Skip to main content
SpringerLink
Log in

Occurrence, distribution, and ecological risk of organophosphorus flame retardants and their degradation products in water and upper sediment of two urban rivers in Shenzhen, China

  • Research Article
  • Published:
Environmental Science and Pollution Research Aims and scope Submit manuscript

Abstract

Organophosphorus flame retardants (OPFRs) are widely used in various industrial manufacturing processes; thus, their environmental impact in agglomerated industrial areas is of great concern. In this study, seventeen kinds of OPFRs and five kinds of organophosphate diesters (Di-OPs) in water and upper sediment samples from two urban rivers in the agglomerated industrial area of Shenzhen city, China, were investigated. The results showed that the total concentrations of detectable OPFRs ranged from 3438.83 to 12,838.87 ng/L with an average of 6494.94 ng/L in water samples and from 47.16 to 524.46 ng/g (dry weight, dw) with an average of 181.48 ng/g dw in sediment. The values were higher than those in other rivers worldwide. Tris(2-chloroethyl) phosphate (TCEP) is the predominant OPFRs in water and upper sediment, up to 10,664.23 ng/L in water and 414.12 ng/g dw in sediment. The total concentration of OPFRs of sediment samples in the Maozhou River was around twice as high as in the Guanlan River. The results indicated that the level of OPFRs was associated with the industrial activity intensity. Di-OPs exhibited lower concentrations than their parent compounds, and can be attributed to the degradation/metabolism of their parent compounds in the river. The sediment–water partition of OPFRs is significantly correlated with their log Kow values. Risk assessment revealed moderate ecological risks posed by OPFRs in water to aquatic organisms. The present study revealed the pollution status of OPFRs in rivers from agglomerated industrial and residential areas.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

Data availability

It is not applicable.

References

  • Arukwe A, Carteny CC, Möder M, Bonini A, Maubach MA, Eggen T (2016) Differential modulation of neuro and interrenal steroidogenesis of juvenile salmon by the organophosphates tris(2-butoxyethyl) and tris(2-cloroethyl) phosphate. Environ Res 148:63–71

    Article  CAS  Google Scholar 

  • Bekele TG, Zhao H, Wang Q, Chen J (2019) Bioaccumulation and trophic transfer of emerging organophosphate flame retardants in the marine food webs of Laizhou Bay. North China Environ Sci Technol 53(22):13417–13426

    Article  CAS  Google Scholar 

  • Cao S, Zeng X, Song H, Li H, Yu Z, Sheng G, Fu J (2012) Levels and distributions of organophosphate flame retardants and plasticizers in sediment from Taihu Lake. China Environ Toxicol Chem 31(7):1478–1484

    Article  CAS  Google Scholar 

  • Chen Y, Fang J, Ren L, Fan R, Zhang J, Liu G, Lu S (2018) Urinary metabolites of organophosphate esters in children in South China: concentrations, profiles and estimated daily intake. Environ Pollut 235:358–364

    Article  CAS  Google Scholar 

  • Chen Y, Jiang L, Lu S, Kang L, Luo X, Liu G, Yu Y (2019) Organophosphate ester and phthalate ester metabolites in urine from primiparas in Shenzhen, China: implications for health risks. Environ Pollut 247:944–952

    Article  CAS  Google Scholar 

  • Chokwe TB, Okonkwo JO (2019) Occurrence, distribution and ecological risk assessment of organophosphorus flame retardants and plasticizers in sediment samples along the Vaal River catchment, South Africa. Emerging Contaminants 5:173–178

    Article  Google Scholar 

  • Cristale J, Vázquez AG, Barata C, Lacorte S (2013a) Priority and emerging flame retardants in rivers: occurrence in water and sediment, Daphnia magna toxicity and risk assessment. Environ Int 59:232–243

    Article  CAS  Google Scholar 

  • Cristale J, Katsoyiannis A, Sweetman AJ, Jones KC, Lacorte S (2013b) Occurrence and risk assessment of organophosphorus and brominated flame retardants in the River Aire (UK). Environ Pollut 179:194–200

