Graphitic carbon nitride/biochar composite synthesized by a facile ball-milling method for the adsorption and photocatalytic degradation of enrofloxacin

In order to enhance the removal performance of graphitic carbon nitride (g-C₃N₄) on organic pollutant, a simultaneous process of adsorption and photocatalysis was achieved via the compounding of biochar and g-C₃N₄. In this study, g-C₃N₄ was obtained by a condensation reaction of melamine at 550°C. Then the g-C₃N₄/biochar composites were synthesized by ball milling biochar and g-C₃N₄ together, which was considered as a simple, economical, and green strategy. The characterization of resulting g-C₃N₄/biochar suggested that biochar and g-C₃N₄ achieved effective linkage. The adsorption and photocatalytic performance of the composites were evaluated with enrofloxacin (EFA) as a model pollutant. The result showed that all the g-C₃N₄/biochar composites displayed higher adsorption and photocatalytic performance to EFA than that of pure g-C₃N₄. The 50% g-C₃N₄/biochar performed best and removed 45.2% and 81.1% of EFA (10 mg/L) under darkness and light with a dosage of 1 mg/mL, while g-C₃N₄ were 19.0% and 27.3%, respectively. Besides, 50% g-C₃N₄/biochar showed the highest total organic carbon (TOC) removal efficiency (65.9%). Radical trapping experiments suggested that superoxide radical (?O₂^?) and hole (h⁺) were the main active species in the photocatalytic process. After 4 cycles, the composite still exhibited activity for catalytic removal of EFA.     

聚烯丙基磺酸钠接枝空心玻璃微珠的制备及其吸附性能研究

通过将烯丙基磺酸钠（SAS）和硅烷偶联剂接枝到空心玻璃微珠表面,制备出新型空心玻璃微珠基吸附剂（KNH-g-PSAS）并采用扫描电子显微镜,能量分散光谱,X射线光电子能谱,傅里叶变换红外光谱,热重分析和X射线衍射仪等对其进行了充分的表征,显示了SAS的成功接枝.此外,系统地研究了溶液的pH值,接触时间,初始浓度和温度对KNH-g-PSAS吸附阳离子染料的影响.准二级动力学模型和Langmuir等温线模型分别很好地描述了吸附动力学和吸附等温线,表明吸附是发生在吸附剂表面且均匀的单层吸附.吸附实验表明,在最佳条件下,KNH-g-PSAS对碱性品红、金胺O、结晶紫和孔雀石绿的吸附能力分别为2247.19mg/g,2317.46mg/g,2557.54mg/g,2808.98mg/g.KNH-g-PSAS具有出色的自上浮性能和回收表现.     

A highly porous animal bone-derived char with a superiority of promoting nZVI for Cr(VI) sequestration in agricultural soils

Paddy soil and irrigation water are commonly contaminated with hexavalent chromium [Cr(VI)] near urban industrial areas, thereby threatening the safety of agricultural products and human health. In this study, we develop a porous and high specific area bone char (BC) to support nanoscale zero-valent iron (nZVI) and apply it to remediate Cr(VI) pollution in water and paddy soil under anaerobic conditions. The batch experiments reveal that BC/nZVI exhibits a higher removal capacity of 516.7 mg/(g?nZVI) for Cr(VI) than nZVI when normalized to the actual nZVI content, which is 2.8 times that of nZVI; moreover, the highest nZVI utilization is the nZVI loading of 15% (BC/nZVI15). The Cr(VI) removal efficiency of BC/nZVI15 decreases with increasing pH (4 – 10). Coexisting ions (phosphate and carbonate) and humic acid can inhibit the removal of Cr(VI) with BC/nZVI15. Additionally, BC exhibits a strong advantage in promoting Cr(VI) removal by nZVI compared to the widely used biochar and activated carbon. Our results demonstrate that reduction and coprecipitation are the dominant Cr(VI) removal mechanisms. Furthermore, BC/nZVI15 shows a significantly higher reduction and removal efficiency as well as a strong anti-interference ability for Cr(VI) in paddy soil, as compared to nZVI. These findings provide a new effective material for remediating Cr(VI) pollution from water and soil.     

