Occurrence of Phthalate Acid Esters (PAEs) in Protected Agriculture Soils and Implications for Human Health Exposure.

This study explored occurrence of phthalic acid esters (PAEs) in protected agriculture soils and assessed their potential health risks to humans. Results showed that DEHP and DBP were the most abundant PAEs congeners, with mean concentrations of 318.68 µg/kg and 137.56 µg/kg, respectively. DOP and BBP concentrations were relatively low, and DMP and DEP were not detected in all samples. DBP concentrations were higher than the allowable concentration standard value. Additionally, soil pH and organic matter were key environmental parameters which may play the vital roles to the occurrence of organic pollutants. Heath risk assessment results indicated that dermal contact was the predominant human exposure route under non-dietary conditions, and children obtained higher health risk scores than adults. In summary, the overall health risk scores were at an acceptable level. These results provide insights for assessing soil environmental safety and ecological risks in protected agricultural soil.

Low-temperature carbonization synthesis of carbon-based super-hydrophobic foam for efficient multi-state oil/water separation.

In view of the complexity and diversity of multi-state oils, the development of green and low-cost materials with high selectivity to oils has important ecological significance in the polluted water treatment. Herein, a simple method was proposed to develop large-scale production of superhydrophobic sponges (CPMF200 sponges) for high-efficiency oil/water separation under different complex environments. The as-prepared CPMF200 sponges possessed many superior properties, including high roughness, well-developed porosity, good thermal stability, excellent chemical stability, and superhydrophobic properties (water contact angle is 152°), which is conducive to high oil adsorption capacity (up to 70-179 times of its own weight) and oil-water separation. More importantly, the CPMF400 sponge has an excellent photothermal conversion capability to improve the fluidity of high viscosity oil for oil recovery. Based on a simple synthesis method, it exhibits high-efficiency absorption of multi-state oils and excellent oil-water separation performance and strongly proves their application prospects in treating oily wastewater.

Removal of chloramphenicol by sulfide-modified nanoscale zero-valent iron activated persulfate: Performance, salt resistance, and reaction mechanisms.

Herein, sulfide-modified nanoscale zero-valent iron (S-nZVI) was prepared by a liquid-phase reduction route and then applied to activate persulfate (PS) for the degradation of chloramphenicol (CAP). The effects of Fe/S molar ratio, catalyst dosage, PS concentration, initial pH, and co-existing ions (Cl-, SO42-, CO32-) on the catalytic performance of S-nZVI/PS system were investigated. Simultaneously, the fluctuations of solution pH, oxidation-reduction potential, dissolved oxygen, and Fe2+ concentration were also monitored during the reaction. Results shown that 98.8 % of CAP could be removed under the optimum reaction conditions (S-nZVI dosage = 0.1 g/L, PS concentration = 3 mM, initial pH = 6.86). Compared to the pristine nZVI, the sulfidation behavior could critically improve the removal efficiency of CAP, ascribe to the enhancements of hydrophobicity of nZVI, production of hydroxyl radicals, and salt resistance. Furthermore, possible degradation pathways of CAP in S-nZVI/PS system were inferred based on liquid chromatography-mass spectrometry (LC-MS) and density functional theory (DFT) calculations. This study proves that the S-nZVI is a more promising catalyst for activating PS than nZVI, especially in the field of saline pharmaceutical wastewater treatment.

Synergistic adjustment of water channels and light absorption pathways to co-generate salt collection and clean water production.

Solar-driven interface evaporation for clean water production has attracted significant concern due to its energy-saving and environmental protection. However, it is still challenging for the evaporator to continuously and efficiently produce clean water in practical applications because of salt particle deposits and insufficient water supply. Here, an improved and easy-to-manufacture solar evaporator device (Co-NCNT-GO system) enhances water supply and light absorption by introducing a water supply layer (melamine sponge) and bamboo-like structure carbon nanotubes embedded with metal cobalt particles (Co-NCNT). The salt accumulation on the edge of the Co-NCNT-GO film is achieved by controlling the concentration gradient of brine in the center area and the edge area of the film. This paper aims to study the photothermal mechanism of the Co-NCNT-GO system through a series of characterization and theoretical calculations (DFT) and discuss the influence of different water supply areas on the salt recovery capacity. The results show that Co-NCNT-GO significantly reduces the band (0.054 au) between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUNO) by graphite nitrogen-doped CNTs, which is beneficial to improve the light-to-heat conversion capability. Furthermore, the Co-NCNT-GO film has good water wettability due to the higher adsorption energy of pyridine nitrogen and water molecules in Co-NCNT (-9.33 kcal/mol). Simultaneously, it is found that the water evaporation capacity and water supply capacity significantly affect whether the salt can be continuously crystallized at the edge of the film. When the ratio of water supply area to light and heat area is 4:2.5, the salt recovery rate is 46.54 g m-2 h-1 during 108 h continuous desalination under one sun illumination. This rationally designed structure and adjustable water transport channel can simultaneously meet high-efficiency evaporation and salt recovery, which can have great potential in practical applications.

