H3PO4 activation mediated the iron phase transformation and enhanced the removal of bisphenol A on iron carbide-loaded activated biochar.

Zero valent iron-loaded biochar (Fe0-BC) has shown promise for the removal of various organic pollutants, but is restricted by reduced specific surface area, low utilization efficiency and limited production of reactive oxygen species (ROS). In this study, iron carbide-loaded activated biochar (Fe3C-AB) with a high surface area was synthesized through the pyrolysis of H3PO4 activated biochar with Fe(NO3)3, tested for removing bisphenol A (BPA) and elucidated the adsorption and degradation mechanisms. As a result, H3PO4 activated biochar was beneficial for the transformation of Fe0 to Fe3C. Fe3C-AB exhibited a significantly higher removal rate and removal capacity for BPA than that of Fe0-BC within a wide pH range of 5.0-11.0, and its performance was maintained even under extremely high salinity and different water sources. Moreover, X-ray photoelectron spectra and density functional theory calculations confirmed that hydrogen bonds were formed between the COOH groups and BPA. 1O2 was the major reactive species, constituting 37.0% of the removal efficiency in the degradation of BPA by Fe3C-AB. Density functional reactivity theory showed that degradation pathway 2 of BPA was preferentially attacked by ROS. Thus, Fe3C-AB with low cost and excellent recycling performance could be an alternative candidate for the efficient removal of contaminants.

Experimental and DFT investigation on N-functionalized biochars for enhanced removal of Cr(VI).

In this study, N-functionalized biochars with varied structural characteristics were designed by loading poplar leaf with different amounts of urea at 1:1 and 1:3 ratios through pyrolysis method. The addition of urea significantly increased the N content of biochar and facilitated the formation of amine (-NH-, -NH2), imine (-HCNH), benzimidazole (-C7H5N2), imidazole (-C3H3N2), and pyrimidine (-C4H3N2) groups due to substitution reaction and Maillard reaction. The effect of pH on Cr(VI) removal suggested that decrease in solution pH favored the formation of electrostatic attraction between the protonated functional groups and HCrO4-. And, experimental and density functional theory study were used to probe adsorption behaviors and adsorption mechanism which N-functionalized biochars interacted with Cr(VI). The protonation energy calculations indicated that N atoms in newly formed N-containing groups were better proton acceptors. Adsorption kinetics and isotherm experiments exhibited that N-functionalized biochars had greater removal rate and removal capacity for Cr(VI). The removal rate of Cr(VI) on N-functionalized biochar was 10.5-15.5 times that of untreated biochar. Meanwhile, N-functionalized biochar of NB3 with the largest number of adsorption sites for -C7H5N2, -NH2, -OH, -C3H3N2, and phthalic acid (-C8H5O4) exhibited the supreme adsorption capacity for Cr(VI) through H bonds and the highest adsorption energy was -5.01 kcal/mol. These mechanistic findings on the protonation and adsorption capacity are useful for better understanding the functions of N-functionalized biochars, thereby providing a guide for their use in various environmental applications.

Study on Survival and Sustainable Development of Small- and Medium-Sized Tourism and Hospitality Enterprises in Macao Based on Regional Soft Environment and Competitive Advantage.

The small- and medium-sized tourism and hospitality enterprises are the main forms of enterprises in Macao. This study put forward a new framework of survival and sustainable development from the perspective of competitive advantage and regional soft environment, which significantly holds theoretical and practical research value. The study obtained cross-sectional data of 317 small- and medium-sized tourism and hospitality enterprises in Macao through a large-scale questionnaire survey. This article used exploratory factor analysis and confirmatory factor analysis to test the reliability and validity of each factor system and its measurement scale. The variance analysis is used to judge the differences between the elements. The regression analysis is used to verify the hypothesis of a causal relationship between factors. The structural equation analysis is used to fit the model and make necessary amendments. The results reveal that the government service environment has a significant positive impact on the ability of an entrepreneur. In addition, the regional soft environment significantly impacts the competitive advantage of small- and medium-sized tourism and hospitality enterprises in Macao. Contrary, the impact of laws of Macao on the acquisition of financial resources and the promotion of entrepreneur ability and innovation ability is found insignificant. In conclusion, the results showed that market of Macao lacks venture investors where enterprises cannot obtain funds through angel financing or risk financing.

Microscopic mechanism about the selective adsorption of Cr(VI) from salt solution on O-rich and N-rich biochars.

