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The full utilization of solar energy has attracted great attention in the photocatalysis and environmental pollutant control. In this study, the local surface plasmon resonance effect of Ag nanoparticles (Ag NPs) with the upconversion property of nitrogen-doped graphene quantum dots (N-GQDs) was first combined for the formation of ternary Ag/N-GQDs/g-C3N4 nanocomposites. The prepared material presents enhanced full-spectrum light response ability, even in near-infrared (NIR) light. The experiment results disclosed that the 0.5% N-GQDs and 2.0% Ag NPs co-doped g-C3N4 show the highest photocatalytic activity, achieving 92.8 and 31.3% removal efficiency under full-spectrum light and NIR light irradiation, respectively, which was three-fold than that of pristine g-C3N4. The boosted photocatalytic activity can be attributed to the synergistic effect among the g-C3N4, N-GQDs, and Ag NPs. The g-C3N4 nanosheets can serve as the reaction matrix and support for the dispersion of N-GQDs and Ag NPs, inhibiting their agglomeration. The existence of Ag NPs and N-GQDs can promote the light absorption and transfer ability, leading to the generation of more photoinduced charges. Simultaneously, N-GQDs and Ag NPs can efficiently transfer and reserve electrons, which can accelerate the photoinduced electrons' migration, inhibiting the recombination. The comprehensive effect of the reasons mentioned above resulted in the unique photocatalytic activity of the prepared Ag/N-GQDs/g-C3N4 nanocomposites. This study provides a new strategy for the formation of highly efficient photocatalysts with broad-spectrum light response ability and the potential for realistic wastewater pollution control.

Nowadays, agricultural contamination is becoming more and more serious due to the rapid growth of agricultural industry, which discharged antibiotics, pesticides or toxic metals into farmlands. A large number of researchers have applied biochar-based functional materials to the treatment of agricultural wastewater contamination. Meanwhile, biochar has also proved to be a very promising and effective technology in water purification field due to its various beneficial properties (e.g., cost effective, high specific surface area, and surface reactive groups). The focus of this review is to highlight the fabrication methods and application of biochar-based functional materials with the removal of different agricultural contaminants, and discuss the underlying mechanisms. However, the application of biochar-based functional materials is currently under its infancy, with the main hindrance is identified as the gap between laboratory scale and field application, immaturity of engineered biochar production technologies, and lack of quality standards. In order to fill these knowledge gaps, more efforts should be made to pay for the relevant research in future studies.

The ordered mesoporous carbon composite functionalized with carboxylate groups and iron oxide nanoparticles (Fe/OMC) was successfully prepared and used to adsorb 2,4-dichlorophenoxyacetic acid (2,4-D) from wastewater. The resultant adsorbent possessed high degree of order, large specific surface area and pore volume, and good magnetic properties. The increase in initial pollutant concentration and contact time would make the adsorption capacity increase, but the pH and temperature are inversely proportional to 2,4-D uptake. The equilibrium of adsorption was reached within 120 min, and the equilibrated adsorption capacity increased from 99.38 to 310.78 mg/g with the increase of initial concentration of 2,4-D from 100 to 500 mg/L. Notablely, the adsorption capacity reached 97% of the maximum within the first 5 min. The kinetics and isotherm study showed that the pseudo-second-order kinetic and Langmuir isotherm models could well fit the adsorption data. These results indicate that Fe/OMC has a good potential for the rapid adsorption of 2,4-D and prevention of its further diffusion.

In this study, nanoscale zero-valent iron particles immobilized on mesoporous silica (nZVI/SBA-15) were successfully prepared for effective degradation of p-nitrophenol (PNP). The nZVI/SBA-15 composites were characterized by N 2 adsorption/desorption, transmission electron microscopy (TEM), UV–vis spectrum and X-ray photoelectron spectroscopy (XPS). Results showed that abundant ultrasmall nanoscale zero-valent iron particles were formed and well dispersed on mesoporous silica (SBA-15). Batch experiments revealed that PNP removal declined from 96.70% to 16.14% as solution pH increased from 3.0 to 9.0. Besides, degradation equilibrium was reached within 5 min, which was independent of initial PNP concentration. Furthermore, only a little PNP elimination on SBA-15 indicated that nZVI immobilized on mesoporous silica was mainly responsible for the target contaminant removal. The UV–vis spectrum and XPS measurement confirmed that the PNP removal was a reductive degradation process, which was further proved by the detected intermediates using gas chromatography–mass spectrometry (GC/MS). The excellent antioxidation ability had been discovered with more than 80% of PNP being removed by nZVI/SBA-15 treated with 30 days’ exposure to air. These results demonstrated the feasible and potential application of nZVI/SBA-15 composites in organic wastewater treatment.

This work has demonstrated an amplified and selective detection platform using enzyme-scaffolded-gold nanoclusters as signal label, coupling with mesoporous carbon nitride (MCN) and gold nanoparticles (GNPs) modified glassy carbon electrode (GCE). Streptavidin-horseradish peroxidase (SA-HRP) has been integrated with gold nanoclusters (GNCs) as scaffold using a simple, fast and non-toxic method. The mechanisms of enzymatic amplification, redox cycling and signal amplification by this biosensor were discussed in detail. GNCs might perform important roles as electrocatalyst as well as electron transducer in these processes. The concentrations of reagents and the reaction times of these reagents were optimized to improve the analytical performances. Under the optimized condition, the signal response to enzyme-scaffolded-gold nanoclusters catalyzed reaction was linearly related to the natural logarithm of the target nucleic acid concentration in the range from 10−17 M to 10–9 M with a correlation coefficient of 0.9946, and the detection limit was 8.0×10−18 M (S/N=3). Besides, synthesized oligonucleotide as well as Phanerochaete chrysosporium MnP fragments amplified using polymerase chain reaction and digested by restriction endonucleases were tested. Furthermore, this biosensor exhibited good precision, stability, sensitivity, and selectivity, and discriminated satisfactorily against mismatched nucleic acid samples of similar lengths.

