Comprehensive evaluation of antibiotics pollution the Yangtze River basin, China: Emission, multimedia fate and risk assessment.

Antibiotics have attracted global attention because of their potential ecological and health risks. The emission, multimedia fate and risk of 18 selected antibiotics in the entire Yangtze River basin were evaluated by using a level Ⅳ fugacity model. High antibiotic emissions were found in the middle and lower reaches of the Yangtze River basin. The total antibiotic emissions in the Yangtze River basin exceeded 1600 tons per year between 2013 and 2021. The spatial distribution of antibiotics concentration was the upper Yangtze River > middle Yangtze River > lower Yangtze River, which is positively correlated with animal husbandry size in the basin. Temperature and precipitation increases may decrease the antibiotic concentrations in the environment. Transfer fluxes showed that source emission inputs, advection processes, and degradation fluxes contributed more to the total input and output. High ecological risks in the water environment were found in 2018, 2019, 2020, and 2021. The comprehensive health risk assessment through drinking water and fish consumption routes showed that a small part of the Yangtze River basin is at medium risk, and children have a relatively high degree of health risk. This study provides a scientific basis for the pollution control of antibiotics at the basin scale.

Multimedia fate model and risk assessment of typical antibiotics in the integrated demonstration zone of the Yangtze River Delta, China.

Due to the widespread consumption of antibiotics by humans and animals, antibiotic residues from human and animal excrements are released into the environment through domestic sewage and breeding wastewater, which ultimately affect the ecological environment and human health. In this study, the concentrations of 10 antibiotics in the air, water, soil, and sediment from 2013 to 2019 in Qingpu District of the integrated demonstration zone of the Yangtze River Delta were predicated by developing a dynamic Level IV fugacity model. The influence of seasonal environmental factors (e.g., temperature, rainfall) on the distribution and migration of antibiotics in multi-media was also explored. The simulation results show that the 10 antibiotics mainly existed in water and sediment. The concentrations of antibiotics in air, water, soil, and sediment were 0-7.629 × 10-14 ng/L, 1.187 × 10-10-16.793 ng/L, 1.042 × 10-14-3.500 × 10-11 ng/g and 8.015 × 10-12-14.188 ng/g, respectively. It was also found that the increase in temperature and rainfall can reduce the migration rate of some antibiotics into the water and sediment phases. The flux analysis of the cross-media migration and transformation of antibiotics in Qingpu District shows that advection was the prime input and output paths of antibiotics in the water. Moreover, the prime input and output paths of antibiotics in sediment were sedimentation from water to sediment and degradation. Sensitivity analysis shows that the characteristics of antibiotic emission, degradation rate, and Koc were the most influential parameters for target chemicals. The results of risk assessment based on Monte Carlo method reveal that the overall risk level of antibiotics in sediment was relatively risk-free, and the risk of antibiotics in water decreased in the order of tetracyclines > ß-lactams > fluoroquinolones > macrolides > sulfonamides.

Sorption-desorption and transport of trimethoprim and sulfonamide antibiotics in agricultural soil: effect of soil type, dissolved organic matter, and pH.

Use of animal manure is a main source of veterinary pharmaceuticals (VPs) in soil and groundwater through a series of migration processes. The sorption-desorption and transport of four commonly used VPs including trimethoprim (TMP), sulfapyridine, sulfameter, and sulfadimethoxine were investigated in three soil layers taken from an agricultural field in Chongming Island China and two types of aqueous solution (0.01 M CaCl2 solution and wastewater treatment plant effluent). Results from sorption-desorption experiments showed that the sorption behavior of selected VPs conformed to the Freundlich isotherm equation. TMP exhibited higher distribution coefficients (K d = 6.73-9.21) than other sulfonamides (K d = 0.03-0.47), indicating a much stronger adsorption capacity of TMP. The percentage of desorption for TMP in a range of 8-12 % is not so high to be considered significant. Low pH (

Sorption of carbamazepine from water by magnetic molecularly imprinted polymers based on chitosan-Fe3O4.

