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Frontiers of Environmental Science & Engineering

ISSN 2095-2201

ISSN 2095-221X(Online)

CN 10-1013/X

Postal Subscription Code 80-973

2018 Impact Factor: 3.883

Front. Environ. Sci. Eng.    2020, Vol. 14 Issue (6) : 111    https://doi.org/10.1007/s11783-020-1290-5
RESEARCH ARTICLE
Diffusive gradients in thin films using molecularly imprinted polymer binding gels for in situ measurements of antibiotics in urban wastewaters
Ying Cui, Feng Tan(), Yan Wang, Suyu Ren, Jingwen Chen
Key Laboratory of Industrial Ecology and Environmental Engineering (MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024, China
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Abstract

• Selective molecularly imprinted polymer (MIP) binding gel was prepared.

• MIP-DGT showed excellent uptake performance for antibiotics.

• In situ measurement of antibiotics in wastewaters via MIP-DGT was developed.

• The MIP-DGT method was robust, reliable, and highly sensitive.

Urban wastewater is one of main sources for the introduction of antibiotics into the environment. Monitoring the concentrations of antibiotics in wastewater is necessary for estimating the amount of antibiotics discharged into the environment through urban wastewater treatment systems. In this study, we report a novel diffusive gradient in thin films (DGT) method based on molecularly imprinted polymers (MIPs) for in situ measurement of two typical antibiotics, fluoroquinolones (FQs) and sulfonamides (SAs) in urban wastewater. MIPs show specific adsorption toward their templates and their structural analogs, resulting in the selective uptake of the two target antibiotics during MIP-DGT deployment. The uptake performance of the MIP-DGTs was evaluated in the laboratory and was relatively independent of solution pH (4.0–9.0), ionic strength (1–750 mmol/L), and dissolved organic matter (DOM, 0–20 mg/L). MIP-DGT samplers were tested in the effluent of an urban wastewater treatment plant for field trials, where three SA (sulfamethoxazole, sulfapyridine, and trimethoprim) and one FQ (ofloxacin) antibiotics were detected, with concentrations ranging from 25.50 to 117.58 ng/L, which are consistent with the results measured by grab sampling. The total removal efficiency of the antibiotics was 80.1% by the treatment plant. This study demonstrates that MIP-DGT is an effective tool for in situ monitoring of trace antibiotics in complex urban wastewaters.

Keywords Diffusive gradients in thin films      Molecularly imprinted polymers      Selective uptake      Antibiotics      Passive sampling     
Corresponding Author(s): Feng Tan   
Issue Date: 28 July 2020
 Cite this article:   
Ying Cui,Feng Tan,Yan Wang, et al. Diffusive gradients in thin films using molecularly imprinted polymer binding gels for in situ measurements of antibiotics in urban wastewaters[J]. Front. Environ. Sci. Eng., 2020, 14(6): 111.
 URL:  
https://academic.hep.com.cn/fese/EN/10.1007/s11783-020-1290-5
https://academic.hep.com.cn/fese/EN/Y2020/V14/I6/111
Fig.1  Schematic diagram for the preparation of MIPs.
Fig.2  Scanning electron microscopy of FQIP particles (a and b) and an optical photograph of MIP gel (c). (a) ×10000; (b) ×80000.
Fig.3  Adsorption isotherms of OFL and SMX on FQIP and SAIP. Error bars represent the standard deviations of triplicates.
Analytes Kd (L/g) α
SAIP/FQIP NIP SAIP/FQIP NIP
SMX/OFL 32556/713 27/166
PA 64/18 23/23 512/39 1/7
TC 12/4 8/8 2691/178 3/21
Tab.1  Selective characteristics of FQIP, SAIP and NIP toward the targets and other compounds
Compounds Ds (106 cm2/s) Compounds Ds(106 cm2/s) 
25℃ 18.3°C 25°C 18.3°C
SMX 4.82±0.05 3.96 OFL 3.21±0.39 2.64
SDI 3.67±0.12 3.01 CIP 2.36±0.59 1.94
SD 3.86±0.39 3.17 ENR 2.38±0.21 1.95
SDZ 4.06±0.09 3.33 SAR 2.19±0.11 1.8
SPD 4.10±0.20 3.37 FLE 3.50±0.20 2.87
ST 4.29±0.55 3.52 LOM 2.97±0.08 2.44
SCT 4.18±0.32 3.43 GAT 3.18±0.50 2.61
SDX 4.10±0.02 3.37 SPA 4.03±0.25 3.31
SPMZ 4.56±0.14 3.74 MOX 2.36±0.22 1.94
TMP 3.51±0.58 2.88 OFL 2.44±0.46 2.64
Tab.2  Diffusion coefficients (Ds) of 20 antibiotics in agarose diffusive gel at 25°C and 18.3°C (n=3)
Fig.4  Uptake masses of FQs (MOX, ENR and OFL) and SAs (SMX, ST and SM2) by MIP-DGTs in solutions with different concentrations (pH= 6.3, temperature: 24℃±1℃). The solid lines are predicted from the known solution concentrations using the Eq. (2). Error bars represent the standard deviations of triplicates.
Fig.5  Effects of pH (a), ionic strength (b) and DOM concentration (c) on the CDGT/CSOLN ratios of antibiotics. CDGT is the concentration measured by the MIP–DGT and CSOLN is the actual concentration in the sample solution. Error bars represent the standard deviations from triplicates.
Fig.6  Accumulated masses of antibiotics by MIP–DGTs in well-stirred solutions (pH 6.3±0.2, 10 mmol/L NaCl) for different operating times. The solid lines are predictions for each operating time using Eq. (2). Error bars represent the standard deviations from triplicates.
Fig.7  Antibiotic concentrations measured by MIP-DGTs in the effluent of a WWTP and grab sampling tests in the influent and effluent of WWTP. ND represents concentrations lower than the MDL. Error bars represent the standard deviations from triplicates.
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