors have contributed to the study conpetion anf design.on of the work. Mengyuan Liang: Formal analysis, writing—originaldraft. Wen Gu: Data curation, Writing—review and editing. Weilong Xing: Supervision, investigation, Yinying Cai and Shuai Sun: Methodology, visualization. Zhen Wang and Deling Fan: Writing—review and editing. Bing Zhang: Investigation and data curation. 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Yan, Z., et al., 2017. Bisphenol analogues in surface water and sediment from the shallow Chinese freshwater lakes: Occurrence, distribution, source apportionment, and ecological and human health risk. Chemosphere. 184 , 318-328. Ye, L., et al., 2021. Establishment of a Target, Suspect, and Functional Group-Dependent Screening Strategy for Organophosphate Esters (OPEs): "Into the Unknown" of OPEs in the Sediment of Taihu Lake, China. Environ Sci Technol. 55 , 5836-5847. You, J., et al., 2022. Occurrence, potential sources and risks of organophosphate esters in the high-elevation region, Tibet, China. Sci Total Environ. 806 , 151348. Zhu, K., et al., 2022. Occurrence, distribution and risk assessment of organophosphate esters (OPEs) in water sources from Northeast to Southeast China. Environ Pollut. 307 , 119461. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-3348402","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":240200148,"identity":"fec63c3e-1fbf-40bc-acd6-fef8004c276c","order_by":0,"name":"Mengyuan Liang","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA+klEQVRIiWNgGAWjYBACPmYUbgUDD0EtbKhazhCjBYXH2EaEw9jYmZ89/JpjkycfkWP4uXDeHRl+/gOMjyt+4XMYm7mx7La0YsMbOcbSM7c945GckcBseLYPnxYGM2nJbYcTN87IMZDm3XaYx+AGA5tkYw8+LezfgFr+g7QY/+adc5jH/vwBQlp4zCQ/bjuQOF8ix0yatwFoC0MCm2TDD7xayqQZtyUnbuB5VmbNc+wwj8SNxGbDxgbcWvj5j2+T/LnNLnF+e/Lm2zw1h+35+w8ffNjwB7cWEGAGRZ/BhQQYn7GBYAQxghwu338AWYyALaNgFIyCUTCiAAC2s0zjiMS1NgAAAABJRU5ErkJggg==","orcid":"","institution":"MEE Nanjing Institute of Environmental Sciences","correspondingAuthor":true,"submittingAuthor":false,"prefix":"","firstName":"Mengyuan","middleName":"","lastName":"Liang","suffix":""},{"id":240200149,"identity":"5ef8c714-7cbf-4d00-9e43-d390facdeb7a","order_by":1,"name":"Wen Gu","email":"","orcid":"","institution":"MEE Nanjing Institute of Environmental Sciences","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Wen","middleName":"","lastName":"Gu","suffix":""},{"id":240200150,"identity":"d089457d-2455-4221-adca-90a97119bc44","order_by":2,"name":"Zhen Wang","email":"","orcid":"","institution":"MEE Nanjing Institute of Environmental Sciences","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Zhen","middleName":"","lastName":"Wang","suffix":""},{"id":240200151,"identity":"93011b70-e0fc-43d2-806d-99e1b922165d","order_by":3,"name":"Weilong Xing","email":"","orcid":"","institution":"MEE Nanjing Institute of Environmental Sciences","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Weilong","middleName":"","lastName":"Xing","suffix":""},{"id":240200152,"identity":"b243b155-f7db-43ca-b1f4-b9b2024f03f2","order_by":4,"name":"Yinying Cai","email":"","orcid":"","institution":"MEE Nanjing Institute of Environmental Sciences","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Yinying","middleName":"","lastName":"Cai","suffix":""},{"id":240200153,"identity":"eb24fe6a-8504-42ea-b6ec-17a2c9aef867","order_by":5,"name":"Deling Fan","email":"","orcid":"","institution":"MEE Nanjing Institute of Environmental Sciences","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Deling","middleName":"","lastName":"Fan","suffix":""},{"id":240200154,"identity":"22fdcb49-568f-41f0-b489-b90741bdfd83","order_by":6,"name":"Shuai Sun","email":"","orcid":"","institution":"MEE Nanjing Institute of Environmental Sciences","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Shuai","middleName":"","lastName":"Sun","suffix":""},{"id":240200155,"identity":"17ba31a1-6eff-4e7c-af2b-4efd78278c7a","order_by":7,"name":"Bing Zhang","email":"","orcid":"","institution":"MEE Nanjing Institute of Environmental Sciences","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Bing","middleName":"","lastName":"Zhang","suffix":""},{"id":240200156,"identity":"97b70989-6fa6-4066-8add-877e0919e842","order_by":8,"name":"Lei Wang","email":"","orcid":"","institution":"MEE Nanjing