In this study, a novel nitrogen-functionalized magnetic ordered mesoporous carbon (N-Fe/OMC) with uniform pore size (3.8 nm) and excellent magnetic property (8.46 emu/g) was fabricated through simple impregnation then polymerization and calcination. The resultant adsorbent exhibited more preferential sorption toward Pb(II) and phenol than simple equivalent mixture of magnetic ordered mesoporous carbon (Fe/OMC) and pristine ordered mesoporous carbon (OMC). Binary adsorption showed that the coexistence of Pb(II) and phenol at low concentrations would slightly accelerate their jointly adsorption because of partial complexation between Pb(II) and phenol. While at high concentrations, Pb(II) adsorption would be inhibited in relation to the competition from phenol, but phenol adsorption was scarcely affected due to the directly phenol molecular adsorption pattern. Pb(II) adsorption was more suitable in alkaline solution and affected by ionic strength on account of electrostatic interaction, whereas phenol adsorption was better in neutral pH and hardly interfered by ionic strength as the adsorption was a physical combination process. Thermodynamics indicated that the uptakes of Pb(II) and phenol were endothermic and exothermic processes, respectively. Moreover, N-Fe/OMC could be regenerated effectively and recycled by using dilute NaOH and acetone solutions. These superior properties demonstrate that N-Fe/OMC is attractive for practical applications in treatment of water contamination by Pb(II) and phenol.

A novel adsorbent was prepared by chelating magnetic mesoporous carbon with polyacrylic acid (PAA) to improve the performance of Cd(II) adsorption. Structure characterization demonstrated that the composites were successfully modified with carboxyl groups and preserved ordered mesostructure after modification. The high saturation magnetization (9.2 emu/g) of the modified composites indicated easy and fast separation from water under a moderate magnetic field. Batch experiments with variable pH, contact time and ionic strength were conducted to evaluate the adsorption performance. The modification accelerated the cadmium adsorption rate. The adsorption kinetics of the two materials followed pseudo-second-order model and exhibited 3-stage intraparticle diffusion mode. Equilibrium data were best described by Langmuir model, and the estimated maximum adsorption capacity for the modified adsorbent increased to 406.6 mg/g, which was 140.8% higher than the pristine materials. Moreover, the Cd(II) loaded adsorbent could be regenerated using 0.1 M ethylenediaminetetraacetic acid solution, and the regenerated adsorbent after five cycles could retain 85.2% of the adsorption capacity for the fresh adsorbent. The results suggested that PAA modified adsorbents could be considered to be very effective and promising materials for Cd(II) removal from waste water.

Cadmium (Cd) is present in soil and water at low concentrations that can be harmful to the biota. A Cd-tolerant plant species named ramie (Boehmeria nivea (L.) Gaudich) was applied to probe the precise Cd tolerance mechanism with different treatment duration and the up-regulation effect for antioxidant capacity by spermidine (Spd) pretreatment. The results showed that short-term (0–7 d) Cd stress resulted in the enhancement of pigment content, the accumulation of soluble sugar and the activation of partial antioxidants, meanwhile reducing the level of malondialdehyde (MDA), which is the indicator of oxidative stress. Spd pretreatment markedly increased the soluble protein, soluble sugar and reduced glutathione (GSH) content in ramie leaves under short-term Cd stress, whereas, it showed no significantly beneficial effects on photosynthesis and other antioxidants. Long-term (0–15 d) Cd stress may lead to growth inhibition which is associated with Cd accumulation, protein oxidation, sugar degradation, MDA surge and antioxidant inactivation. Spd application markedly alleviated long-term Cd toxicity by decreasing Cd accumulation, stabilizing cellular macromolecules such as pigments, soluble protein and sugar and inhibiting peroxidase (POD), catalase (CAT) and malate dehydrogenase (MDH) inactivation and GSH degradation. Our present work concluded that ramie could tolerate moderate Cd stress during a certain time span. Spd application could play a vital role in the promotion of Cd tolerance by adjusting different kinds of parameters.

This study demonstrates a novel biosensor for silver(I) ion detection based on nanoporous gold (NPG) and duplex-like DNA scaffolds with anionic intercalator. The hairpin structure was formed initially through hybridization with the unlabeled probe (S1 + S2 + S3). In the presence of Ag+, the structure of immobilized DNA changed to duplex-like structure, and formed a C–Ag+–C complex at electrode surface. The response current of the modified electrode after immersing in the disodium anthraquinone-2,6-disulfonate (AQDS) as the signal agent was changed. And an increased current was obtained, corresponding to Ag+ concentration. NPG provided faster electron transfer and an excellent platform for DNA immobilization. Under optimal conditions, silver(I) ion could be detected in the range from 1 × 10−10 M to 1 × 10−6 M, and the lower detection limit of the biosensor for Ag+ is 4.8 × 10−11 M with good specificity. The results showed that this novel approach provided a reliable method for the quantification of Ag+ with sensitivity and specificity, which was potential for practical applications.

A polycyclic aromatic hydrocarbon (PAH)-degrading microbe was isolated and the effect of Pb(II) on the degradation of phenanthrene (PHE) by this microbe was studied in this research. The changes in the metabolism, protein content, enzyme activity and PHE degradation induced by Pb(II) were investigated to elucidate the effect of Pb(II) on the degradation of PHE. The protein content, catechol 2,3-dioxygenase activity and phenanthrene-degrading ability of the enzymes were all enhanced at low concentrations of Pb(II) (below 50 mg L−1) but decreased at relatively higher concentrations (100 to 300 mg L−1) of Pb(II). These results indicate that the presence of Pb(II) is relevant to enzymatic changes in this PAH-biodegrading microbe: it helps the process of PHE biodegradation at low concentrations, but impairs PHE biodegradation at excessive concentrations.

Based on ecological niche theory, Microcystis Aeruginosa (MA) immobilized in the complex of polyvinyl alcohol (PVA) and sodium alginate (SA) crosslinked by CaCl2, was treated as a new kind of special species, and its properties were investigated. Chlorophyll a was used to characterize the bioactivity of the immobilized MA. Results reveal that the gel beads have mechanical strength and chemical stability even under non-sterile harsh conditions, which may be attributed to the rarely seen structure (including three different layers: dense surface, tubular-shaped divergent structure and honeycomb crystal lattice layer) of the immobilized MA determined by scanning electron microscope (SEM). SEM also displays that more quantity of MA is attached to the inwall after cultivation, which demonstrates that the MA within beads maintains high bioactivity. Removal capacities on phosphorous (P) removal in wastewater in the presence and absence of the BG-11 medium were examined, and the removal ratios are 80.3% and 76.7%, respectively, which indicates that the beads without providing ample nutrients still have high capacity of P removal. In addition, control experiment, utilizing polyvinyl alcohol and sodium alginate (PVA-SA) beads without immobilized MA, demonstrates that MA within beads plays the key role in absorbing P.