    Article  CAS  Google Scholar 

  • Cristale J, Ramos DD, Dantas RF, Junior AM, Lacorte S, Sans C et al (2016) Can activated sludge treatments and advanced oxidation processes remove organophosphorus flame retardants? Environ Res 144:11–18

    Article  CAS  Google Scholar 

  • Dodson RE, Perovich LJ, Covaci A, Van den Eede N, Ionas AC, Dirtu AC, Rudel RA (2012) After the PBDE phase-out: a broad suite of flame retardants in repeat house dust samples from California. Environ Sci Technol 46(24):13056–13066

    Article  CAS  Google Scholar 

  • Fang Y, Kim E, Strathmann TJ (2018) Mineral-and base-catalyzed hydrolysis of organophosphate flame retardants: potential major fate-controlling sink in soil and aquatic environments. Environ Sci Technol 52(4):1997–2006

    Article  CAS  Google Scholar 

  • Fu L, Du B, Wang F, Lam JC, Zeng L, Zeng EY (2017) Organophosphate triesters and diester degradation products in municipal sludge from wastewater treatment plants in China: spatial patterns and ecological implications. Environ Sci Technol 51(23):13614–13623

    Article  CAS  Google Scholar 

  • Fu J, Fu K, Gao K, Li H, Xue Q, Chen Y, Jiang G (2020) Occurrence and trophic magnification of organophosphate esters in an Antarctic ecosystem: insights into the shift from legacy to emerging pollutants. J Hazard Mater 396:122742

    Article  CAS  Google Scholar 

  • Gao X, Xu Y, Ma M, Huang Q, Wang Z (2020) Distribution, sources and transport of organophosphorus flame retardants in the water and sediment of Ny-ÅLesund, Svalbard, the Arctic. Environ Pollut 264:114792

    Article  CAS  Google Scholar 

  • Giulivo M, Capri E, Kalogianni E, Milacic R, Majone B, Ferrari F, Barceló D (2017) Occurrence of halogenated and organophosphate flame retardants in sediment and fish samples from three European river basins. Sci Total Environ 586:782–791

    Article  CAS  Google Scholar 

  • Green N, Schlabach M, Bakke T, Brevik E, Dye C, Herzke D ... Vogelsang C (2008) Screening of selected metals and new organic contaminants 2007. Phosphorus flame retardents, polyfluorinated organic compounds, nitro-PAHs, silver, platinum and sucralose in air, wastewater treatment falcilities, and freshwater and marine recipients. Norwegian Institute for Water Research (NIVA)

  • Hill KL, Hamers T, Kamstra JH, Willmore WG, Letcher RJ (2018) Organophosphate triesters and selected metabolites enhance binding of thyroxine to human transthyretin in vitro. Toxicol Lett 285:87–93

    Article  CAS  Google Scholar 

  • Hou R, Xu Y, Wang Z (2016) Review of OPFRs in animals and humans: absorption, bioaccumulation, metabolism, and internal exposure research. Chemosphere 153:78–90

    Article  CAS  Google Scholar 

  • Hou R, Liu C, Gao X, Xu Y, Zha J, Wang Z (2017) Accumulation and distribution of organophosphate flame retardants (pfrs) and their di-alkyl phosphates (daps) metabolites in different freshwater fish from locations around Beijing China. Environ Pollut 229(Oct):548–556

    Article  CAS  Google Scholar 

  • Hou L, Jiang J, Gan Z, Dai Y, Yang P, Yan Y, Bao X (2019) Spatial distribution of organophosphorus and brominated flame retardants in surface water, sediment, groundwater, and wild fish in Chengdu, China. Arch Environ Contam Toxicol 77(2):279–290

    Article  CAS  Google Scholar 

  • Hu YX, Sun YX, Li X, Xu WH, Zhang Y, Luo XJ, Mai BX (2017) Organophosphorus flame retardants in mangrove sediments from the Pearl River Estuary, South China. Chemosphere 181:433–439

    Article  CAS  Google Scholar 

  • Kim UJ, Oh JK, Kannan K (2017) Occurrence, removal, and environmental emission of organophosphate flame retardants/plasticizers in a wastewater treatment plant in New York State. Environ Sci Technol 51(14):7872–7880