The adsorption of Cr(VI) on biochars can be suppressed by coexisting anions, but the roles of O-containing functional groups and in particular N-containing functional groups are unclear. In this study, we combined spectroscopic and molecular simulation approaches to investigate the selective adsorption of Cr(VI) on the O-rich (PB, UB1) and N-rich (UB3, UB5) biochars under strong competition of anions. The elemental analysis and pyrolysis-gas chromatography/mass spectrometry indicated that the structures of PB and UB1 were similar, and so were the UB3 and UB5. Quantification of functional groups showed that for UB1, 75.3% of Cr(VI) removal was attributed to O-containing groups, while 53.3-72.7% of that was mediated by N-containing groups in UB3 and UB5. X-ray photoelectron spectra and density functional theory calculations confirmed that for O-rich biochars, surface complexation and strong H-bonds between carboxyl/hydroxyl and HCrO4- improved Cr(VI) removal in the presence of anions, while for N-rich biochars, Cr(VI) adsorption was depressed by coexisting anions in the order of Cl->NO3- >SO42- because of the weaker H-bond between protonated amino groups and HCrO4-. This study presents a novel approach for quantitative, molecular-level evaluation of the roles of biochar functional groups in the Cr(VI) removal from complex environmental systems.

Cardamine hupingshanensis aqueous extract improves intestinal redox status and gut microbiota in Se-deficient rats.

BACKGROUND: As an essential trace element for mammalian species, selenium (Se) possesses powerful antioxidant properties and is a potential regulator of intestinal microbiota. However, effects of Cardamine hupingshanensis aqueous extract (CE), rich in Se, on balancing the intestinal redox status and regulating gut microbiota have been neglected. RESULTS: An Se-deficient rat model was established by feeding a low-Se diet (LD) for 5 weeks and CE was then supplemented to LD or normal-Se-diet (ND) rats. Antioxidant enzyme activities and short-chain fatty acids (SCFA) concentration were increased by CE in both LD and ND rats. CE improved the intestinal morphology of LD rats impaired by deficient Se. Intestinal microbiota demonstrated various changes; for example, Butyrivibrio was increased in LD rats, while Bacteroides, Christensenellaceae, Clostridiaceae and Blautia were enhanced in ND rats. CONCLUSION: Our findings provide evidence that CE shows potential in improving intestinal redox status and regulating gut microbiota. © 2020 Society of Chemical Industry.

Chlortetracycline hydrochloride removal by different biochar/Fe composites: A comparative study.

In the last years, the synthesis and applications of biochar/Fe composites have been extensively studied, but only few papers have systematically evaluated their removal performances. Herein, we successfully synthesized and structurally characterized Fe0, Fe3C, and Fe3O4-coated biochars (BCs) for the removal of chlortetracycline hydrochloride (CH). Evaluation of their removal rate and affinity revealed that Fe0@BC could achieve better and faster CH removal and degradation than Fe3C@BC and Fe3O4@BC. The removal rate was controlled by the O-Fe content and solution pH after the reaction. The CH adsorption occurred on the O C groups of Fe0@BC and the OC and OFe groups of Fe3C@BC and Fe3O4@BC. Electron paramagnetic resonance analysis and radical quenching experiments indicated that HO and 1O2/ O2- were mainly responsible for CH degradation by biochar/Fe composites. Additional parameters, such as effects of initial concentrations and coexisting anions, regeneration capacity, cost and actual wastewater treatment were also explored. Principal component analysis was applied for a comprehensive and quantitative assessment of the three materials, indicating Fe0@BC is the most beneficial functional material for CH removal.

Singlet oxygen mediated the selective removal of oxytetracycline in C/Fe3C/Fe0 system as compared to chloramphenicol.

Reactive oxygen species (ROS) production for Fe0 is limited because of the formed iron corrosion products. In this study, C/Fe3C/Fe0 composite which produces enhanced ROS has been specifically designed and fabricated to remove typical antibiotics (i.e., oxytetracycline (OTC) and chloramphenicol (CAP)) as a heterogeneous Fenton-like catalyst. The C/Fe3C/Fe0 composite demonstrated excellent performance for both OTC and CAP removal as compared with Fe0 and biochar. Furthermore, X-ray photoelectron spectrometry, Fourier transform infrared spectrometry, high performance liquid chromatography-mass spectra and electron spin resonance analyses were conducted to elucidate the adsorption and degradation mechanisms. The adsorption of OTC and CAP was mainly dominated by H bonds and the electron-acceptor-acceptor on the surface of the C/Fe3C/Fe0 composite, respectively. In particular, OH simultaneously induced the degradation of OTC and CAP, while 1O2 presented the selective oxidation to OTC. More specifically, the degradation of OTC over C/Fe3C/Fe0 was stronger and faster than that of CAP, leading to 65.84% and 16.84% of removal efficiency for OTC and CAP, respectively. Furthermore, C/Fe3C/Fe0 exhibited superior reusability and stability after regeneration, but regenerated Fe0 almost lost its reactivity. Therefore, the efficiency in situ generation of 1O2 using C/Fe3C/Fe0 would shed new light on the selective oxidation of aqueous organic compounds.