In-situ synthesis of manganese oxide­carbon nanocomposite and its application in activating persulfate for bisphenol F degradation.

In this work, manganese oxide­carbon nanocomposite catalytic materials (MnO@CNs) with a "core-shell" structure were synthesized in the one-step synthesis using sodium alginate as a template. XRD and Raman spectroscopy proved that high calcination temperatures were beneficial to the graphitization of carbon and the formation of Mn7C3. Both SEM and TEM images of MnO@CNs identified that MnO nanoparticles were encapsulated in a three-dimensional carbon matrix and simultaneously protected by a "carbon-shell" with an adherent graphite structure, which could facilitate electron transfer. The MnO@CNs could activate PS to degrade BPF completely within 30 min in solutions with a wide pH range or coexisting anions and organics. The valence change of Mn could promote the generation and conversion of various free radicals and non-radicals, of which O2·- played a leading role in the decomposition of BPF. In addition, the potential degradation pathways and degradation mechanisms of BPF in the MnO@CNs/PS system were also explored according to DFT calculations and product detection results.

A tunable amphiphilic Enteromorpha-modified graphene aerogel for oil/water separation.

Three-dimensional graphene aerogel materials used for treatment of oily wastewater with sophisticated composition remains a challenge due to volume shrinkage, resulting in single-function and low adsorption capacity. In this work, renewable Enteromorpha was introduced into the graphene aerogel via facile hydrothermal-freeze casting treatment, forming the compression, ultralight and amphiphilic adsorbent for oil spill cleanup and water pollution remediation. Meanwhile, further freeze casting avoids aerogel collapse for capillary tension during drying and produce more hierarchical pores. As for oil spill clean up, the Enteromorpha modified graphene aerogel (EGA) exhibits excellent adsorption capacity towards oil and organic solvents than pristine graphene aerogel (GA). Even after several cycles by compression and heat treatment, it still has a stable adsorption capacity for oil and organic solvents. The EGA also showed high ability to absorb water-soluble pollutants, such as dyes through hydrogen bonding and electrostatic reactions between dye molecules and aerogel. The facile strategy to fabricate the Enteromorpha-based amphiphilic EGA broadens the applications in water treatment through the high-value utilization of Enteromorpha.

Co-monomer polymer anion exchange resin for removing Cr(VI) contaminants: Adsorption kinetics, mechanism and performance.

Modified anion exchange resin (EDE-D301) was synthesized by mixing monomers: epichlorohydrin (ECH), dimethylamine (DMA), ethylenediamine (EDA) with the weakly alkaline anion exchange resin D301 through in-situ polymerization method. Adsorption performance of EDE-D301 for removing Cr(VI) contaminants was investigated in batch and column systems. Physicochemical properties of the anion exchange resins were characterized to determine the adsorption mechanism and regeneration ability. Characteristic results revealed that EDE-D301 showed enhanced surface area, positive charge and contents of N and Cl elements, indicating that the modifying reagents of monomers were successfully polymerized in the resin. The experimental adsorption data fitted well to the pseudo-second-order kinetic model and the Langmuir isotherm model. The fixed-bed experiments showed that the exhaustion time increased with increasing the bed depth, and decreased with increasing the flowrate and influent concentration. Adsorption capacity for Cr(VI) onto EDE-D301 was determined at a maximum level of 298 mg·g-1, and remained at 93% after four consecutive cycles. FTIR and XPS analysis indicated that the ion exchange and complexation were responsible for the Cr(VI) adsorption.

Effects of green synthesis, magnetization, and regeneration on ciprofloxacin removal by bimetallic nZVI/Cu composites and insights of degradation mechanism.