    Article  CAS  Google Scholar 

  • Kojima H, Takeuchi S, Itoh T, Iida M, Kobayashi S, Yoshida T (2013) In vitro endocrine disruption potential of organophosphate flame retardants via human nuclear receptors. Toxicology 314(1):76–83

    Article  CAS  Google Scholar 

  • Lee S, Cho HJ, Choi W, Moon HB (2018) Organophosphate flame retardants (OPFRs) in water and sediment: occurrence, distribution, and hotspots of contamination of Lake Shihwa, Korea. Mar Pollut Bull 130:105–112

    Article  CAS  Google Scholar 

  • Lee JS, Morita Y, Kawai YK, Covaci A, Kubota A (2020) Developmental circulatory failure caused by metabolites of organophosphorus flame retardants in zebrafish. Danio Rerio Chemosphere 246:125738

    Article  CAS  Google Scholar 

  • Li W, Wang Y, Kannan K (2019a) Occurrence, distribution and human exposure to 20 organophosphate esters in air, soil, pine needles, river water, and dust samples collected around an airport in New York State. United States Environ Int 131:105054

    Article  CAS  Google Scholar 

  • Li H, La Guardia MJ, Liu H, Hale RC, Mainor TM, Harvey E, Fu J (2019b) Brominated and organophosphate flame retardants along a sediment transect encompassing the Guiyu, China e-waste recycling zone. Sci Total Environ 646:58–67

    Article  CAS  Google Scholar 

  • Li BB, Hu LX, Yang YY, Wang TT, Liu C, Ying GG (2020) Contamination profiles and health risks of PFASs in groundwater of the Maozhou River basin. Environ Pollut 260:113996

    Article  CAS  Google Scholar 

  • Liang X, Junaid M, Wang Z et al (2019) Spatiotemporal distribution, source apportionment and ecological risk assessment of PBDEs and PAHs in the Guanlan River from rapidly urbanizing areas of Shenzhen, China [J]. Environ Pollut 250:695–707

    Article  CAS  Google Scholar 

  • Liu C, Wang Q, Liang K, Liu J, Zhou B, Zhang X, Yu H (2013) Effects of tris (1, 3-dichloro-2-propyl) phosphate and triphenyl phosphate on receptor-associated mRNA expression in zebrafish embryos/larvae. Aquat Toxicol 128:147–157

    Article  Google Scholar 

  • Liu J, He LX, Zeng XY et al (2016) Occurrence and distribution of organophosphorus flame retardants/ plasticizer in surface sediments from the Pearl River and Dongjiang River. Asian J Ecotoxicol 11:436–443 (in Chinese)

    Google Scholar 

  • Liu YE, Tang B, Liu Y, Luo XJ, Mai BX, Covaci A, Poma G (2019a) Occurrence, biomagnification and maternal transfer of legacy and emerging organophosphorus flame retardants and plasticizers in water snake from an e-waste site. Environ Int 133:105240

    Article  CAS  Google Scholar 

  • Liu X, Cai Y, Wang Y, Xu S, Ji K, Choi K (2019b) Effects of tris (1, 3-dichloro-2-propyl) phosphate (TDCPP) and triphenyl phosphate (TPP) on sex-dependent alterations of thyroid hormones in adult zebrafish. Ecotoxicol Environ Saf 170:25–32

    Article  CAS  Google Scholar 

  • Lu SY, Li YX, Zhang T, Cai D, Ruan JJ, Huang MZ, Qiu RL (2017) Effect of e-waste recycling on urinary metabolites of organophosphate flame retardants and plasticizers and their association with oxidative stress. Environ Sci Technol 51(4):2427–2437

    Article  CAS  Google Scholar 

  • Matsukami H, Suzuki G, Someya M, Uchida N, Tue NM, Viet PH, Takigami H (2017) Concentrations of polybrominated diphenyl ethers and alternative flame retardants in surface soils and river sediments from an electronic waste-processing area in Northern Vietnam, 2012–2014. Chemosphere 167:291–299