A cutinase loaded nanoporous gold-polyethyleneimine (NPG-PEI) was fabricated for the application in simultaneous removal of DEHP and Pb(II) from contaminated water. The thermal stability, acid and alkali resistance, storage stability and reutilization of immobilized cutinase were enhanced. The removal kinetics of DEHP and Pb(II) were described by a pseudo-second-order kinetic model, and the adsorption isotherms for Pb(II) were fitted by a Langmuir model. Pb(II) had a suppression effect on DEHP uptake in the simultaneous removal and DEHP preloading experiments. The overall DEHP removal efficiency was about 90.9%, in which enzymatic hydrolysis contributed about 81.9%, and the enzymatic degradation products of DEHP were mainly non-toxic 1,3-isobenzofurandione (IBF). In simultaneous removal of DEHP and Pb(II) at low concentrations, the cutinase loaded NPG-PEI can be used more than five times before regeneration. Due to its high removal capacity, easy separation and effective reusability, cutinase loaded NPG-PEI presented excellent potential in wastewater treatment.

In this study, a novelly synthesized magnetic mesoporous silica composite with high uniformity and polyaniline (PANI) grafted was successfully applied to highly efficient Cr(VI) removal. With the assistance of high adsorption capacity of protonated PANI and the magnetic mesoporous composite at low pH, Cr(VI) was adsorbed and then reduced to less toxic Cr(III) by PANI. The resultant adsorbent was characterized by TEM and FTIR, nitrogen adsorption–desorption measurements were carried out, and the zeta potentials of the prepared adsorbent were also measured at different pH. The adsorption and synergistic reduction route was particularly deduced by analyzing the existing forms of PANI and Cr by XPS. Pseudo-second-order model could well fit the data obtained from batch Cr(VI) removal experiments for the kinetic study, and Langmuir model well described the sorption isotherms with the maximum adsorption capacity of 193.85 mg/g. Competition from coexisting ions (K+, Na+, Ca2+, Cl−, SO42−, NO3−) was proved to be insignificant. Moreover, the exhausted adsorbent could be well regenerated and kept above 83% removal efficiency in the first three cycles, which demonstrated that it was cost-effective. The results suggested that this novel magnetic adsorbent may offer a simple adsorption and synergistic reduction treatment option to remove Cr(VI) contamination from industrial wastewater and natural water bodies.

In this work, a field test was conducted to investigate the effects of heavy metal stabilizer addition on brown rice and microbial variables in a cadmium (Cd)-contaminated farmland from April to October in 2016. Compared with the control, red mud-based stabilizer (RMDL) effectively reduced the concentration of Cd in brown rice (with the removal rate of 48.14% in early rice, 20.24 and 47.62% in late rice). The results showed that adding 0.3 kg m−2 RDML in early rice soil or soil for both early and late rice increased the microbial biomass carbon (MBC), the number of culturable heterotrophic bacteria and fungi, and the catalase activity in soil at different stages of paddy rice growth. Furthermore, there was no notable difference in the diversity of the bacterial species, community composition, and relative abundance at phylum (or class) or operational taxonomic unit (OTU) levels between the control and treatment (RMDL addition) groups. In a word, RMDL could be highly recommended as an effective remediation stabilizer for Cd-contaminated farmland, since its continuous application in paddy soil cultivating two seasons rice soil could effectively decrease the Cd content in brown rice and had no negative impact on soil microorganisms.

To realize the full utilization of solar energy, the design of highly efficient photocatalyst with improved visible-near-infrared photocatalysis performance has attracted great attentions for environment pollutant removal. In this work, we rationally employed the surface plasmon resonance effect of metallic Ag in the phosphorus doped ultrathin g-C

In recent years, advanced oxidation processes (AOPs), especially sulfate radical based AOPs have been widely used in various fields of wastewater treatment due to their capability and adaptability in decontamination. Recently, metal-free carbon materials catalysts in sulfate radical production has been more and more concerned because these materials have been demonstrated to be promising alternatives to conventional metal-based catalysts, but the review of metal-free catalysts is rare. The present review outlines the current state of knowledge on the generation of sulfate radical using metal-free catalysts including carbon nanotubes, graphene, mesoporous carbon, activated carbon, activated carbon fiber, nanodiamond. The mechanism such as the radical pathway and non-radical pathway, and factors influencing of the activation of sulfate radical was also be revealed. Knowledge gaps and research needs have been identified, which include the perspectives on challenges related to metal-free catalyst, heterogeneous metal-free catalyst/persulfate systems and their potential in practical environmental remediation.

To realize the sustainable employment of solar energy in contaminant degradation and environmental recovery, design and development of an efficient photocatalyst is urgently needed. Herein, a novel direct Z-scheme composite photocatalysts consist of phosphorous-doped ultrathin g-C3N4 nanosheets (PCNS) and bismuth vanadate (BiVO4) are developed via a one-pot impregnated precipitation method. The as-prepared hybrid nanocomposite was utilized for the degradation tetracycline (TC) under visible light irradiation. Among the composites with various PCNS/BiVO4 ratios, the prepared PCNS/BVO-400 photocatalyst presents the best performance, showing a TC (10mg/L) removal efficiency of 96.95% within 60min, more than double that of pristine BiVO4 (41.45%) and higher than that of pure PCNS (71.78%) under the same conditions. The effects of initial TC concentration, catalyst dosage, pH value and different water sources have been studied in detail. The improved photocatalytic performance of the as-prepared PCNS/BiVO4 nanocomposites could be attributed to the promoted separation efficiency of the photogenerated electrons and the enhanced charge carrier lifetime (1.65ns) owing to the synergistic effect between the PCNS and BiVO4. The degradation intermediates and decomposition pathway of TC were also analyzed and proposed. Additionally, radical trapping experiments and ESR measurement indicated that the photogenerated holes (h+), superoxide radical (O2-) and hydroxyl radical (OH) all participated in the TC removal procedure in the reaction system. The high performance of PCNS/BVO-400 in real wastewater indicated the potential of the prepared composite in practical application. This work provides an efficient and promising approach for the formation of high performance Z-scheme photocatalyst and study the possibility for real wastewater treatment.

