Shubo Deng

Pharmaceuticals and personal care products in the aquatic environment in China: a review.

Pharmaceuticals and personal care products (PPCPs) have been detected as contaminants of emerging concern ubiquitously in the aquatic environment in China and worldwide. A clear picture of PPCP contamination in the Chinese aquatic environment is needed to gain insight for both research and regulatory needs (e.g. monitoring, control and management). The occurrence data of 112 PPCPs in waters and sediments in China has been reviewed. In most cases, the detected concentration of these PPCPs in waters and sediments were at ng/L and ng/g levels, which were lower than or comparable to those reported worldwide. A screening level risk assessment (SLERA) identified six priority PPCPs in surface waters, namely erythromycin, roxithromycin, diclofenac, ibuprofen, salicylic acid and sulfamethoxazole. The results of SLERA also revealed that the hot spots for PPCP pollution were those river waters affected by the megacities with high density of population, such as Beijing, Tianjin, Guangzhou and Shanghai. Limitations of current researches and implications for future research in China were discussed. Some regulatory issues were also addressed.

Sorption of perfluorooctane sulfonate and perfluorooctanoate on activated carbons and resin: Kinetic and isotherm study.

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) have increasingly attracted global concerns in recent years due to their global distribution, persistence, strong bioaccumulation and potential toxicity. The feasibility of using powder activated carbon (PAC), granular activated carbon (GAC) and anion-exchange resin (AI400) to remove PFOS and PFOA from water was investigated with regard to their sorption kinetics and isotherms. Sorption kinetic results show that the adsorbent size influenced greatly the sorption velocity, and both the GAC and AI400 required over 168h to achieve the equilibrium, much longer than 4h for the PAC. Two kinetic models were adopted to describe the experimental data, and the pseudo-second-order model well described the sorption of PFOS and PFOA on the three adsorbents. The sorption isotherms show that the GAC had the lowest sorption capacity both for PFOS and PFOA among the three adsorbents, while the PAC and AI400 possessed the highest sorption capacity of 1.04mmolg(-1) for PFOS and 2.92mmolg(-1) for PFOA according to the Langmuir fitting. Based on the sorption behaviors and the characteristics of the adsorbents and adsorbates, ion exchange and electrostatic interaction as well as hydrophobic interaction were deduced to be involved in the sorption, and some hemi-micelles and micelles possibly formed in the intraparticle pores.

Occurrence and removal of pharmaceuticals, caffeine and DEET in wastewater treatment plants of Beijing, China

The occurrence and removal of 13 pharmaceuticals and 2 consumer products, including antibiotic, antilipidemic, anti-inflammatory, anti-hypertensive, anticonvulsant, stimulant, insect repellent and antipsychotic, were investigated in four wastewater treatment plants (WWTPs) of Beijing, China. The compounds were extracted from wastewater samples by solid-phase extraction (SPE) and analyzed by ultra-performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS). Most of the target compounds were detected, with the concentrations of 4.4 ng L(-1)-6.6 microg L(-1) and 2.2-320 ng L(-1) in the influents and secondary effluents, respectively. These concentrations were consistent with their consumptions in China, and much lower than those reported in the USA and Europe. Most compounds were hardly removed in the primary treatment, while their removal rates ranging from -12% to 100% were achieved during the secondary treatment. In the tertiary treatment, different processes showed discrepant performances. The target compounds could not be eliminated by sand filtration, but the ozonation and microfiltration/reverse osmosis (MF/RO) processes employed in two WWTPs were very effective to remove them, showing their main contributions to the removal of such micro-pollutants in wastewater treatment.

Selective removal of perfluorooctane sulfonate from aqueous solution using chitosan-based molecularly imprinted polymer adsorbents

Perfluorooctane sulfonate (PFOS) pollution in aqueous environment is a problem of global concern. A novel chitosan-based molecularly imprinted polymer (MIP) was prepared by crosslinking with epichlorohydrin (ECH) in the presence of PFOS as the template. During the preparation of the MIP adsorbents, the template amount and crosslinking agents significantly affected the imprinting effect. The optimized MIP adsorbents had a sorption amount of 560 micromol g(-1) for PFOS, while the sorption amount of the non-imprinted polymer (NIP) was only 258 micromol g(-1). The sorption behaviors of the MIP adsorbents including sorption kinetics, isotherms, effect of pH, ionic strength and selective sorption were investigated in detail. Sorption experimental results showed that the MIP adsorbents had good selectivity for PFOS, while other anionic contaminants with different structure had little influence on the sorption of the target PFOS. It was found that the electrostatic interaction played an important role in recognizing the target compound in the sorption process. Additionally, the MIP adsorbents could be used at least five times without any loss in sorption capacity. The chitosan-based MIP adsorbents may find potential application in water or wastewater treatment for the selective removal of PFOS.