In this study, nanoscale zerovalent iron (nZVI) with copper (Cu) bimetallic particles, whichare applied for degradation of Ciprofloxacin (CIP) under weak magnetic field (WMF), were synthesized using green tea extracts (GT-nZVI/Cu). The surface morphology and physicochemical properties of the novel catalytic materials were characterized. It was found that GT-nZVI was more stable and performed better in oxidation resistance than the nZVI synthesized by traditional chemical methods. Besides, the catalytic reactivity of GT-nZVI/Cu was measured with and without WMF, it is obvious from the experimental results the performance of GT-nZVI/Cu system was enhanced significantly with WMF. Moreover, WMF still had a certain effect even after being removed, which is called remanence effect. The mass spectrometry (MS) was utilized to analyze the degradation products of CIP, and the contribution of adsorption and Fenton/Fenton-like oxidation of GT-nZVI/Cu during CIP removal process was further evaluated. It was found that as the removal process progressed, the contribution ratio of Fenton/Fenton-like oxidation rose rapidly and exceeded adsorption after 20 min. Eventually, attempts have been made to regenerate GT-nZVI/Cu, in which physical recovery (ultrasonic) was the main route, and the CIP removal rate decreased as the regeneration times increased. This research provides new insights into the green synthesis and regeneration of nZVI and is expected to realize the practical application of nZVI.

Performance optimization of CdS precipitated graphene oxide/polyacrylic acid composite for efficient photodegradation of chlortetracycline.

Here a CdS embedded poly acrylic acid (PAA)/graphene oxide (GO) polymeric composite was prepared for the efficient degradation of chlortetracycline (CTC) driven by visible light irradiation. The structure-activity relationship of GO/PAA-CdS was confirmed through the photocatalytic evaluation of a series of samples prepared by varying GO concentration, molar ratio of Cd:S and the amount of crosslinking agent. Through the composition, morphology, photoelectrochemical characterizations and degradation kinetic studies, it could be confirmed that the enhanced photocatalytic activity is attributed to the controlled growth of CdS nanoparticles by polymer net structure and effective electron transfer along GO nanosheets. The photodegradation of CTC was confirmed to be mainly governed by O2- and OH radicals generated from GO/PAA-CdS. The degradation intermediates of CTC were confirmed by LC-MS, and possible degradation pathways were proposed based on the prediction of radical attacking sites according to Fukui function values obtained through Density Functional Theory (DFT). Moreover, it was found that the catalytic activity of the photocatalyst was maintained after several cycles confirming the enhanced anti-photocorrosion of GO/PAA-CdS. This research provided an efficient approach by a novel photocatalyst for the removal of CTC from wastewater.

A facile approach to ultralight and recyclable 3D self-assembled copolymer/graphene aerogels for efficient oil/water separation.

In this paper, a facile approach was developed for highly effective oil/water separation by incorporating of the dimethyldiallylammonium chloride acrylamide polymer (P(AM-DMDAAC)) into graphene aerogels. The functionalized 3D graphene aerogel integrated a series of excellent physical properties, including low density (11.4 mg/cm3), large specific surface area (206.591 m2/g), and great hydrophobicity (contact angle of 142.7°). The modified aerogel showed excellent adsorption capacity for oils and organic solvents (up to 130 g/g). The saturation can be reached in a short time and the adsorption capacity remained nearly unchanged after repeated heating cycles. Meanwhile, we found a simple method to achieve controlled wettability transition of P(AM-DMDAAC)/graphene aerogels (PGAs) by changing the pH values. The hydrophobic PGA prepared at pH 2.03 showed outstanding oil/water separation performance (130 g/g). As the pH increased, the oil adsorption capabilities of PGAs decreased slightly, but the adsorption performance for the hydrophilic organic dye was significantly improved. Therefore, as a recyclable and efficient water purification material, the sustainable and environment-friendly polymer-modified graphene aerogel has great application potential.

Adsorption of Cd2+ on GO/PAA hydrogel and preliminary recycle to GO/PAA-CdS as efficient photocatalyst.

In this work, a GO (graphene oxide)/PAA (poly acrylic acid) hydrogel was prepared by graft polymerization between GO and AA. It was employed as highly efficient adsorbent for Cd2+ removal from wastewater. The GO/PAA-Cd2+ composite after the adsorption process was recycled through in-situ precipitation to obtain GO/PAA-CdS composites. During the synthesis process, the amounts of GO and AA were optimized to enable the hydrogel with maximum adsorption of Cd2+ (316.4 mg/g at 25 °C). The structure and chemical composites of GO/PAA hydrogel were investigated through FTIR spectra, Raman spectra, and TGA. The adsorption kinetics and isotherms of Cd2+ on GO/PAA were analyzed. The synthesized products served as an efficient adsorbent for Cd2+ and a suitable matrix for the CdS quantum dots formation which was confirmed by various characterizations, including XPS, SEM-EDS and HRTEM. The roles of GO and PAA in the successive adsorption-photocatalyst process were proved to be complementary: PAA improved the adsorption of Cd2+ while GO enhanced the photocatalyst efficiency. The photodegradation rate of MB (30 mg/L) was over 90% within 2 h.

