Fabrication of magnetic multi-template molecularly imprinted polymer composite for the selective and efficient removal of tetracyclines from water

• Magnetic multi-template molecularly imprinted polymer composite was synthesized. • MIP composite was used as the adsorbent for removal of tetracyclines from water. • MIP composite showed excellent adsorption selectivity toward tetracyclines. • MIP composite possessed good reusability. Antibiotic contamination of the water environment has attracted much attention from researchers because of their potential hazards to humans and ecosystems. In this study, a multi-template molecularly imprinted polymer (MIP) modified mesoporous silica coated magnetic graphene oxide (MGO@MS@MIP) was prepared by the surface imprinting method via a sol-gel process and was used for the selective, efficient and simultaneous removal of tetracyclines (TCs), including doxycycline (DC), tetracycline (TC), chlorotetracycline (CTC) and oxytetracycline (OTC) from water. The synthesized MIP composite was characterized by Fourier transform infrared spectroscopy, transmission electron microscope and thermogravimetric analysis. The adsorption properties of MGO@MS@MIP for these TCs were characterized through adsorption kinetics, isotherms and selectivity tests. The MIP composite revealed larger adsorption quantities, excellent selectivity and rapid kinetics for these four tetracyclines. The adsorption process was spontaneous and endothermic and followed the Freundlich isotherm model and the pseudo-second-order kinetic model. The MGO@MS@MIP could specifically recognize DC, TC, CTC and OTC in the presence of some chemical analogs. In addition, the sorption capacity of the MIP composite did not decrease significantly after repeated application for at least five cycles. Thus, the prepared magnetic MIP composite has great potential to contribute to the effective separation and removal of tetracyclines from water.     

Nanoscale zero-valent iron supported on biochar for the highly efficient removal of nitrobenzene

• Biochar supported nanoscale zero-valent iron composite (nZVI/BC) was synthesized. • nZVI/BC quickly and efficiently removed nitrobenzene (NB) in solution. • NB removal by nZVI/BC involves simultaneous adsorption and reduction mechanism. • nZVI/BC exhibited better catalytic activity, stability and durability than nZVI. The application of nanoscale zero-valent iron (nZVI) in the remediation of contaminated groundwater or wastewater is limited due to its lack of stability, easy aggregation and iron leaching. To address this issue, nZVI was distributed on oak sawdust-derived biochar (BC) to obtain the nZVI/BC composite for the highly efficient reduction of nitrobenzene (NB). nZVI, BC and nZVI/BC were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). For nZVI/BC, nZVI particles were uniformly dispersed on BC. nZVI/BC exhibited higher removal efficiency for NB than the simple summation of bare nZVI and BC. The removal mechanism was investigated through the analyses of UV-Visible spectra, mass balance and XPS. NB was quickly adsorbed on the surface of nZVI/BC, and then gradually reduced to aniline (AN), accompanied by the oxidation of nZVI to magnetite. The effects of several reaction parameters, e.g., NB concentration, reaction pH and nZVI/BC aging time, on the removal of NB were also studied. In addition to high reactivity, the loading of nZVI on biochar significantly alleviated Fe leaching and enhanced the durability of nZVI.     

Synthesis of vinasse-dolomite nanocomposite biochar via a novel developed functionalization method to recover phosphate as a potential fertilizer substitute