Identification of visible colored dissolved organic matter in biological and tertiary municipal effluents using multiple approaches including PARAFAC analysis

This study provided insights into the persistent yellowish color in biological and tertiary effluents of municipal wastewater through a multi-characterization approach and fluorescence excitation-emission matrix-parallel factor (EEM-PARAFAC) analysis. The characterization was performed on three to five full-scale municipal wastewater treatment plants (WWTPs), including differential log-transformed absorbance (DLnA) spectroscopy, resin fractionation, size-exclusion chromatography for apparent molecular weight analysis (SEC-AMW), and X-ray photoelectron spectroscopy (XPS) analysis. Hydrophobic acids (HPOA) were abundant in visible colored dissolved organic matter (DOM). The SEC-AMW result showed that the molecular weight of the colored substances in the secondary effluents is mainly distributed in the range of 2–3 kDa. Through XPS analysis, C-O/C-N and pyrrolic/pyridonic (N-5) were found to be positively correlated with chroma. PARAFAC component models were built on biological (two components) and tertiary effluent (three components) and the correlation analysis revealed that PARAFAC component 2 in biological effluent (BE-C2) and component 1 in tertiary effluent (TE-C1), which were ascribed to Hydrophobic acids and Humic acid-like, were the responsible visible colored DOM components cause yellowish color. In addition, component similarity testing found that the identified visible colored DOM PARAFAC BE-C2, and PARAFAC TE-C1 were identical (0.96) in physicochemical properties, with 4% removal efficacy on average, compared with 11% for invisible colored DOM. This implied that tertiary effluents containing colorants (TE-C1) were resistant to degradation/removal using different disinfection and filtration processes in advanced treatments. This sheds light on many physicochemical aspects of PARAFAC-identified visible colored DOM components and provides spectral data to build an online monitoring system.     

Remediation of preservative ethylparaben in water using natural sphalerite: Kinetics and mechanisms

As a typical class of emerging organic contaminants(EOCs), the environmental transformation and abatement of preservative parabens have raised certain environmental concerns. However, the remediation of parabens-contaminated water using natural matrixes(such as, naturally abundant minerals) is not reported extensively in literature. In this study, the transformation kinetics and the mechanism of ethylparaben using natural sphalerite(NS) were investigated. The results show that around 63% of ethy...     

Evaluation of offline sampling for atmospheric C3-C11 non-methane hydrocarbons

The concentration variation of C3-C11 non-methane hydrocarbons(NMHCs) collected in several types of commercial flexible bags and adsorption tubes was systematically investigated using a gas chromatography-flame ionization detector(GC-FID) system. The percentage loss of each NMHC in the polyvinyl fluoride(PVF) bags was less than 5% during a 7-hr storage period; significant NMHCs loss was detected in aluminum foil composite film and fluorinated ethylene propylene bags. The thermal desorption effic...     

A mechanistic study of ciprofloxacin adsorption by goethite in the presence of silver and titanium dioxide nanoparticles

The adsorption behaviors of ciprofloxacin (CIP), a fluoroquinolone antibiotic, onto goethite (Gt) in the presence of silver and titanium dioxide nanoparticles (AgNPs and TiO₂NPs) were investigated. Results showed that CIP adsorption kinetics in Gt with or without NPs both followed the pseudo-second-order kinetic model. The presence of AgNPs or TiO₂NPs inhibited the adsorption of CIP by Gt. The amount of inhibition of CIP sorption due to AgNPs was decreased with an increase of solution pH from 5.0 to 9.0. In contrast, in the presence of TiO₂NPs, CIP adsorption by Gt was almost unchanged at pHs of 5.0∼6.5 but was decreased with an increase of pH from 6.5 to 9.0. The mechanisms of AgNPs and TiO₂NPs in inhibiting CIP adsorption by Gt were different, which was attributed to citrate coating of AgNPs resulting in competition with CIP for adsorption sites on Gt, while TiO₂NPs could compete with Gt for CIP adsorption. Additionally, CIP was adsorbed by Gt or TiO₂NPs through a tridentate complex involving the bidentate inner-sphere coordination of the deprotonated carboxylic group and hydrogen bonding through the adjacent carbonyl group on the quinoline ring. These findings advance our understanding of the environmental behavior and fate of fluoroquinolone antibiotics in the presence of NPs.     