    Article  CAS  Google Scholar 

  • Nantaba F, Palm WU, Wasswa J, Bouwman H, Kylin H, Kuemmerer K (2021) Temporal dynamics and ecotoxicological risk assessment of personal care products, phthalate ester plasticizers, and organophosphorus flame retardants in water from Lake Victoria. Uganda Chemosphere 262:127716

    Article  CAS  Google Scholar 

  • Quintana JB, Rodil R, Reemtsma T (2006) Determination of phosphoric acid mono-and diesters in municipal wastewater by solid-phase extraction and ion-pair liquid chromatography− tandem mass spectrometry. Anal Chem 78(5):1644–1650

    Article  CAS  Google Scholar 

  • Shi Y, Gao L, Li W, Wang Y, Liu J, Cai Y (2016) Occurrence, distribution and seasonal variation of organophosphate flame retardants and plasticizers in urban surface water in Beijing, China. Environ Pollut 209:1–10

    Article  CAS  Google Scholar 

  • Su G, Crump D, Letcher RJ, Kennedy SW (2014) Rapid in vitro metabolism of the flame retardant triphenyl phosphate and effects on cytotoxicity and mRNA expression in chicken embryonic hepatocytes. Environ Sci Technol 48(22):13511–13519

    Article  CAS  Google Scholar 

  • Tan XX, Luo XJ, Zheng XB, Li ZR, Sun RX, Mai BX (2016) Distribution of organophosphorus flame retardants in sediments from the Pearl River Delta in South China. Sci Total Environ 544:77–84

    Article  CAS  Google Scholar 

  • Van der Veen I, de Boer J (2012) Phosphorus flame retardants: properties, production, environmental occurrence, toxicity and analysis. Chemosphere 88(10):1119–1153

    Article  Google Scholar 

  • Verbruggen EMJ, Rila JP, Traas TP, Posthuma-Doodeman CJAM, Posthumus R (2005) Environmental risk limits for several phosphate esters, with possible application as flame retardant. RIVM rapport 601501024

  • Wang XW, Liu JF, Yin YG (2011) Development of an ultra-high-performance liquid chromatography–tandem mass spectrometry method for high throughput determination of organophosphorus flame retardants in environmental water. J Chromatogr A 1218(38):6705–6711

    Article  CAS  Google Scholar 

  • Wang X, He Y, Lin L, Zeng F, Luan T (2014) Application of fully automatic hollow fiber liquid phase microextraction to assess the distribution of organophosphate esters in the Pearl River Estuaries. Sci Total Environ 470:263–269

    Article  Google Scholar 

  • Wang R, Tang J, Xie Z, Mi W, Chen Y, Wolschke H, Ebinghaus R (2015) Occurrence and spatial distribution of organophosphate ester flame retardants and plasticizers in 40 rivers draining into the Bohai Sea, North China. Environ Pollut 198:172–178

    Article  CAS  Google Scholar 

  • Wolschke H, Sühring R, Xie Z, Ebinghaus R (2015) Organophosphorus flame retardants and plasticizers in the aquatic environment: a case study of the Elbe River, Germany. Environ Pollut 206:488–493

    Article  CAS  Google Scholar 

  • Wu D, Zhou Y, Lu G, Hu K, Yao J, Shen X, Wei L (2019) The occurrence and risks of selected emerging pollutants in drinking water source areas in Henan, China. Int J Environ Res Public Health 16(21):4109

    Article  CAS  Google Scholar 

  • Xu L, Hu Q, Liu J, Liu S, Liu C, Deng Q et al (2019) Occurrence of organophosphate esters and their diesters degradation products in industrial wastewater treatment plants in china: implication for the usage and potential degradation during productionprocessing. Environmental Pollution 250(JUL):559–566

    Article  CAS  Google Scholar 

  • Xu L, Zhang B, Hu Q, Liu Y, Shang T, Zeng X, Yu Z (2021) Occurrence and spatio-seasonal distribution of organophosphate tri-and di-esters in surface water from Dongting Lake and their potential biological risk. Environ Pollut 282:117031