A novel magnetic-molecularly imprinted polymer (MMIP) based on chitosan-Fe3O4 has been synthesized for fast separation of carbamazepine (CBZ) from water. During polymerization, the modified chitosan-Fe3O4 was used not only as supporter but also as functional monomer. The properties of obtained MMIP were characterized by scanning electron and transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectra, thermo-gravimetric analysis and so on. The sorption equilibrium data was well described by Freundlich isotherm model and the increase in the temperature generated an increase in the sorption amount, indicating endothermic nature of adsorption process. Sorption kinetics followed the pseudo-second-order model. The feasibility of selective sorption of CBZ from real water by the MMIP was analyzed by using spiked real water samples. The result showed that the sorption capacity of MMIP has no obvious decrease in different water samples whereas there was obvious decline in the sorption amount of the MNIP.

Removal of carbamazepine and clofibric acid from water using double templates-molecularly imprinted polymers.

A novel double templates-molecularly imprinted polymer (MIP) was prepared by precipitation polymerization using carbamazepine (CBZ) and clofibric acid (CA) as the double templates molecular and 2-vinylpyridine as functional monomer. The equilibrium data of MIP was well described by the Freundlich isotherm model. Two kinetic models were adopted to describe the experimental data, and the pseudo second-order model well-described adsorption of CBZ and CA on the MIP. Adsorption experimental results showed that the MIP had good selectivity and adsorption capacity for CBZ and CA in the presence of competitive compounds compared with non-imprinted polymer, commercial powdered activated carbon, and C18 adsorbents. The feasibility of removing CBZ and CA from water by the MIP was demonstrated using tap water, lake water, and river water.

Selective trace enrichment of acidic pharmaceuticals in real water and sediment samples based on solid-phase extraction using multi-templates molecularly imprinted polymers.

A novel multi-templates molecularly imprinted polymer (MIP), using acidic pharmaceuticals mixture (ibuprofen (IBP), naproxen (NPX), ketoprofen (KEP), diclofenac (DFC), and clofibric acid (CA)) as the template, was prepared as solid-phase extraction (SPE) material for the quantitative enrichment of acidic pharmaceuticals in environmental samples and off-line coupled with liquid chromatography-mass spectrometry (LC/MS/MS). Washing solvent was optimized in terms of kind and volume for removing the matrix constituents nonspecifically adsorbed on the MIP. When 1L of water sample spiked at 1µg/L was loaded onto the cartridge, the binding capacity of the MIP cartridge were 48.7µg/g for KEP, 60.7µg/g for NPX, 52µg/g for CA, 61.3µg/g for DFC and 60.7µg/g for IBP, respectively, which are higher than those of the commercial single template MIP in organic medium (e.g. toluene) reported in the literature. Recoveries of the five acidic pharmaceuticals extracted from 1L of real water samples such as lake water and wastewater spiked at 1µg/L were more than 95%. The recoveries of acidic pharmaceuticals extracted from 10-g sediment sample spiked at the 10ng/g level were in the range of 77.4-90.6%. To demonstrate the potential of the MIP obtained, a comparison with commercial C18 SPE cartridge was performed. Molecularly imprinted solid-phase extraction (MISPE) cartridge showed higher recoveries than commercial C18 SPE cartridge for acidic pharmaceuticals. These results showed the suitability of the MISPE method for the selective extraction of a group of structurally related compounds such as acidic pharmaceuticals.

Comparative study of the degradation of carbamazepine in water by advanced oxidation processes.

Degradation of carbamazepine (CBZ) using ultraviolet (UV), UV/H2O2, Fenton, UV/Fenton and photocatalytic oxidation with TiO2 (UV/TiO2) was studied in deionized water. The five different oxidation processes were compared for the removal kinetics of CBZ. The results showed that all the processes followed pseudo-first-order kinetics. The direct photolysis (UV alone) was found to be less effective than UV/H2O2 oxidation for the degradation of CBZ. An approximate 20% increase in the CBZ removal efficiency occurred with the UV/Fenton reaction as compared with the Fenton oxidation. In the UV/TiO2 system, the kinetics of CBZ degradation in the presence of different concentrations of TiO2 followed the pseudo-first order degradation, which was consistent with the Langmuir-Hinshelwood (L-H) model. On a time basis, the degradation efficiencies ofCBZ were in the following order: UV/Fenton (86.9% +/- 1.7%) > UV/TiO2 (70.4% +/- 4.2%) > Fenton (67.8% +/- 2.6%) > UV/H2O2 (40.65 +/- 5.1%) > UV (12.2% +/- 1.4%). However, the lowest cost was obtained with the Fenton process.