Institute of Environmental Sciences","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Lei","middleName":"","lastName":"Wang","suffix":""}],"badges":[],"createdAt":"2023-09-12 11:56:16","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-3348402/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-3348402/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":44813634,"identity":"591b5cfa-c366-4b29-a50d-0df8a5cb45e0","added_by":"auto","created_at":"2023-10-17 22:20:27","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":114844,"visible":true,"origin":"","legend":"\u003cp\u003eLocations and distribution of sampling sites. (F: Fangting River; Y: Yi River; LMH: Luoma Lake; Z: Zhangyun River; X: Zhangsan Gate.).\u003c/p\u003e","description":"","filename":"floatimage1.png","url":"https://assets-eu.researchsquare.com/files/rs-3348402/v1/e705ef946b4ee98a7a113a41.png"},{"id":44812760,"identity":"dec77d51-a03f-4d7e-955f-7d295c4beb71","added_by":"auto","created_at":"2023-10-17 22:12:27","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":327073,"visible":true,"origin":"","legend":"\u003cp\u003eConcentration and distribution of ∑\u003csub\u003e11\u003c/sub\u003e OPEs in surface water from Luoma Lake. (\u003cstrong\u003eA\u003c/strong\u003e) distribution of ∑\u003csub\u003e11\u003c/sub\u003e OPEs in each surface water, (\u003cstrong\u003eB\u003c/strong\u003e) relative abundance of target OPEs in each surface water.\u003c/p\u003e","description":"","filename":"floatimage2.png","url":"https://assets-eu.researchsquare.com/files/rs-3348402/v1/19f171bfa38ae00527d5ac37.png"},{"id":44812763,"identity":"c3bd7e47-dc78-4623-886e-56a24a1a0ef9","added_by":"auto","created_at":"2023-10-17 22:12:27","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":119975,"visible":true,"origin":"","legend":"\u003cp\u003eConcentration and distribution of ∑\u003csub\u003e11\u003c/sub\u003e OPEs in sediment samples from Luoma Lake. (\u003cstrong\u003eA\u003c/strong\u003e) distribution of ∑\u003csub\u003e11\u003c/sub\u003e OPEs in each sediment samples, (\u003cstrong\u003eB\u003c/strong\u003e) relative abundance of target OPEs in each sediment samples.\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-3348402/v1/7d2064f3bd395ed5e0685e69.png"},{"id":44812762,"identity":"3e7d689c-c867-4258-80c8-f345a933ffba","added_by":"auto","created_at":"2023-10-17 22:12:27","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":143094,"visible":true,"origin":"","legend":"\u003cp\u003eThe risk assessment of OPEs in surface water of Luoma Lake.\u003c/p\u003e","description":"","filename":"floatimage4.png","url":"https://assets-eu.researchsquare.com/files/rs-3348402/v1/b870ee74ca553eeab3ee8e38.png"},{"id":46506821,"identity":"c454fdbf-0205-4881-841b-9df27a1a4601","added_by":"auto","created_at":"2023-11-15 19:34:00","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":683950,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-3348402/v1/487e469c-01f3-40b3-a837-d22718c68818.pdf"},{"id":44812765,"identity":"fdfd2f03-1a54-46e0-af04-baf044c8316f","added_by":"auto","created_at":"2023-10-17 22:12:27","extension":"docx","order_by":6,"title":"","display":"","copyAsset":false,"role":"supplement","size":221024,"visible":true,"origin":"","legend":"","description":"","filename":"supplementaryinformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-3348402/v1/b2767d1aee45cdaa3b53225f.docx"}],"financialInterests":"","formattedTitle":"Occurrence and ecological risk assessment for organophosphate esters in Luoma Lake","fulltext":[{"header":"1 Introductions","content":"\u003cp\u003eOrganophosphate esters (OPEs), a kind of synthetic additive flame retardant, has good flame retardance and plasticity, and is widely used in a variety of products, such as textiles, electronic products and so on, involving all aspects of people's life (Cai et al., \u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e2008\u003c/span\u003e; Wang et al., \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). Since the polybrominated diphenyl ethers (PBDEs) was banned, as the substitutes of PBDEs, OPEs has been increasingly produced and used (Xing et al., \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). Until 2016, the global consumption of OPEs reached up to 405,000 tons (Lu et al., \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e2020\u003c/span\u003e; Wang et al., \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e2013\u003c/span\u003e). As the largest consumer of OPEs, China accounts for a quarter of global OPEs consumption each year (Lin et al., \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). OPEs are added into products as additive material with a non-chemical bands, resulting in their easy release from the product into environment (Lin et al., \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2022\u003c/span\u003e; Pantelaki and Voutsa, \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). With the extensive use of OPEs, a large quantities of OPES are released into the environment during production, use and disposal (Lv et al., \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). Resent years, OPEs are frequently detected in various environment matrices, such as water (Ding et al., \u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e2015\u003c/span\u003e; Shi et al., \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e2020\u003c/span\u003e; Zhu et al., \u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e2022\u003c/span\u003e), soil (You et al., \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). Sediment (Liao et al., \u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e2020\u003c/span\u003e; Ye et al., \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e2021\u003c/span\u003e), air (Cao et al., \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2019\u003c/span\u003e), organisms (Greaves and Letcher, \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; Guo et al., \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e2017\u003c/span\u003e), and so on. Additional, OPEs have been detected in wildlife tissues (Pantelaki and Voutsa, \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e2020\u003c/span\u003e) and human serum (Hu et al., \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e2021\u003c/span\u003e; Ma et al., \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). Toxicological studies reported that OPEs have a variety of toxic, such as neurotoxicity, carcinogenicity, endocrine disruption, developmental and reproductive toxicity, and genetic toxicity (Li et al., \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). Some halogenated OPEs are restricted in many countries and organizations due to their dangerous properties (ECHA, \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). Therefore, it have been attracted extensive attention that the occurrence and potential ecological effects of OPEs in the environment.\u003c/p\u003e \u003cp\u003eLuoma Lake is one of the four freshwater lake with the total water surface area of 260 km (Xing et al., \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). It is located in the northern of the Jiangsu province, where belonging to the three economic belts (coastal economic belt, along the Yangtze River Economic Belt, Longhai Economic Belt) cross radiation area. Luoma Lake is also the centralized public drinking water source in Jiangsu province. Lake water quality is very important to local public drinking water safety and regional ecological environment safety. As it is surrounded by multiple villages and factories, a large amount of domestic and industrial sewage flows directly or indirectly into Luoma Lake each year through tributaries, which are potential sources of pollution for OPEs (Dan et al., \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; Yan et al., \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). However, there are few study focusing on occurrence and distribution of OPEs in Luoma Lake.\u003c/p\u003e \u003cp\u003eHence, the pollution and ecological risk of OPEs in freshwater lakes have received increasing attention. Studies have found that TCEP, TCPP, and TDCPP have potential carcinogenic. In the study, 11 OPEs containing the above 3 were selected for analysis in water and sediment of Luoma Lake. The objectives of this study were to: 1) investigate the concentration level and distribution characters Luoma Lake, 2) investigate the trend growth of OPEs, and 3) evaluate the ecological risk according to the risk quotient (RQ).