A biodegradable biomass-based polymeric composite for slow release and water retention.

Slow-release fertilizer has been proven to be more effective than traditional fertilizer for providing a long-term stable nutrient supply. Although such fertilizers have been widely investigated, their water-retention properties and biodegradability have not been fully analysed. Composites of fertilizers and polymers provide opportunities to prepare new types of fertilizer with enhanced properties for real applications. Chicken feather protein-graft-poly(potassium acrylate)-polyvinyl alcohol semi-interpenetrating networks forming a super absorbent resin combined with nitrogen (N) and phosphorus (P) (CFP-g-PKA/PVA/NP semi-IPNs SAR) was prepared. The chemically bonded or physically embedded fertilizer compound could be released form the resin matrix to the surrounding soil under irrigation. The synthesis mechanism, morphology, and chemical and mechanical structure of the synthesized composites were investigated. The reactant doses were optimized through response surface methodology (RSM). A 30-day field trial of the prepared SAR was applied to detect the influence of sample particle size, soil salinity, pH, and moisture content on the slow-release behaviour of N and P. The maximum release values of N and P from the composites were 69.46% N and 65.23% P. A 120-day soil burying experiment and 30-day Aspergillus niger (A. niger) inoculation were performed, and the biodegradability and change in microstructure were monitored. The addition of SAR to soil could also improve the water-retention ability of the soil.

Preparation of wheat straw-supported Nanoscale Zero-Valent Iron and its removal performance on ciprofloxacin.

Wheat straw-supported Nanoscale Zero-Valent Iron particles (WS-NZVI) were successfully synthesized, which were used for Ciprofloxacin hydrochloride (CIP) removal in simulation wastewater. The structure, chemical composition and micro-morphology of WS-NZVI and Nanoscale Zero-Valent Iron (NZVI) were characterized by scanning electron microscopy analysis (SEM), X-ray diffraction (XRD), as well as the Fourier Transformed IR spectra (FT-IR). XRD results proved the existence of Fe°, and SEM images indicated that the agglomeration of NZVI was effectively inhibited when loaded on wheat straw. Besides, the effects of initial solution pH, CIP concentration, adsorbents dosage and contacting time on the removal efficiency of CIP by WS-NZVI and NZVI were investigated. The experimental results showed that, compared with NZVI and wheat straw, WS-NZVI possessed higher removal efficiency for CIP, and the maximum removal capacity of CIP by WS-NZVI was 363.63 mg g-1 (25 °C). Furthermore, WS-NZVI was suitable for wider pH range (pH = 4-10) in comparison with NZVI. For the WS-NZVI, the kinetic was better fitted with pseudo-second-order equation, rather than pseudo-first-order equation. The Mass spectrometry (MS) analysis deduced that the degradation reaction mainly occurred on quinolone groups piperazinyl ring. Therefore, it is feasible that using wheat straw as a support material to enhance the performance of NZVI, and the synthesized WS-NZVI has a potential in the organic compounds elimination because of its redox reaction activity.

Preparation of green alga-based activated carbon with lower impregnation ratio and less activation time by potassium tartrate for adsorption of chloramphenicol.

Potassium tartrate (C4H6K2O7) was utilized as a novel activating agent to prepare activated carbon with relatively high specific surface area by using less activating agent and activation time from marine waste-green alga (Enteromorpha prolifera) for the first time. The influences of activation temperature, impregnation ratio and activation time on the pore structure were investigated to obtain the optimum conditions (activation temperature: 700°C, impregnation ratio: 1:1, and activation time: 30min). Meanwhile, the activation temperature was evaluated to be the essential factor that dominated the form of pore structure in activated carbon. The green alga-based activated carbon that was prepared under optimum conditions has shown the high surface area of 1692m2/g and total pore volume of 1.22cm3/g, which could be used as an effective adsorbent to remove chloramphenicol. The thermodynamic data of chloramphenicol were well fitted by Langmuir isotherm model and the green alga-based activated carbon has showed high adsorption capacity of 709.2mg/g towards chloramphenicol.