Metal–organic frameworks (MOFs) with Fe content are gradually developing into an independent branch in environmental remediation, requiring economical, effective, low-toxicity strategies to the complete procedure. In this review, recent advancements in the structure, synthesis, and environmental application focusing on the mechanism are presented. The unique structure of novel design proposed specific characteristics of different iron-containing MOFs with potential innovation. Synthesis of typical MILs, NH2-MILs and MILs based materials reveal the basis and defect of the current method, indicating the optimal means for the actual requirements. The adsorption of various contamination with multiple interaction as well as the catalytic degradation over radicals or electron–hole pairs are reviewed. This review implied considerable prospects of iron-containing MOFs in the field of environment and a more comprehensive cognition into the challenges and potential improvement.

Aiming at developing a safe and efficient alternative to traditional drinking water disinfection, this work successfully synthesized a novel antibacterial material with high surface area, ultra large pore size and tunable loading of immobilized lysozyme. The immobilized enzymes exhibit high antibacterial efficacy without forming carcinogenic disinfection byproducts. Critical immobilization parameters were optimized to keep the activity of the immobilized enzyme at a high level. The immobilization of lysozymes on 3DOm COOH could be confirmed by the characterizations of transmission electron microscopy, X-ray diffraction and Zeta-Potential. In addition, the structural stability of lysozymes on 3DOm COOH were studied by Fourier transform infrared spectroscopy. The antibacterial performance of 3DOm COOH-Lyz were specifically investigated based on the disinfection efficacy of Staphylococcus aureus in water. The results revealed that the immobilization capacity and relative activity of immobilized lysozyme were 814mg/g carrier and 80%, respectively, under the optimal immobilization conditions. And the antibacterial material with the initial mass ratio of lysozyme and 3DOm COOH as 3:1 exhibited maximum bacteria removal efficiency (98.1%) at pH 5. Moreover, the reusability test indicated that 3DOm COOH-Lyz has certain operational stability, and remains 82% bacterial removal efficiency even in the fifth cycle, which provides a promising application for safe and efficient drinking water disinfection in small-scale and emergency water treatment.

Highly efficient simultaneous removal of atrazine and Cu(II) was accomplished using synthesized polyacrylic acid-functionalized magnetic ordered mesoporous carbon (P-MMC) as compared to magnetic ordered mesoporous carbon (MMC) and ordered mesoporous carbon (OMC). The mutual effects and interactive mechanism of their adsorption onto P-MMC were investigated systematically by binary, preloading and thermodynamic adsorption procedures. In both binary and preloading systems, the adsorption of atrazine was inhibited to some extent by the presence of Cu(II) because of selective recognition and direct competition, but the presence of atrazine had negligible effect on Cu(II) desorption. With the coexistence of humic acid (0–20 mg L−1), both atrazine and Cu(II) sorption increased slightly in sole and binary systems. With the concentration of coexisting NaCl increasing from 0 to 100 mM, the adsorption capacity for Cu(II) slightly decreased, but as for atrazine adsorption, it decreased at first, and then increased slightly in sole and binary systems. P-MMC was applied to treat real environmental samples, and the sorption capacities for atrazine and Cu(II) in real samples were all more than 91.47% and 96.43% of those in lab ultrapure water, respectively. Finally, comprehensively considering the relatively good renewability and the superior behavior in the application to real water samples, P-MMC has potential in removal of atrazine, Cu(II) and possibly other persistent organic pollutants from wastewater.

The fabrication and evaluation of a glassy carbon electrode (GCE) modified with ordered mesopo- rous carbon (OMC), 2-mercaptoethanesulfonate (MES)- tethered polyaniline (PANI) and bismuth for simultane- ous determination of trace Cd 2 + and Pb 2 + by differential pulse anodic stripping voltammetry (DPASV) are pre- sented here. The morphology and electrochemical proper- ties of the fabricated electrode were respectively charac- terized by scanning electron microscopy (SEM) and elec- trochemical impedance spectroscopy (EIS). Experimental parameters such as PANI disposition, preconcentration potential, preconcentration time and bismuth concentra- tion were optimized. Under optimum conditions, the fab- ricated electrode exhibited linear calibration curves ranged from 1 to 120 nM for Cd 2 + and Pb 2 + . The limits of detection (LOD) were 0.26 nM for Cd 2 + and 0.16 nM for Pb 2 + (S/N = 3), respectively. Additionally, repeatabili- ty, reproducibility, interference and application were also investigated, and the proposed electrode exhibited excel- lent performance. The proposed method could be extend- ed for the development of other new sensors for heavy metal determination.

Cobalt nanoparticles-embedded magnetic ordered mesoporous carbon (Co/OMC), prepared through a simple method involving infusing and calcination, was used as a highly effective adsorbent for rhodamine B (Rh B) removal. Several techniques, including SEM, HRTEM, nitrogen adsorption–desorption isotherms, XRD, Raman spectra, EDX, zeta potential and VSM measurement, were applied to characterize the adsorbent. Batch tests were conducted to investigate the adsorption performance. The adsorption capacity of the resultant adsorbent was relatively high compared with raw ordered mesoporous carbon (OMC) and reached an equilibrium value of 468 mg/g at 200 mg/L initial Rh B concentration. Removal efficiency even reached 96% within 25 min at 100 mg/L initial Rh B concentration. Besides, the adsorption amount increased with the increase of solution pH, adsorbent dose and initial Rh B concentration. Kinetics study showed that the adsorption agreed well with pseudo-second-order model ( R 2 = 0.999) and had a significant correlation with intra-particle diffusion model in the both two adsorption periods. Furthermore, thermodynamics research indicated that the adsorption process was endothermic and spontaneous in nature. The adsorption isotherms fitted well with Langmuir model, demonstrating the formation of mono-molecular layer on the surface of Co/OMC during adsorption process. The results confirmed that Co/OMC has the potential superiority in removal of Rh B from aqueous solution.