\u003c/p\u003e"},{"header":"2 Materials and methods","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1 Chemical and reagents\u003c/h2\u003e \u003cp\u003eHPLC grade methanol, acetonitrile and ethyl acetate were purchased from Merck (Darmstadt, Germany). HPLC grade formic acid and ammonium hydroxide were purchased from Sigma Aldrich (St. Louis, MO, USA). Deionized water (18.2 MΩ) was prepared with Milli-Q unit (Millipore, USA). The SPE cartridges Oasis HLB 500 mg were acquired from Waters Technology co. LTD (Massachusetts, USA).\u003c/p\u003e \u003cp\u003eOrganophosphate esters standards: Tributyl phosphate (TBP, 99.0%), tris(1,3-dichloro-2-propyl)phosphate (TDCPP, 96.0%), triphenyl phosphate (TPhP, 98.0%), Tris(2-chloroethyl) phosphate (TCEP, 98.0%), Triethyl phosphate (TEP, 99.7%), trimethyl phosphate (TMP, 98.0%), tripropyl phosphate (TPrP, 99.0%), tri-iso-butyl phosphate (TiBP, 98.0%), tri-o-tolyl phosphate (ToTP, 99.0%) were purchased from AMPE Technology co. LTD (Jiangsu, China). Tri-m-tolyl phosphate (TmTP, 98.0%), tris (2-chloroisopropyl) phosphate (TCIPP, 99.0%), Tri-p-tolyl phosphate (TPTP, 98.0%) were purchased from J\u0026amp;K scientific (Beijing, China). The properties of 12 organophosphates were listed in Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2 Sample collection\u003c/h2\u003e \u003cp\u003eThe water and sediment samples from 21 sites around Luoma Lake were collected in August 2019(summer, wet season). As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e1\u003c/span\u003e, 14 sites (LMH1-LMH14) were located at the Luoma Lake, 4 samples were obtained from Fangting River (F1, F2) and Yi River (Y1, Y2), two inflowing river, and 3 samples points were collected from outflowing river, Zhangshan Gate (X1) and the southern section of the Zhongyun River (Z1, Z2). Water samples were collected at an underwater depth of 0.5-1m, and stored in brown glass bottle. In addition, 6 sampling sites were chosen at LMH1, 3, 9, 10, 11 and 12 to collect sediment samples. The sediment samples were collected using a grab sampler at depth of 10 cm from the top, and stored in stainless steel boxes. All samples were taken back to laboratory in low-temperature (0\u0026ndash;4℃) and dark conditions. The water samples were filtered through a glass fiber filters and stored at 4℃ before preparation. The sediment samples were air-dried at room temperature, then ground and sieved by a 60-mesh screen.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3 Sample preparation\u003c/h2\u003e \u003cp\u003e500 mL water sample was measured accurately and conducted as the following method. The HLB cartridges were pre-activated with 5 mL of ethyl acetate, 5 mL of methanol and 5 mL of ultrapure water respectively. Then water samples passed through the cartridge at 3\u0026ndash;5 mL/min. After sample loading, rinse the HLB cartridges with 10 mL of ultrapure water. Then the cartridges were dried at least 30 min under negative pressure. Finally, the analyses from the cartridges were eluted with 10mL of ethyl acetate. All eluents was collected, and dried with weak nitrogen concentrator. The residue was diluted and vortexed with 1.0 mL n-hexane. Then the extraction filtered through a 0.22 \u0026micro;m organic filter into amber vials, and stored at 4℃ until GC-MS/MS analysis.\u003c/p\u003e \u003cp\u003e5.0 g of air-dried sediments were extracted twice by ultrasonic extraction with 25 ml ethyl acetate for 30 min each time. Then, the samples were centrifuge at 6000 rpm for 5 min. the supernatant were collected into a flash. The extract was combined, and concentrated to dry. After which, the residue was redissolved to 1.0 mL n-hexane. Finally, the extraction filtered through a 0.22 \u0026micro;m organic filter into amber vials, and stored at 4℃ until GC-MS/MS analysis.