Recovery of the biological function of ethylenediaminetetraacetic acid-washed soils: Roles of environmental variations and microbes.

To understand the recovery of the biological functions of washed soil, we studied changes in the microbial communities of soils washed with 10 or 60 mmol kg-1 ethylenediaminetetraacetic acid (EDTA) for 90 d of incubation. The relative abundance of tolerant or degrading species decreased, while that of microorganisms with chemical autotrophic ability increased as the incubation time increased. The changes in the enzyme activity followed different trends. As an intracellular enzyme, dehydrogenase was initially most severely damaged by the washing process but could recover over time, while the activity of urease increased after washing with EDTA, which may be related to the use of N as a nutrient source by microorganisms. Phosphatase did not significantly change over time. The redundancy discriminant analyses indicated that there were distinct factors driving such changes in the soils washed with different EDTA dosages. For the soil washed with 10 mmol kg-1 EDTA, bacteria with tolerance or degradation capacity of toxic pollutants, such as Nocardioidaceae, played a more important role in the recovery of soil functions; therefore, the EDTA stress indicator was the main driving factor. However, in the soil washed with 60 mmol kg-1 EDTA, chemolithoautotrophic bacteria, such as Nitrososphaeraceae, exerted a greater influence on the recovery of biological functions due to the higher loss of nutrients and EDTA residue; therefore, the main driving factor was the nutrients supply.

Effects of Zn in sludge-derived biochar on Cd immobilization and biological uptake by lettuce.

Considering the high Zn content of municipal sewage sludge and its competition with Cd during plant uptake due to their similar properties, the presence of Zn in sludge-derived biochar (SDBC) may affect Cd immobilization and uptake by plants. To confirm this, SDBC samples with different Zn contents were prepared and characterized. Their Cd immobilization behavior was studied by conducting batch sorption experiments, and their effects on Cd uptake by lettuce were explored by conducting hydroponic experiments. The results reveal that some Zn contained in the sewage sludge was transformed into ZnO during pyrolysis. The Brunauer-Emmett-Teller (BET) surface area of the SDBC samples containing 2324 mg kg-1 Zn (BC-2324) was 18.3 m2 g-1, which was 132% larger than that of the samples containing 1438 mg kg-1 Zn (BC-1438). The SDBC samples containing 1901 mg kg-1 (BC-1901) exhibited the highest Langmuir sorption capacity of 3476 mg kg-1, which is 115% higher than that of SB-1438. Furthermore, the lettuce remedied with SB-1901 exhibited 44% more biomass; lower peroxidase, catalase, and malondialdehyde activity; and 18.4% less Cd in the leaves of the lettuce than the lettuce remedied with BC-1438, suggesting the potential benefits of using Zn-rich SDBC for soil amendment.

Structure characteristics for intestinal uptake of flavonoids in Caco-2 cells.

Flavonoids are a large group of polyphenols and widely distributed in plant foods. Flavonoids exhibit various biological activities, such as anti-cancer, antioxidant and anti-inflammatory while poor oral bioavailability has been considered as a major hurdle in their use as functional foods. Cellular uptake and efflux of flavonoid implicates their bioavailability. To investigate the cellular uptake and efflux of flavonoids, 27 flavonoids were measured for their cellular uptake in Caco-2 cells with (CUV) and without (CU) the inhibitor of P-glycoprotein (P-gp) verapamil. Then, a quantitative structure-absorption relationship (QSAR) model containing 21 compounds as training set was obtained from their corresponding CU. The model showed good robustness and predictivity with a high cross-validation coefficient (Q2) value of 0.809 and Log of the octanol/water partition coefficient (SlogP) and atomic charge on carbon 5 (QC5) were related to flavonoid uptake. The CUV of some flavonoids were significantly (p<0.05 or p<0.01) higher than their CU, suggesting that specific flavonoids are pumped out by P-gp. The structure-affinity relationship of flavonoids as substrates of P-gp was determined with the presence of 4'-OCH3, 3'-OCH3 and the absence of 3'-OH, 3-OH and 4'-OH favorable for the affinity of flavonoids. These results provide valuable information for screening flavonoids with good absorption and low affinity with transporters.