Formation of sulfur oxide groups by SO2 and their roles in mercury adsorption on carbon-based materials

The presence of SO₂ display significant effect on the mercury (Hg) adsorption ability of carbon-based sorbent. Yet the adsorption and oxidation of SO₂ on carbon with oxygen group, as well as the roles of different sulfur oxide groups in Hg adsorption have heretofore been unclear. The formation of sulfur oxide groups by SO₂ and their effects on Hg adsorption on carbon was detailed examined by the density functional theory. The results show that SO₂ can be oxidized into SO₃ by oxygen group on carbon surface. Both C-SO₂ and C-SO₃ can improve Hg adsorption on carbon site, while the promotive effect of C-SO₂ is stronger than C-SO₃. Electron density difference analyses reveal that sulfur oxide groups enhance the charge transfer ability of surface unsaturated carbon atom, thereby improving Hg adsorption. The experimental results confirm that surface active groups formed by SO₂ adsorption is more active for Hg adsorption than the groups generated by SO₃.     

Decoupling the adsorption mechanisms of arsenate at molecular level on modified cube-shaped sponge loaded superparamagnetic iron oxide nanoparticles

In this study, a commercial cube-shaped open-celled cellulose sponge adsorbent was modified by in-situ co-precipitation of superparamagnetic iron oxide nanoparticles (SPION) and used to remove As(V) from aqueous solutions. Fe K-edge X-ray absorption spectroscopy (XAS) and TEM identified maghemite as the main iron phase of the SPION nanoparticles with an average size 13 nm. Batch adsorption experiments at 800 mg/L showed a 63% increase of adsorption capacity when loading 2.6 wt.% mass fraction of SPION in the cube-sponge. Experimental determination of the adsorption thermodynamic parameters indicated that the As(V) adsorption on the composite material is a spontaneous and exothermic process. As K-edge XAS results confirmed that the adsorption enhancement on the composite can be attributed to the nanoparticles loaded. In addition, adsorbed As(V) did not get reduced to more toxic As(III) and formed a binuclear corner-sharing complex with SPION. The advantageous cube-shape of the sponge-loaded SPION composite together with its high affinity and good adsorption capacity for As(V), good regeneration capability and the enhanced-diffusion attributed to its open-celled structure make this adsorbent a good candidate for industrial applications.     

Evaluation of natural goethite on the removal of arsenate and selenite from water

Elevated arsenic and selenium concentrations in water cause health problems to both humans and wildlife. Natural and anthropogenic activities have caused contamination of these elements in waters worldwide, making the development of efficient cost-effective methods in their removal essential. In this work, removal of arsenate and selenite from water by adsorption onto a natural goethite(α-FeO OH) sample was studied at varying conditions. The data was then compared with other arsenate, selenite/goethite adsorption systems as much of literature shows discrepancies due to varying adsorption conditions. Characterization of the goethite was completed using inductively coupled plasma mass spectrometry, X-ray diffraction, Fouriertransform infrared spectroscopy, scanning electron microscopy, and Brunauer–Emmett–Teller surface area analysis. Pseudo-first order(PFO) and pseudo-second order(PSO) kinetic models were applied; including comparisons of different regression methods. Various adsorption isotherm models were applied to determine the best fitting model and to compare adsorption capacitates with other works. Desorption/leaching of arsenate and selenite was studied though the addition of phosphate and hydroxyl ions. Langmuir isotherm modeling resulted in maximum adsorption capacities of 6.204 and 7.740 mg/g for arsenate and selenite adsorption,respectively. The PSO model applied with a non-linear regression resulted in the best kinetic fits for both adsorption and desorption of arsenate and selenite. Adsorption decreased with increasing pH. Phosphate induced desorption resulted in the highest percentage of arsenate and selenite desorbed, while hydroxide induced resulted in the fastest desorption kinetics.