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e2.4 Instrumental analysis\u003c/h2\u003e \u003cp\u003eThe GC-MS/MS system consisted of a Trace 1310 gas chromatograph coupled to a TSQ 9000 MS/MS triple quadrupole mass spectrometer (Thermo fisher) equipped with an electron impact ion source (EI). The separation of the analyte was mainly performed by a TG-5 capillary column (30m\u0026times;0.25mm, 0.25\u0026micro;m, Thermo fisher, USA). The temperatures of sample inject, transfer line and ion source were 250℃, 280℃ and 300℃, respectively. The temperature program proceeded as followed: the GC oven was initially held at 50℃ for 2min, increased to 150℃ at a rate of 20℃/min and held 1 min, then to 250℃ at a rate of 25℃/min, and held 3 min, finally to 280℃ at a rate of 20℃/min, held for a final 3 min. Helium was the carrier gas with 1.2 ml/min flow rate. Quantitative analysis of 12 OPEs was performed by multiple reaction-monitoring mode (MRM), and the MS parameters are show in Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003e2.5 Method validation\u003c/h2\u003e \u003cp\u003eIn order to ensure accuracy, the glassware was selected to instead of plastic and rubber materials throughout the experiment. Before using, all glassware were heated at 450℃ for at least 4 h and then washed with acetone. A strict QA/QC protocol was used to guarantee quality of the data. The standard calibration curve contains six point calibration plots (10\u0026ndash;500 \u0026micro;g/L), and the assessment was based on the obtained correlation coefficients (R\u003csup\u003e2\u003c/sup\u003e༞0.990). The instrumental limits of detection (LOD) was defined as being three-fold of signal-to-noise (S/N), and the limit of quantification was ten- fold of signal-to-noise (S/N). The LODs rang of 12 OPEs was 0.0140-1.50 \u0026micro;g/L, and the LOQs ranges was 0.0462-4.59 \u0026micro;g/L. The recovery analysis was applied to determine the accuracy of the method. Recovery experiments were performed using black water and sediment as matrix spiked with 100 ng targets analyte. The spiked recoveries of 11 OPEs ranged from 62.9%-115% in water matrix, while only 54% recovery was achieved for TMP. The relative standard deviations (RSDs) in the spiked matrix samples ranged from 2.54%~8.71%. The spiked recoveries ranged from 42.6%-82.3% in sediment matrix, and the relative standard deviations (RSD) ranged from 3.65%~9.85% (Table S2).\u003c/p\u003e \u003c/div\u003e"},{"header":"3 Results and discussion","content":"\u003cdiv id=\"Sec9\" class=\"Section2\"\u003e \u003ch2\u003e3.1 Distribution profile of OPE in Luoma Lake\u003c/h2\u003e \u003cp\u003eThe concentrations of 12 OPEs detected in samples collected from Luoma Lake was shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e2\u003c/span\u003e. Except for TmTP not detected in any samples, 11 OPEs were identified in water and sediment samples to different degrees. Most of the OPEs appeared at all sampling sites. 8 target analysis were identified with detection frequencies 100% in water samples, excluding TMP (90.5%), ToTP (90.5%), and TPTP (42.9%). However, 11 OPEs were found in all sediment samples. The results are consistent with the previous studies (Cristale et al., \u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e2013\u003c/span\u003e). The concentrations of 11 OPEs were higher in sediments than water samples, with mean concentrations of \u0026sum;\u003csub\u003e11\u003c/sub\u003e OPEs of 2.76 \u0026micro;g/L and 36.8 \u0026micro;g/kg (dw) in water and sediment samples, respectively, which were consistent with their Log \u003cem\u003eK\u003c/em\u003e\u003csub\u003e\u003cem\u003eow\u003c/em\u003e\u003c/sub\u003e values. The 11 OPEs was constituted by 4 alkyl-OPEs (TBP, TEP, TMP, TiBP, TPrP), 3 aryl-OPEs (TCEP, TCIPP, TDCPP) and 3 chlorinated OPEs (ToCP, TPCP, TPhP). The concentrations level of aryl-OPEs and chlorinated OPEs were higher than alkyl-OPEs in all samples (Fig. \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e).\u003c/p\u003e \u003cdiv id=\"Sec10\" class=\"Section3\"\u003e \u003ch2\u003e3.1.1 Concentration and distributions of OPEs in surfaces water sites\u003c/h2\u003e \u003cp\u003eThe concentrations range, median, mean, detection frequencies (df) and \u0026sum;\u003csub\u003e11\u003c/sub\u003e OPEs from surface water sites were shown in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. The concentration range of \u0026sum;\u003csub\u003e11\u003c/sub\u003e OPEs from surface water was 1751\u0026ndash;3967 ng/L, with an average value of 2764 ng/L. Low concentrations of TMP (average value of 24.6 ng/L) were detected in all surface water samples, which related to its variability. While TCEP (average value of 680 ng/L), TPhP (average