In this study, a magnetic iron nanoparticles doped ordered mesoporous carbon (Fe/CMK-3) was successfully prepared for highly effective removal of Cr(VI). The resultant carbon material maintained ordered mesostructure, high surface area of 679.4 m 2 g −1 with 4.42 wt% magnetic nanoparticles (Fe 0 , Fe 3 O 4 and λ-Fe 2 O 3 ) inside, and excellent magnetic property. Batch experiments were conducted to investigate the removal performance. Fe/CMK-3 exhibited higher Cr(VI) removal efficiency (∼97%), broader pH scope of application and easier separation compared with pristine ordered mesoporous carbon (CMK-3). The kinetics data were well described by pseudo-second-order kinetic model, and Langmuir model fitted the sorption isotherms commendably. Moreover, the Cr loaded Fe/CMK-3 could be regenerated by 0.01 mol L −1 NaOH solution, and the removal capacity decreased by ∼22% in the seventh cycle. X-ray photoelectron spectroscopy (XPS) analysis demonstrated that the Cr(VI) removal was a adsorption and synergistic reduction process owing to trivalent chromium Cr(III) occurring on the surface of Fe/CMK-3. The results suggested that Fe/CMK-3 had potential superiority in removal of Cr(VI) from wastewater.

The present study developed an α-ketoglutaric acid-modified magnetic chitosan (α-KA-Fe 3 O 4 /CS) for highly efficient adsorption of Cd(II) from aqueous solution. Several techniques, including transmission electron microscopy (TEM), Fourier transform infrared (FTIR) and vibrating sample magnetometer (VSM), were applied to characterize the adsorbent. Batch tests were conducted to investigate the Cd(II) adsorption performance of α-KA-Fe 3 O 4 /CS. The maximum adsorption efficiency of Cd(II) appeared at pH 6.0 with the value of 93%. The adsorption amount was large and even reached 201.2 mg/g with the initial Cd(II) concentration of 1000 mg/L. The adsorption equilibrium was reached within 30 min and commendably described by pseudo-second-order model, and Langmuir model fitted the adsorption isotherm better. Furthermore, thermodynamic parameters, free energy (Δ G ), enthalpy (Δ H ) and entropy (Δ S ) of Cd(II) adsorption were also calculated and showed that the overall adsorption process was endothermic and spontaneous in nature because of positive Δ H values and negative Δ G values, respectively. Moreover, the Cd(II)-loaded α-KA-Fe 3 O 4 /CS could be regenerated by 0.02 mol/L NaOH solution, and the cadmium removal capacity could still be kept around 89% in the sixth cycle. All the results indicated that α-KA-Fe 3 O 4 /CS was a promising adsorbent in environment pollution cleanup.

Magnetic mesoporous carbon incorporated with polyaniline (PANI–Fe/OMC) is developed for enhanced adsorption and reduction of toxic Cr(VI) to non-toxic Cr(III). Several physicochemical techniques including TEM, FTIR and XPS analyses confirmed that magnetic iron nanoparticles and amino groups have been successfully bound on the mesoporous matrix. The adsorption capacity of the functionalized material is two- and ten-fold that of the magnetic mesoporous carbon (Fe/OMC) and pristine mesoporous silicon (SBA-15), respectively. Solution pH exhibited a remarkable impact on the Cr(VI) adsorption and the maximum uptake amount (172.33 mg g−1) occurred at pH 2.0. The good fitting of adsorption process using pseudo-second-order and Langmuir models indicated the chemisorption process of Cr(VI) removal. The regeneration study revealed that PANI–Fe/OMC can be reused without loss of their activity in repetitive adsorption tests. Moreover, the resultant adsorbent can be effectively applied in actual wastewater treatment due to the excellent removal performance in fixed-bed column and real water samples. The interaction between Cr(VI) and PANI–Fe/OMC was investigated by FTIR and XPS analyses. The results indicate that the amino groups on the surface of PANI–Fe/OMC are involved in Cr(VI) uptake, and simultaneously some toxic Cr(VI) are reduced to non-toxic Cr(III) during the removal process.

This study demonstrates a new, unlabeled immobilized DNA-based biosensor with ordered mesoporous carbon nitride material (MCN) for the detection of Ag(+) by electrochemical impedance spectroscopy (EIS) with [Fe(CN)6](4-/3-) as the redox couple. The unlabeled immobilized DNA initially formed the hairpin-like structure through hybridization with the probe, and then changed to duplex-like structure upon interaction with Ag(+) in solution to form a C-Ag(+)-C complex at electrode surface. As a result, the interfacial charge-transfer resistance of the electrode towards the [Fe(CN)6](4-/3-) redox couple was changed. Thus, a declined charge transfer resistance (Rct) was obtained, corresponding to Ag(+) concentration. MCN provide an excellent platform for DNA immobilization and faster electron transfer. Impedance data were analyzed with the help of Randles equivalent circuit. The lower detection limit of the biosensor for Ag(+) is 5 × 10(-11) M with good specificity. All results showed that this novel approach provides a reliable method for Ag(+) detection with sensitivity and specificity, potentially useful for practical applications. Moreover, other DNA detection methods for more heavy metals may be obtained from this idea and applied in the environmental field.

Phosphate (P) removal is significant for the prevention of eutrophication in natural waters. In this paper, a novel adsorbent for the removal of P from aqueous solution was synthesized by loading zirconium oxide and iron oxide onto activated carbon nanofiber (ACF-ZrFe) simultaneously. The adsorbent was characterized by scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The results showed that P adsorption was highly pH dependent and the optimum pH was found to be 4.0. The isotherm of adsorption could be well described by the Langmuir model and the maximum P adsorption capacity was estimated to be 26.3mgP/g at 25°C. The kinetic data were well fitted to the pseudo-second-order equation, indicating that chemical sorption was the rate-limiting step. Moreover, co-existing ions including sulfate (SO42-), chloride (Cl-), nitrate (NO3-) and fluoride (F-) exhibited a distinct effect on P adsorption with the order of F->NO3->Cl->SO42-. Further investigations by FT-IR spectroscopy and pH variations associated with the adsorption process revealed that ligands exchange and electrostatic interactions were the dominant mechanisms for P adsorption. The findings reported in this work highlight the potential of using ACF-ZrFe as an effective adsorbent for the removal of P in natural waters.