    Article  CAS  Google Scholar 

  • Zeng X, Sun H, Huang Y, Liu J, Yu L, Liu C, Wang J (2018) Effects of environmentally relevant concentrations of tris (2-butoxyethyl) phosphate on growth and transcription of genes involved in the GH/IGF and HPT axes in zebrafish (Danio rerio). Chemosphere 212:376–384

    Article  CAS  Google Scholar 

  • Yu K, Duan Y, Liao P, Xie L, Li Q, Ning Z, Liu C (2020) Watershed-scale distributions of heavy metals in the hyporheic zones of a heavily polluted Maozhou River watershed, southern China. Chemosphere 239:124773

    Article  CAS  Google Scholar 

  • Zhang S, Yang C, Liu M, Zhao W, Li Y, Meng XZ, Cai M (2021) Occurrence of organophosphate esters in surface water and sediment in drinking water source of Xiangjiang River. China Sci Total Environ 781:146734

    Article  CAS  Google Scholar 

  • Zhao F, Wan Y, Zhao H, Hu W, Mu D, Webster TF, Hu J (2016) Levels of blood organophosphorus flame retardants and association with changes in human sphingolipid homeostasis. Environ Sci Technol 50(16):8896–8903

    Article  CAS  Google Scholar 

Download references

Funding

The present study was supported by the project of “Toxicity Assessment of Major Organic Pollutants in Sediments from Typical Water Environment in Shenzhen and Application in Environmental Assessment” funded by the Ecology Environment Bureau of Shenzhen Municipality.

Author information

Authors and Affiliations

  1. Hubei Key Laboratory of Yangtze Catchment Environmental Aquatic Science, School of Environmental Studies, China University of Geosciences, Wuhan, 430074, People’s Republic of China

    Yunlang Liu & Zuoming Xie

  2. State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan, 430074, People’s Republic of China

    Zuoming Xie

  3. State Environmental Protection Key Laboratory of Managing Technology of Drinking Water Source, Shenzhen Key Laboratory of Emerging Contaminants Detection & Control in Water Environment, Shenzhen Academy of Environmental Science, Shenzhen, 518001, People’s Republic of China

    Tingting Zhu, Chen Deng, XiuJuan Qi, Rong Hu, Jinglin Wang & Jianyi Chen

Authors
  1. Yunlang Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Zuoming Xie
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Tingting Zhu
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Chen Deng
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. XiuJuan Qi
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Rong Hu
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Jinglin Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Jianyi Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Yunlang Liu: sampling, investigation, chemical and instrumental analyzing, methodology, data curation, and writing—original draft preparation. Zuoming Xie: conceptualization, methodology, writing—review and editing. Tingting Zhu: chemical and instrumental analyzing and writing—editing. Chen Deng, XiuJuan Qi, Rong Hu, Jinglin Wang, and Jianyi Chen have participated in sample analyses.

Corresponding author

Correspondence to Zuoming Xie.

Ethics declarations

Ethical approval

It is not applicable.

Consent to participate

All authors consent to participate.

Consent to publish

All authors consent to publish.

Competing interests

The authors declare no competing interests.

Additional information

Responsible Editor: Roland Peter Kallenborn

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Highlights

• The co-occurrence of OPFRs and Di-OPs was measured in water and sediment samples from two urban rivers in the industrial area of Shenzhen city.

• The concentrations of Cl-alkyl OPFRs in water and sediment were much higher than reported in other locations globally.

• TCEP is the predominant OPFR among all in water and sediment.

• First report about the presence of BBOEHP and BBOEP in river water.

• The moderate ecological risks of OPFRs (especially TCEP) in water were of particular concern.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (DOCX 55 KB)

Rights and permissions

Springer Nature or its licensor holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Liu, Y., Xie, Z., Zhu, T. et al. Occurrence, distribution, and ecological risk of organophosphorus flame retardants and their degradation products in water and upper sediment of two urban rivers in Shenzhen, China. Environ Sci Pollut Res 30, 14932–14942 (2023). https://doi.org/10.1007/s11356-022-23088-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11356-022-23088-4

Keywords

Search

Navigation