value of 688 ng/L) and TCIPP (average value of 433 ng/L) were found to be of high concentration in most surface water samples. Similar results have been found in surface water in the Haihe River (Niu et al., \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e2019\u003c/span\u003e) and Pearl River (Shi et al., \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e2020\u003c/span\u003e), which demonstrated that human activity have a significant effect on the global environment. The TCEP and TPhP were detected as the most contamination species with maximum concentration of 1695ng/L and 1052 ng/L respectively, which was consistent with the previous studies (Xing et al., \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e2018\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eIn this study, except for sites of LMH1, 4 and 13, the concentration of \u0026sum;\u003csub\u003e11\u003c/sub\u003e OPEs in other sites was higher than 2000 ng/ L. However, the \u0026sum;\u003csub\u003e11\u003c/sub\u003e OPEs concentration from 7 samples, including LMH2, 5, 7, 8, F1, F2 and Z1, exceeded 3000 ng/L, among the LMH8 concentration was as high as 3967 ng/L. the concentration of TMP, TEP, TCEP and TPhP were higher in this study than in previous that was detected in 2018, which needs to be further investigated Luoma Lake has two inflowing rivers, namely Fangting River and Yi River. The concentration of \u0026sum;\u003csub\u003e11\u003c/sub\u003e OPEs detected at the Fangting River is higher than that in the Yi River, which indicated that Fangting River might contribute more contamination level then Yi River to the Luoma Lake. Similarly, considerably higher levels of \u0026sum;\u003csub\u003e11\u003c/sub\u003e OPEs were detected in the west of Luoma River and Z1 than that in other areas. However, the \u0026sum;\u003csub\u003e11\u003c/sub\u003e OPEs concentrations of samples near the outlet of Luoma River was generally low, which may be related to Log \u003cem\u003eK\u003c/em\u003e\u003csub\u003e\u003cem\u003eow\u003c/em\u003e\u003c/sub\u003e value that OPEs were more easily enriched in sediment.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec11\" class=\"Section3\"\u003e \u003ch2\u003e3.1.2 Concentration and distributions of OPEs in sediment\u003c/h2\u003e \u003cp\u003e6 sediment samples were collected at sites LMH1, LMH3, LMH9, LMH10, LMH11 and LMH12 of Luoma River. Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e summarizes the concentrations range, median, mean, detection frequencies (df) and \u0026sum;\u003csub\u003e11\u003c/sub\u003eOPEs from sediment. Within 12 OPEs targets, 11 OPEs were detected in all sediment samples. The concentrations of \u0026sum;\u003csub\u003e11\u003c/sub\u003e OPEs in sediment ranged from 288 \u0026micro;g/kg to 513 \u0026micro;g/kg (dw), with the mean of 365 \u0026micro;g/kg (dw). It was noted in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e3\u003c/span\u003e that TPTP and TCIPP were identified as the dominant species with average value of 92.3 \u0026micro;g/kg and 79.3 \u0026micro;g/kg, respectively. However, researches showed that the dominant species and concentration of OPEs in sediment varied with sampling and regional feature. It was notable that the concentrations of TMP in sediment were low, consistent with the observation in surface water.\u003c/p\u003e \u003cp\u003eThe concentrations of \u0026sum;\u003csub\u003e11\u003c/sub\u003e OPEs ranges from 288 \u0026micro;g/kg to 513 \u0026micro;g/kg, Compared with other available investigations on OPEs that in Luoma Lake, the results of the present study were slightly higher, that may be related to the differences in sampling time and depth. Among, the maximum concentrations of \u0026sum;\u003csub\u003e11\u003c/sub\u003e OPEs was S10 with 513 \u0026micro;g/kg, followed by the S3 at inflowing river of Fangting River. It was similarly that 11 OPEs detected in S1 and S12. The lowest levels were found in S9 with 288 \u0026micro;g/kg (dw). The concentration of OPEs was comparable to the levels observed the River Arga (292 ng/g) and Pearl River Estuary (322 ng/L) (Pintado-Herrera et al., \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e2017\u003c/span\u003e).