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Frontiers of Environmental Science & Engineering

ISSN 2095-2201

ISSN 2095-221X(Online)

CN 10-1013/X

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2018 Impact Factor: 3.883

Front. Environ. Sci. Eng.    2024, Vol. 18 Issue (3) : 34    https://doi.org/10.1007/s11783-024-1794-5
RESEARCH ARTICLE
Composition characterization and transformation mechanism of dissolved organic phosphorus in wastewater treatment using 31P NMR spectroscopy
Yuting Zhang1,2, Wei Shang1(), SoonThiam Khu2, Xingcan Zheng1, Yongli Sun1, Pengfeng Li1, Miao Gu1, Wen-an Zhang1, Huanmei Ma1
1. National Engineering Research Center For Urban Water & Wastewater, North China Municipal Engineering Design & Research Institute Co., Ltd., Tianjin 300381, China
2. School of Environment Science & Engineering, Tianjin University, Tianjin 300350, China
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Abstract

● The appropriate enrichment method for wastewater was assessed.

● Mono-P and Di-P were efficiently removed in biological treatment.

● Mechanism of P-components migration and transformation were established in WWTP.

The migration and transformation of phosphorus components in wastewater treatment plants (WWTPs) play a crucial role in the convergence and circulation of phosphorus. However, the composition and variation of dissolved organic phosphorus (DOP) in WWTPs were unclear because of its complex nature, hindering its efficient detection. In this study, the DOP species and their transformation during the treatment process in WWTP were comprehensively analyzed. First, two enrichment methods were assessed for their effectiveness at facilitating wastewater analysis: lyophilization and aluminum salt precipitation. Aluminum salt precipitation was found to be better because its application allowed 31P nuclear magnetic resonance (31P NMR) spectroscopy to identify more species in the secondary effluent: orthophosphate (Ortho-P) (81.1%–89.3% of the dissolved total phosphorus), pyrophosphates (Pyro-P) (0%–2.3%), orthophosphate monoesters (Mono-P) (7.0%–10.77%), orthophosphate diesters (Di-P) (1.0%–2.96%), and phosphonate (Phos-P) (1.7%–5.16%). Furthermore, the variation and transformation mechanism of phosphorus, particularly those of DOP, during the entire sewage-treatment process were elucidated. Among the treatment steps, biological treatment combined tertiary treatment achieved better DOP removal efficiencies. Therein, biological treatment mainly removed Mono-P and Di-P with removal efficiencies of 33.3% and 41.7% compared with the effluent of the grit chamber. Di-P has higher bioavailability and is more easily converted and utilized by microorganisms than Mono-P. However, Phos-P, with low bioavailability, was hardly utilized by microorganisms, which showed only 18.4% removal efficiency in biological treatment. In tertiary treatment, coagulation process exhibited higher removal ability of Ortho-P (69.1%) and partial removal efficiencies of DOP, resulting in an increase in the DOP proportion in TP. In addition, Phos-P could not be effectively removed through the biological treatment and was only partially reduced via the adsorption process by large particles, zoogloea or multinuclear hydroxyl complexes. The results of this study can provide a theoretical basis for efficient phosphorus removal in WWTPs.

Keywords Municipal wastewater      Dissolved organic phosphorus      Composition      Transformation      31P nuclear magnetic resonance     
Corresponding Author(s): Wei Shang   
Issue Date: 04 December 2023
 Cite this article:   
Yuting Zhang,Wei Shang,SoonThiam Khu, et al. Composition characterization and transformation mechanism of dissolved organic phosphorus in wastewater treatment using 31P NMR spectroscopy[J]. Front. Environ. Sci. Eng., 2024, 18(3): 34.
 URL:  
https://academic.hep.com.cn/fese/EN/10.1007/s11783-024-1794-5
https://academic.hep.com.cn/fese/EN/Y2024/V18/I3/34
ParameterspHTP (mg/L)DTP (mg/L)Ortho-P (mg/L)DOP (mg/L)TDS (mg/L)
Secondary ef?uent7.84 ± 0.20.65 ± 0.030.58 ± 0.030.52 ± 0.020.06 ± 0.02495 ± 15
Tab.1  Water quality parameters of secondary ef?uents in municipal wastewater treatment plant
Fig.1  31P NMR spectra of dissolved phosphorus samples from secondary effluent with different enrichment methods.
Ortho-P (NMR, %)Mono-P (NMR, %)Di-P (NMR, %)Phos-P (NMR, %)Pyro-P (NMR, %)Mono-P/OP (NMR, %)Di-P/OP (NMR, %)Phos-P/OP (NMR, %)
Lyophilizing method (10 L)89.210.8100
Flocculation method (10 L)89.37.01.02.765.49.325.3
Flocculation method (30 L)85.29.01.81.72.378.111.010.9
Tab.2  Relative content of phosphorus species of secondary effluent in 31P NMR by different enrichment methods
Fig.2  Variation of phosphorous concentration during wastewater treatment.
Fig.3  Variation of chemical functional groups (FT-IR) of organics and phosphrous species during wastewater treatment.
Ortho-P (NMR, %)Mono-P (NMR, %)Di-P (NMR, %)Phos-P (NMR, %)Pyro-P (NMR, %)Mono-P/OP (NMR, %)Di-P/OP (NMR, %)Phos-P/OP (NMR, %)
Influent80.0011.524.304.1357.7621.5720.68
EffGrit chambers81.7911.453.113.6562.8817.6920.01
EffBiological chambers79.1812.413.614.8159.5917.3323.09
EffSecondary81.1110.772.965.1657.0115.6927.3
Effluent72.1417.643.246.9863.2911.6425.06
PPInfluent91.853.663.431.0551.6148.39
PPGrit chambers91.123.004.980.8937.5962.41
SPBiological chambers85.4812.042.4882.9417.06
SPEnrichment tank82.6614.792.5585.2914.71
Tab.3  Relative content of phosphorus species in 31P NMR during wastewater treatment
Fig.4  31P NMR spectra of dissolved phosphorus samples, particulate phosphorus and sludge phosphorus during wastewater treatment. (a) DOP species in wastewater samples; (b) particulate phosphorus and sludge phosphorus species.
TP (mg/kg in sludge; mg/L in wastewater)Ca (mg/kg in sludge; mg/L in wastewater)Mg (mg/kg in sludge; mg/L in wastewater)Fe (mg/kg in sludge; mg/L in wastewater)Mn (mg/kg in sludge; mg/L in wastewater)Al (mg/kg in sludge; mg/L in wastewater)
SPBiological chambers33376164851271782845405420
SPEnrichment tank37092171901280829945503467
Influent6.0661.9036.390.440.130.02
EffGrit chambers4.5562.7636.780.700.220.02
EffBiological chambers2.0163.2535.320.030.010.09
EffSecondary1.0265.5434.140.010.080.01
Effluent0.3667.4435.210.010.010.01
Tab.4  Contents of TP and metal ions in sludge and wastewater samples
Fig.5  The migration and transformation of phosphorus components in different forms. (a) DOP species in wastewater samples (b) particulate phosphorus species.
Fig.6  Mechanism of phosphorus composition migration and transformation in WWTP.
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