Synthesis by precipitation polymerization of molecularly imprinted polymer for the selective extraction of diclofenac from water samples.

A molecularly imprinted polymer (MIP) was synthesized by precipitation polymerization using diclofenac (DFC) as a template, 2-vinylpyridine (2-VP) as functional monomer, ethylene glycol dimethacrylate (EGDMA) as cross-linker, and toluene as porogen. The MIP showed outstanding affinity toward DFC in aqueous solution with a binding site capacity (Q(max)) of 324.8 mg/g (1.09 mmol/g) and was used as solid-phase extraction (SPE) material for the quantitative enrichment of DFC in environmental water samples and off-line coupled to a reversed-phase HPLC/DAD. Various parameters including washing solvent, elution solvent and breakthrough volume affecting the extraction efficiency of the polymers have been evaluated to achieve the selective preconcentration of DFC from water samples and to reduce non-specific interactions. Recoveries of DFC extracted from tap water, river water and wastewater samples were higher than 95%, and no significant DFC recovery difference was obtained among the different water matrix. The stability of MIP was tested by consecutive percolation of water sample, and it was shown that the performance of the MIP did not vary even after 30 adsorption and desorption cycles. Furthermore, the MISPE was used for the analysis of DFC in river water and wastewater samples and revealed DFC concentrations of 0.69±0.002 µg/L (n=3) and 0.31±0.004µg/L (n=3), respectively. The results were in good agreement with corresponding LC-MS/MS data.

Selective removal of diclofenac from contaminated water using molecularly imprinted polymer microspheres.

A molecularly imprinted polymer (MIP) was synthesized by precipitation polymerization using diclofenac (DFC) as a template. Binding characteristics of the MIP were evaluated using equilibrium binding experiments. Compared to the non-imprinted polymer (NIP), the MIP showed an outstanding affinity towards DFC in an aqueous solution with a binding site capacity (Q(max)) of 324.8 mg/g and a dissociation constant (K(d)) of 3.99 mg/L. The feasibility of removing DFC from natural water by the MIP was demonstrated by using river water spiked with DFC. Effects of pH and humic acid on the selectivity and adsorption capacity of MIP were evaluated in detail. MIP had better selectivity and higher adsorption efficiency for DFC as compared to that of powdered activated carbon (PAC). In addition, MIP reusability was demonstrated for at least 12 repeated cycles without significant loss in performance, which is a definite advantage over single-use activated carbon.

Performance evaluation and application of molecularly imprinted polymer for separation of carbamazepine in aqueous solution.

A molecularly imprinted polymer (MIP) for selective adsorption of carbamazepine (CBZ) in aqueous solution was synthesized by precipitation polymerization using CBZ as a template molecule and methacrylic acid (MAA) as a functional monomer. The performance of the CBZ-MIP was evaluated in terms of selectivity, adsorption capacity, binding characteristics, loading volume, and elution volume. The CBZ-MIP exhibited a high affinity for CBZ over the competitive compound (Diclofenac) and was more suitable to remove low concentrations of CBZ in large-volume water samples. A binding performance experiment indicated that the adsorption of CBZ-MIP was characterized by both specific and non-specific binding interactions. Moreover, the regenerability of the MIP was affirmed in ten sequential cycles of adsorption/desorption without a significant loss in recovery. Finally, the CBZ-MIP was applied to enrich CBZ in environmental water samples, and the CBZ concentrations were subsequently determined using HPLC-UV. The results were in good agreement with corresponding LC-MS/MS data.