\u003c/p\u003e \u003c/div\u003e \u003c/div\u003e \u003cdiv id=\"Sec12\" class=\"Section2\"\u003e \u003ch2\u003e3.2 Ecological risk assessment\u003c/h2\u003e \u003cp\u003eMore and more attention has been paid to their effects on ecosystem due to the accumulation and potential toxicity in the environment. The RQ (risk quotient) value is a commonly used index for evaluating chemical potential risks (Shi et al., \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e2016\u003c/span\u003e; Yan et al., \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). In this study, the ecological risk assessment to aquatic organisms was performed in 8 OPEs, except for TOCP, TPCP and TPrP due to their relevant toxicological missing data. And the ecological risk of 8 OPEs in Luoma Lake water were characterized by RQ value. The calculation formula is as follow: RQ\u0026thinsp;=\u0026thinsp;MEC/PNEC, where MEC is the measured environmental concentration, PNEC is the predicted no effect concentration (Xing et al., \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). According to the default classification standard, it is generally considered that low risk with RQ\u0026thinsp;\u0026lt;\u0026thinsp;0.1, moderate risk with 0.1\u0026thinsp;\u0026lt;\u0026thinsp;RQ\u0026thinsp;\u0026lt;\u0026thinsp;1, and high risk with RQ\u0026thinsp;\u0026gt;\u0026thinsp;1 (Dan et al., \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; Yan et al., \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). By collecting the median lethal (effect) concentration of different aquatic organisms at three trophic levels, the most sensitive biological toxicity data was selected and divided by assessment factors (AF) to obtain the corresponding PNEC, as shown in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e.\u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e4\u003c/span\u003e show the RQ range of target OPEs in Luoma Lake. The related toxicity data were obtained from the European Chemicals Agency database (\u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://echa.europa.eu/brief-profile/-/briefprofile/100.003.744\u003c/span\u003e\u003cspan address=\"https://echa.europa.eu/brief-profile/-/briefprofile/100.003.744\" targettype=\"URL\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e) and the USEPA ECOTOX database (\u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttp://cfpob.epa.-gov/ecotox\u003c/span\u003e\u003cspan address=\"http://cfpob.epa.-gov/ecotox\" targettype=\"URL\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e). The RQ values of 6 OPEs (TCEP, TiBP, TBP, TCIPP, TMP, TPrP) were below 0.1, indicating no/low risk to aquatic organisms in Luoma Lake. However, the concentration of TPhP and TDCPP reveal a moderate risk to high risk for aquatic organisms at all sampling sites. The TPhP show a high potential effect on aquatic organisms at sampling sites LMH2-3, 5\u0026ndash;10, and 10\u0026ndash;14, X1, Y1-2, Z1, and moderate risk at sampling sites LMH1, 4, 11 and Z2. The concentration of TDCPP indicates high risk for aquatic organisms at sampling sites LMH3 and 8, and moderate risk to other sites. On the whole, it is further indicted that TPhP and TCIPP are the dominant pollution in Luoma Lake.\u003c/p\u003e \u003c/div\u003e"},{"header":"4 Conclusions","content":"\u003cp\u003eThis study investigated the concentration, distribution, and ecological risk of OPEs in Luoma Lake, Fangting River, Yi River, Zhangshan Gate and Xi River. All 11 OPEs were detested in surface water and sediment with total concentration varied from 1751 ng/L to 3967 ng/L in surface water, and from 288 \u0026micro;g/kg to 513 \u0026micro;g/kg (ww) in sediment. It was found that TCEP and TPhP were the dominated pollution in surface water, as well as TPTP and TCIPP were the most abundant OPEs in sediment. The contamination level was higher in the west of Luoma Lake. For the ecology risk assessment, it indicated most OPEs posed low risk to the aquatic environment, whereas the TPhP and TCIPP posed a potential medium to high risk threat to the aquatic environment of Luoma Lake. Hence, it is necessary to conduct regular monitoring of OPEs in Luoma Lake.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis study was financially supported by the Central Scientific Research Projects for Public Welfare Research Institutes (ZX2023QT003) and Provincial Ecological Environment Science Program of Jiangsu (2022015).