Seasonal variation in the occurrence and removal of pharmaceuticals and personal care products in different biological wastewater treatment processes.

The occurrence of 12 pharmaceuticals and personal care products (PPCPs) in two wastewater treatment plants in Beijing was studied monthly over the course of one year. The removal of PPCPs by three biological treatment processes including conventional activated sludge (CAS), biological nutrient removal (BNR), and membrane bioreactor (MBR) was compared during different seasons. Seasonal variations of PPCPs in the wastewater influent were discrepant, while in the wastewater effluent, most PPCPs had lower concentrations in the summer than in the winter. For the easily biodegradable PPCPs, the performance of MBR was demonstrated to be more stable than CAS or BNR especially during winter months. Diclofenac, trimethoprim, metoprolol, and gemfibrozil could be moderately removed by MBR, while their removal by CAS and BNR was much lower or even negligible. Nevertheless, no removal was achieved regardless of the season or the treatment processes for the recalcitrant PPCPs. Studies on the contribution of each tank of the MBR process to the total removal of four biodegradable PPCPs indicated the oxic tank was the most important unit, whereas membrane filtration made a negligible contribution to their elimination.

Behaviors and mechanisms of copper adsorption on hydrolyzed polyacrylonitrile fibers

Polyacrylonitrile fiber (PANF) was hydrolyzed in a solution of sodium hydroxide and the hydrolyzed polyacrylonitrile fiber (HPANF) was used as an adsorbent to remove copper ions from aqueous solution. Scanning electron microscopy (SEM) showed that the hydrolysis process made the surface of HPANF rougher than that of PANF. Fourier transform infrared (FTIR) spectroscopy revealed that the HPANF contained conjugated imine (-Cz=Nz-) sequences. Batch adsorption results indicated that the HPANF was very effective in adsorbing copper, and the adsorption equilibrium could be reached within 10-20 min. Atomic force microscopy (AFM) showed that some aggregates formed on the surface of the HPANF after copper ion adsorption and the average surface roughness (R(a)) value of the HPANF changed from 0.363 to 3.763 nm due to copper adsorption. FTIR analysis indicated that copper adsorption caused a decrease of the light adsorption intensity of the imine (-Cz=Nz-) groups at 1573 and 1406 cm(-1) wavenumbers, and X-ray photoelectron spectroscopy (XPS) showed that the binding energy (BE) of some of the nitrogen atoms in the HPANF increased to a greater value due to copper adsorption. The FTIR and XPS results suggest that the adsorption of copper ions to the HPANF is attributed to the imine groups on the surface of the HPANF.

Efficient Electrochemical Oxidation of Perfluorooctanoate Using a Ti/SnO2-Sb-Bi Anode

The electrochemical decomposition of persistent perfluorooctanoate (PFOA) with a Ti/SnO2-Sb-Bi electrode was demonstrated in this study. After 2 h electrolysis, over 99% of PFOA (25 mL of 50 mg·L(-1)) was degraded with a first-order kinetic constant of 1.93 h(-1). The intermediate products including short-chain perfluorocarboxyl anions (CF3COO-, C2F5COO-, C3F7COO-, C4F9COO-, C5F11COO-, and C6F13COO-) and F- were detected in the aqueous solution. The electrochemical oxidation mechanism was revealed, that PFOA decomposition first occurred through a direct one electron transfer from the carboxyl group in PFOA to the anode at the potential of 3.37 V (vs saturated calomel electrode, SCE). After that, the PFOA radical was decarboxylated to form perfluoroheptyl radical which allowed a defluorination reaction between perfluoroheptyl radical and hydroxyl radical/O2. Electrospray ionization (ESI) mass spectrum further confirmed that the oxidation of PFOA on the Ti/SnO2-Sb-Bi electrode proceeded from the carboxyl group in PFOA rather than C-C cleavage, and the decomposition processes followed the CF2 unzipping cycle. The electrochemical technique with the Ti/SnO2-Sb-Bi electrode provided a potential method for PFOA degradation in the aqueous solution.