Highly efficient simultaneous removal of Pb(II) and p-nitrophenol (PNP) contamination from water was accomplished by nitrogen-functionalized magnetic ordered mesoporous carbon (N-Fe/OMC). The mutual effects and inner mechanisms of their adsorption onto N-Fe/OMC were systematically investigated by sole and binary systems, and thermodynamic, sorption isotherm and adsorption kinetics models. The liquid-film diffusion step might be the rate-limiting step for PNP and Pb(II). The fitting of experimental data with Temkin model indicates that the adsorption process of PNP and Pb(II) involve physisorption and chemisorption. There exist site competition and enhancement of PNP and Pb(II) on the sorption to N-Fe/OMC. Moreover, N-Fe/OMC could be regenerated effectively and recycled by using dilute NaOH and acetone. These demonstrated superior properties of N-Fe/OMC indicate that it could be applied to treatment of wastewaters containing both lead and PNP.

A label–free electrochemical sensor, based on a classic lead ions (Pb 2+ )–dependent GR–5DNAzyme as the catalytic unit, disodium–anthraquinone–2,6–disulfonate (AQDS) as DNA intercalator, and nanoporous gold (NPG) for signal amplification, was designed for sensitive and selective detection of Pb 2+ . Firstly, NPG modified electrode surface were employed as a platform for the immobilization of thiolated probe DNA, and then, hybridized with DNAzyme catalytic beacons. The Pb 2+ –induced catalytic reaction makes the substrate strand break at the cleavage sitGe irreversibly, which disturbs the formation of DNA strands. AQDS served as an indicator that intercalated into the base–pairing regions of DNAzyme, resulting in a strong electrochemical signal. In the presence of Pb 2+ , the complementary regions were reduced, due to the fracture of the DNA strand, resulting in the release of AQDS. And a decreased current was obtained, corresponding to Pb 2+ concentration. Taking advantage of the amplification effect of NPG electrode for increasing the reaction sites of thiol modified capture probe, the proposed electrochemical biosensor could detect Pb 2+ quantitatively, in the range of 1–120 nM, with a limit of detection as low as 0.02 nM, which is much lower than the maximum contamination level for Pb 2+ in drinking water defined by the U.S. Environmental Protection Agency. The electrochemical sensor was also used to detect Pb 2+ from real water samples, and the results showed excellent agreement with the values determined by inductively coupled plasma mass spectroscopy. This biosensor showed a promising potential for on–site detecting Pb 2+ in aqueous environment.

Noble metal nanoparticles (NPs) applied in heterogeneous catalysis have attracted considerable attention due to their highly efficient catalytic performance. Pd/Au bimetallic NPs were successfully decorated on the ultrathin graphitic carbon nitride nanosheets (g-C3N4-N) by a facile one-pot deposition reduction method. The obtained results show that Pd/Au NPs with average diameter around 8 nm are homogeneously dispersed on the surface of unmodified g-C3N4-N. The obtained materials were characterized via transmission electron microscopy (TEM), high-resolution TEM, energy-dispersive X-ray spectroscopy, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). In addition, considering the large surface area and special π-bonded planar structure, the unique ultrathin g-C3N4-N behave as an excellent carrier and stabilizer in this synthesis. The as-synthesized Pd/Au bimetallic nanohybrids show superior catalytic performance and stability for reduction of p-nitrophenol (p-NP), which is better than either of pure Pd or Au nanohybrids. Besides, the catalytic activities of Pd/Au@g-C3N4-N nanohybrids were found to be controlled by altering the Pd versus Au mass ratio in the preparation process.

A simple, practical and reusable electrochemical aptasensor, based on thymine-Hg

Sulfidated nanoscale zerovalent iron (S-NZVI) is attracting considerable attention due to its easy production and high reactivity to pollutants. We studied the reactivity of optimized S-NZVI (Fe/S molar ratio 6.9), comparing with pristine nanoscale zerovalent iron (NZVI), at various pH solutions (6.77-9.11) towards p-nitrophenol (PNP) under aerobic and anoxic conditions. Studies showed that the optimized extent of sulfidation could utterly enhance PNP degradation compared to NZVI. Batch experiments indicated that in anoxic S-NZVI systems the degradation rate constant increased with increasing pH up to 7.60, and then declined. However, in aerobic S-NZVI, and in anoxic or aerobic NZVI systems, it decreased as pH increased. It was manifested that anoxic S-NZVI systems preferred to weaker alkaline solutions, whereas aerobic S-NZVI systems performed better in acidic solutions. The highest TOC removal efficiency of PNP (17.59%) was achieved in the aerobic S-NZVI system at pH 6.77, revealing that oxygen improved the degradation of PNP by excessive amounts of hydroxyl radicals in slightly acidic conditions, and the TOC removal efficiency was supposed to be further improved in moderate acidic solutions. Acetic acid, a nontoxic ring opening by-product, confirms that the S-NZVI system could be a promising process for industrial wastewater containing sulfide ions.

Many types of electrochemical biosensors employ magnetic nanoparticles which have been surface functionalized to recognize specific molecular targets. Here the paper emphatically introduced the operation principle of biosensing magnetic nanoparticles, the overall strategy for fabricating magnetic nanoparticles-based biosensor and the latest application progress in detecting lignocellulase activity and gene expression by electrochemical biosensors.

The magnetic chitosan microparticles were prepared by microemulsion method and raid removal of Cd(Ⅱ) and Pb(Ⅱ). Batch tests were carried out to investigate the adsorption performance. It was found that adsorption of Pb2+ and Cd2+ was dependent on pH, and increasing the pH is favorable for heavy metal ions removal. The sorption isotherms of the adsorbent for these metals fitted better with Freundlich model than the Langmuir model, with maximum adsorption capacities of 69.83 mg/g and 18.03 mg/g for Pb2+ and Cd2+, respectively. The adsorption equilibrium was reached within 15 min. The temperature effects revealed that the adsorption capacity increased significantly with increasing temperature, and the adsorption process was endothermic in nature at 25°C to 75°C.