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting interests\u003c/strong\u003e Non-financial interests to disclose\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contribution\u003c/strong\u003e\u0026nbsp; \u0026nbsp;All authors have contributed to the study conpetion anf design.on of the work. Mengyuan Liang: Formal analysis, writing\u0026mdash;originaldraft. Wen Gu: Data curation, Writing\u0026mdash;review and editing. Weilong Xing: Supervision, investigation, Yinying Cai and Shuai Sun: Methodology, visualization. Zhen Wang and Deling Fan: Writing\u0026mdash;review and editing. Bing Zhang: Investigation and data curation. Lei Wang: Project administration, writing\u0026mdash;review and editing, funding acquisition.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eEthical approval\u003c/strong\u003e Not applicable.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConsent to Participate\u003c/strong\u003e Not applicable.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConsent to Publish\u0026nbsp;\u003c/strong\u003eAll authors have approved publication.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eCai, Q. Y., et al., 2008. The status of soil contamination by semivolatile organic chemicals (SVOCs) in China: a review. Sci Total Environ. 389\u003cstrong\u003e,\u003c/strong\u003e 209-24.\u003c/li\u003e\n\u003cli\u003eCao, D., et al., 2019. Presence and human exposure assessment of organophosphate flame retardants (OPEs) in indoor dust and air in Beijing, China. 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Environ Pollut. 307\u003cstrong\u003e,\u003c/strong\u003e 119461.\u003c/li\u003e\n\u003c/ol\u003e"},{"header":"Tables","content":"\u003cp\u003e\u003cimg src=\"https://myfiles.space/user_files/122228_c8a1650c59388082/122228_custom_files/img1697580072.png\"\u003e\u003c/p\u003e\n\u003cp\u003e\u003cimg src=\"https://myfiles.space/user_files/122228_c8a1650c59388082/122228_custom_files/img1697580088.png\"\u003e\u003cbr\u003e\u003c/p\u003e\n"}],"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":"organophosphate esters, GC-MS/MS, Luoma Lake, surface water, sediment, risk assessment","lastPublishedDoi":"10.21203/rs.3.rs-3348402/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-3348402/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eOrganophosphate esters (OPEs) as plasticizers and flame retardants are ubiquitous in various environments. The concentration, distribution and risk of OPEs has caused global concern in recent years. The Luoma Lake is one of drinking water source and four major freshwater in the Jiangsu provinces. The aim of this study is to investigate the pollution level of 11 OPEs in surface water and sediment of Luoma Lake within inflowing and outflowing river. The total concentration of 11 OPEs in the water and sediment were 1751\u0026ndash;3967 ng/L and 288\u0026ndash;513 \u0026micro;g/kg (ww), respectively. The concentration of 11 OPEs in Fangting River were higher than that in Yi River. Tris (2-chloroethyl) phosphate (TCEP) and triphenyl phosphate (TPhP) were the most abundant in the surface water. Tri-p-tolyl phosphate (TPTP) and Tris (1-chloro-2-propyl) phosphate (TCIPP) were the most abundant in the sediment. From the ecological risk, TPhP and TCIPP were the most significant contributors with moderate to high risk at all sampling sites, whereas most other OPEs posed low risk to the aquatic environment.\u003c/p\u003e","manuscriptTitle":"Occurrence and ecological risk assessment for organophosphate esters in Luoma Lake","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2023-10-17 22:12:22","doi":"10.21203/rs.3.rs-3348402/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":"cff49cdf-c0bb-4148-884c-c03c8d02b871","owner":[],"postedDate":"October 17th, 2023","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2023-11-15T19:25:53+00:00","versionOfRecord":[],"versionCreatedAt":"2023-10-17 22:12:22","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-3348402","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-3348402","identity":"rs-3348402","version":["v1"]},"buildId":"7rjqhiLT3MXkJMwkYKINL","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}