Granular Bamboo-Derived Activated Carbon for High CO2 Adsorption: The Dominant Role of Narrow Micropores

Cost-effective biomass-derived activated carbons with a high CO(2) adsorption capacity are attractive for carbon capture. Bamboo was found to be a suitable precursor for activated carbon preparation through KOH activation. The bamboo size in the range of 10-200 mesh had little effect on CO(2) adsorption, whereas the KOH/C mass ratio and activation temperature had a significant impact on CO(2) adsorption. The bamboo-derived activated carbon had a high adsorption capacity and excellent selectivity for CO(2) , and also the adsorption process was highly reversible. The adsorbed amount of CO(2) on the granular activated carbon was up to 7.0 mmol g(-1) at 273 K and 1 bar, which was higher than almost all carbon materials. The pore characteristics of activated carbons responsible for high CO(2) adsorption were fully investigated. Based on the analysis of narrow micropore size distribution of several activated carbons prepared under different conditions, a more accurate micropore range contributing to CO(2) adsorption was proposed. The volume of micropores in the range of 0.33-0.82 nm had a good linear relationship with CO(2) adsorption at 273 K and 1 bar, and the narrow micropores of about 0.55 nm produced the major contribution, which could be used to evaluate CO(2) adsorption on activated carbons.

Mn–Ce oxide as a high-capacity adsorbent for fluoride removal from water

A novel Mn-Ce oxide adsorbent with high sorption capacity for fluoride was prepared via co-precipitation method in this study, and the granular adsorbent was successfully prepared by calcining the mixture of the Mn-Ce powder and pseudo-boehmite. High-resolution transmission electron microscopy (TEM) image showed that the Mn-Ce adsorbent consisted of about 4.5 nm crystals, and X-ray diffraction (XRD) analysis indicated the formation of solid solution by Mn species entering CeO(2) lattices. The surface hydroxyl group density on the Mn-Ce adsorbent was determined to be as high as 15.3 mmol g(-1), mainly responsible for its high sorption capacity for fluoride. Sorption isotherms showed that the sorption capacities of fluoride on the powdered and granular adsorbent were 79.5 and 45.5 mg g(-1) respectively at the equilibrium fluoride concentration of 1 mg L(-1), much higher than all reported adsorbents. Additionally, the adsorption was fast within the initial 1 h. Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) analysis revealed that the hydroxyl groups on the adsorbent surface were involved in the sorption of fluoride. Both anion exchange and electrostatic interaction were involved in the sorption of fluoride on the Mn-Ce oxide adsorbent.

Adsorption behavior and mechanism of perfluorinated compounds on various adsorbents--a review.

Perfluorinated compounds (PFCs) have drawn great attention recently due to their wide distribution in aquatic environments and potential toxic to animals and human beings. Adsorption not only is an effective technology to remove PFCs from water or wastewater, but also affects PFC distribution at solid-liquid interfaces and their fate in aquatic environments. This article reviews the adsorption behavior of different PFCs (mainly perfluorooctane sulfonate and perfluorooctanoate) on various adsorptive materials. Some effective adsorbents are introduced in detail in terms of their preparation, characteristics, effects of solution chemistry and PFC properties on adsorption. Adsorption mechanisms of PFCs on different adsorbents are summarized, and various interactions including electrostatic interaction, hydrophobic interaction, ligand exchange, and hydrogen bond are fully reviewed. The adsorbents with amine groups generally have high adsorption capacity for PFCs, and formation of micelles/hemi-micelles plays an important role in achieving high adsorption capacity of perfluorinated surfactants on some porous adsorbents. Hydrophobic interaction is mainly responsible for PFC adsorption, but the difference between PFCs and traditional hydrocarbons has not clearly clarified. This review paper would be helpful for the preparation of effective adsorbents for PFC removal and understanding interfacial process of PFCs during their transport and fate in aquatic environments.