The authors herein described an amplified detection strategy employing nanoporous Au (NPG) and gold nanoparticles (AuNPs) to detect Pb(2+) ions in aqueous solution. The thiol modified Pb(2+)-specific DNAzyme was self-assembled onto the surface of the NPG modified electrode for hybridizing with the AuNPs labeled oligonucleotide and for forming the DNA double helix structure. Electrochemical signal, redox charge of hexaammineruthenium(III) chloride (RuHex), was measured by chronocoulometry. Taking advantage of amplification effects of the NPG electrode for increasing the reaction sites of capture probe and DNA-AuNPs complexes for bringing about the adsorption of large numbers of RuHex molecules, this electrochemical sensor could detect Pb(2+) quantitatively, in the range of 0.05-100nM, with a limit of detection as low as 0.012nM. Selectivity measurements revealed that the sensor was specific for Pb(2+) even with interference by high concentrations of other metal ions. This sensor was also used to detect Pb(2+) ions from samples of tap water, river water, and landfill leachate samples spiked with Pb(2+) ions, and the results showed good agreement with the found values determined by an atomic fluorescence spectrometer. This simple aptasensor represented a promising potential for on-site detecting Pb(2+) in drinking water.

This paper investigated the key factors and mechanisms of sulfamethazine (SMT) sorption on a novel carbonaceous nanocomposite, and the effects of harsh aging on SMT sorption in the presence and absence of soil and before as well as after aging. The carbonaceous nanocomposites were synthesized by dip-coating straw biomass in carboxyl functionalized multi-walled carbon nanotubes solution and then pyrolyzed at 300 °C and 600 °C in the absence of air. The sorption performance of high temperature carbonaceous nanocomposite on SMT was excellent, as measured sorption distribution coefficient in the order of 10 3 –10 5.5 L kg −1 . Carbonaceous nanocomposites were aged either alone or mixed with soil via exposure to nutrients and soil extract (biological aging) or 80 °C for 100 d (chemical aging). No obvious effects of harsh aging on SMT sorption were observed in the presence of soil and/or biological and chemical aging. The primary mechanisms for SMT sorption included partition caused by Van der Waals forces and adsorption caused by hydrogen bonding and π-π electron-donor-acceptor interaction. Comprehensively considering the cost, renewability, and the application to real water samples, the carbonaceous nanocomposites have potential in removal of SMT and possibly other persistent organic pollutants from wastewater.

The fabrication and evaluation of a glassy carbon electrode (GCE) modified with self-doped polyaniline nanofibers (SPAN)/mesoporous carbon nitride (MCN) and bismuth for simultaneous determination of trace Cd2+ and Pb2+ by square wave anodic stripping voltammetry (SWASV) are presented here. The morphology properties of SPAN and MCN were characterized by transmission electron microscopy (TEM), and the electrochemical properties of the fabricated electrode were characterized by cyclic voltammetry (CV). Experimental parameters, such as deposition time, pulse potential, step potential, bismuth concentration and NaCl concentration, were optimized. Under the optimum conditions, the fabricated electrode exhibited linear calibration curves ranging from 5 to 80 nM for Cd2+ and Pb2+. The limits of detection (LOD) were 0.7 nM for Cd2+ and 0.2 nM for Pb2+ (S/N = 3). Additionally, the repeatability, reproducibility, anti-interference ability and application were also investigated, and the proposed electrode exhibited excellent performance. The proposed method could be extended for other heavy metal determination.

Cadmium (Cd) is a detrimental metal in the environment and it is easily taken up by plants, thus entering the food chain and posing a severe threat to human health. Phytoremediation being low cost, highly stable, and environmentally friendly has been considered as a promising green technology for Cd remediation. The addition of exogenous substances to the culture media has been recognized as an efficient strategy to improve plant phytoremediation capability. Pot trials were conducted to investigate the combined effects of exogenous calcium (Ca) and spermidine (Spd) on Cd-induced toxicity in Boehmeria nivea (L.) Gaudich. (ramie). Results showed that the application of 5-mM exogenous Ca significantly alleviated Cd toxicity in ramie by reducing Cd accumulation, depressing H2O2 and malondialdehyde contents, increasing plants dry weights and chlorophyll concentrations, as well as altering the activities of total superoxide dismutase and guaiacol peroxidase. Furthermore, as a non-Cd hyperaccumulator plant, ramie hyperaccumulated Cd and suffered more severe toxic effects of Cd by the treatment of 1 mM Ca/Cd. The aggravated Cd toxicity could be compensated by the addition of exogenous Spd via the promotion of plant growth and the reduction of the oxidative stress. Overall, the combination effects of 1 mM Ca and Spd appeared to be more superior compared to other treatments in the plants under Cd stress with a higher Cd accumulation ability and the evaluated Cd stress tolerance.

Photocatalytic degradation is an alternative method to remove pharmaceutical compounds in water, however it is hard to achieve efficient rate because of the poor solubility of pharmaceutical compounds in water. This study investigated the photodegradation of norfloxacin in a nonionic surfactant Triton-X100 (TX100)/Bi2WO6 dispersion under visible light irradiation (400-750nm). It was found that the degradation of poorly soluble NOF can be strongly enhanced with the addition of TX100. TX100 was adsorbed strongly on Bi2WO6 surface and accelerated NOF photodegradation at the critical micelle concentration (CMC=0.25mM). Higher TX100 concentration (>0.25mM) lowered the degradation rate. In the presence of TX100, the degradation rate reached the maximum value when the pH value was 8.06. FTIR analyses demonstrated that the adsorbed NOF on the catalyst was completely degraded after 2h irradiation. According to the intermediates identified by HPLC/MS/MS, three possible degradation pathways were proposed to include addition of hydroxyl radical to quinolone ring, elimination of piperazynilic ring in fluoroquinolone molecules, and replacement of F atoms on the aromatic ring by hydroxyl radicals.

A novel label-free impedimetric sensing system based on DNAzyme and ordered mesoporous carbon-gold nanoparticle (OMC-GNPs) for the determination of Pb(2+) concentration was developed in the present study. Firstly, gold nanoparticles deposited on the modified electrode surface were employed as a platform for the immobilization of thiolated probe DNA, and then hybridized with DNAzyme catalytic beacons. Subsequently, in the presence of Pb(2+), the DNAzyme could be activated to cleave the substrate strand into two DNA fragments, which causes differences in the electrical properties of the film. Randles equivalent circuit was employed to evaluate the electrochemical impedance spectroscopy (EIS) result. The charge transfer resistance (R(CT)) value for the [Fe(CN)6](3-/4-) redox indicator was remarkably decline after hybridization with Pb(2+). The difference in RCT values before and after hybridization with Pb(2+) showed a linear relation with the concentration of the Pb(2+) in a range of 5×10(-10)-5×10(-5) M, with a detection limit of 2×10(-10) M (S/N=3). Furthermore, with the application of Pb(2+) dependent 8-17DNAzyme, the proposed sensing system exhibited high selectivity without using any labeled probes. This biosensor demonstrated a promising potential for Pb(2+) detection in real sample.

Magnetic Fe/Ni nanoparticles doped bimodal mesoporous carbon (MBMC) was prepared for highly effective adsorption of cationic dye methylene blue (MB) and anionic dye methyl orange (MO). Structure characterization demonstrated that Fe/Ni nanoparticles were embedded into the interior of the mesoprous carbon, and MBMC maintained ordered and bimodal mesopores. The effects of several parameters such as contact time, pH, temperature, ionic strength and dye molecular structure on the adsorption were investigated. Alkaline pH was better for MB adsorption, while acidic pH was more favorable for MO uptake. The adsorption capacity was slightly enhanced when existing ion concentrations increased. Adsorption on MBMC was affected by the molecular structures of different dyes, and both primary and secondary pores of MBMC were involved in dye adsorption. The adsorption kinetics fitted well with pseudo-second-order model and exhibited 3-stage intraparticle diffusion mode. Equilibrium data were best described by Langmuir model, and the estimated maximum adsorption capacity for MB and MO was 959.5mg/g and 849.3mg/g, respectively. Thermodynamic studies indicated that the adsorption process was spontaneous and endothermic. Moreover, the adsorbent could be regenerated using ethanol, and the regenerated adsorbent after seven cycles could retain over 80% of the adsorption capacity for the fresh adsorbent. The results suggested that MBMC could be considered as very effective and promising materials for both anionic and cationic dyes removal from wastewater.

Herein, we reported here a promising biosensor by taking advantage of the unique ordered mesoporous carbon nitride material (MCN) to convert the recognition information into a detectable signal with enzyme firstly, which could realize the sensitive, especially, selective detection of catechol and phenol in compost bioremediation samples. The mechanism including the MCN based on electrochemical, biosensor assembly, enzyme immobilization, and enzyme kinetics (elucidating the lower detection limit, different linear range and sensitivity) was discussed in detail. Under optimal conditions, GCE/MCN/Tyr biosensor was evaluated by chronoamperometry measurements and the reduction current of phenol and catechol was proportional to their concentration in the range of 5.00 × 10(-8)-9.50 × 10(-6)M and 5.00 × 10(-8)-1.25 × 10(-5)M with a correlation coefficient of 0.9991 and 0.9881, respectively. The detection limits of catechol and phenol were 10.24 nM and 15.00 nM (S/N=3), respectively. Besides, the data obtained from interference experiments indicated that the biosensor had good specificity. All the results showed that this material is suitable for load enzyme and applied to the biosensor due to the proposed biosensor exhibited improved analytical performances in terms of the detection limit and specificity, provided a powerful tool for rapid, sensitive, especially, selective monitoring of catechol and phenol simultaneously. Moreover, the obtained results may open the way to other MCN-enzyme applications in the environmental field.

A novel biosensor was developed based on tyrosinase immobilization with ordered mesoporous carbon-Au (OMC-Au), L-lysine membrane and Au nanoparticles on a glassy carbon electrode (GCE). It was applied for the simultaneous determination of dihydroxybenzene isomers using differential pulse voltammetry (DPV). The tyrosinase/OMC-Au/L-lysine/Au film was characterized by scanning electron microscopy (SEM) and impedance spectra. Under optimized conditions, the DPV study results for two isomers, hydroquinone (HQ, 1,4-dihydroxybenzene) and catechol (CC, 1,2-dihydroxybenzene) showed low peak potentials, and the peak-to-peak difference was about 135.85 mV, which ensured the anti-interference ability of the biosensor and made simultaneous detection of dihydroxybenzene isomers possible in real samples. DPV peak currents increased linearly with concentration over the range of 4.0 × 10(-7) to 8.0 × 10(-5) M, and the detection limits of hydroquinone and catechol were 5 × 10(-8) M and 2.5 × 10(-8) M (S/N = 3), respectively. The tyrosinase biosensor exhibited good repeatability and stability. In addition, the response mechanism of enzyme catalysed redox on the OMC-Au/L-lysine/Au film modified electrode based on electrochemical study was discussed. The proposed method could be extended for the development of other enzyme-based biosensors.

The fabrication and evaluation of a glassy carbon electrode (GCE) modified with self-doped polyaniline nanofibers (SPAN)/mesoporous carbon nitride (MCN) and bismuth for simultaneous determination of trace Cd2+ and Pb2+ by square wave anodic stripping voltammetry (SWASV) are presented here. The morphology properties of SPAN and MCN were characterized by transmission electron microscopy (TEM), and the electrochemical properties of the fabricated electrode were characterized by cyclic voltammetry (CV). Experimental parameters, such as deposition time, pulse potential, step potential, bismuth concentration and NaCl concentration, were optimized. Under the optimum conditions, the fabricated electrode exhibited linear calibration curves ranging from 5 to 80 nM for Cd2+ and Pb2+. The limits of detection (LOD) were 0.7 nM for Cd2+ and 0.2 nM for Pb2+ (S/N = 3). Additionally, the repeatability, reproducibility, anti-interference ability and application were also investigated, and the proposed electrode exhibited excellent performance. The proposed method could be extended for other heavy metal determination.