• Nanocomposites were prepared by adding dolomite to vinasse at different ratio. • Textural and morphological features of adsorbents were studied in detail. • CCD based RSM was used for investigation of P ion removal by nanocomposite. • The q_m based on Langmuir model for modified vinasse biochar was 178.57 mg/g. • P loaded nanocomposite improved plant growth and could be utilized as P-fertilizer. The effectiveness of phosphate (P) removal from aqueous solutions was investigated by novel low-cost biochars synthesized from vinasse and functionalized with calcined dolomite. The vinasse-derived biochar, synthesized via pyrolysis at different temperatures, showed easy preparation and a large surface area. The novel vinasse biochar nanocomposites were prepared by adding dolomite to the vinasse biochars with different weight percentages (10, 20 and 30%). The characteristics of the prepared materials were identified for further understanding of the inherent adsorption mechanism between P ions and vinasse biochars. Vinasse-dolomite nanocomposite was very effective in the adsorption of P species from aqueous media. The effect of the operational factors on Vinasse-dolomite nanocomposite was explored by applying response surface methodology (RSM). According to RSM results, the optimum condition was achieved to be contact time 90 (min), 250 (mg/L) of P concentration and pH 7. Thermodynamic isotherm and kinetic studies were applied on experimental data to understand the adsorption behavior. The Vinasse-dolomite nanocomposite revealed preferential P species adsorption in the presence of co-existing anions. The P species could be recovered by 1.0 M HCl where the efficiency was not affected up to the fifth cycle. The P-loaded Vinasse-dolomite nanocomposite was successfully tested on a plant; it significantly improved its growth and proved its potency as a P-based fertilizer substitute.     

Bioinspired cellulose-based membranes in oily wastewater treatment

• Cellulose-based membrane separates oily wastewater mimicking the living things. • The three central surface mechanisms were reviewed. • Preparation, performance, and mechanism are critically evaluated. • First review of wettability based cellulose membrane as major material. • The current and future importance of the research are discussed. It is challenging to purify oily wastewater, which affects water-energy-food production. One promising method is membrane-based separation. This paper reviews the current research trend of applying cellulose as a membrane material that mimics one of three typical biostructures: superhydrophobic, underwater superoleophobic, and Janus surfaces. Nature has provided efficient and effective structures through the evolutionary process. This has inspired many researchers to create technologies that mimic nature’s structures or the fabrication process. Lotus leaves, fish scales, and Namib beetles are three representative structures with distinct functional and surface properties: superhydrophobic, underwater superoleophobic, and Janus surfaces. The characteristics of these structures have been widely studied and applied to membrane materials to improve their performance. One attractive membrane material is cellulose, which has been studied from the perspective of its biodegradability and sustainability. In this review, the principles, mechanisms, fabrication processes, and membrane performances are summarized and compared. The theory of wettability is also described to build a comprehensive understanding of the concept. Finally, future outlook is discussed to challenge the gap between laboratory and industrial applications.     

Adsorption characteristics of ciprofloxacin onto g-MoS2 coated biochar nanocomposites

• The g-MoS₂ coated composites (g-MoS₂-BC) were synthesized. • The coated g-MoS₂ greatly increased the adsorption ability of biochar. • The synergistic effect was observed for CIP adsorption on g-MoS₂-RC700. • The adsorption mechanisms of CIP on g-MoS₂-BC were proposed. The g-MoS₂ coated biochar (g-MoS₂-BC) composites were synthesized by coating original biochar with g-MoS₂ nanosheets at 300°C(BC300)/700°C (BC700). The adsorption properties of the g-MoS₂-BC composites for ciprofloxacin (CIP) were investigated with an aim to exploit its high efficiency toward soil amendment. The specific surface area and the pore structures of biochar coated g-MoS₂ nanosheets were significantly increased. The g-MoS₂-BC composites provided more π electrons, which was favorable in enhancing the π-π electron donor-acceptor (EDA) interactions between CIP and biochar. As a result, the g-MoS₂-BC composites showed faster adsorption rate and greater adsorption capacity for CIP than the original biochar. The coated g-MoS₂ nanosheets contributed more to CIP adsorption on the g-MoS₂-BC composites due to their greater CIP adsorption capacity than the original biochar. Moreover, the synergistic effect was observed for CIP adsorption on g-MoS₂-BC700, and suppression effect on g-MoS₂-BC300. In addition, the adsorption of CIP onto g-MoS₂-BC composites also exhibited strong dependence on the solution pH, since it can affect both the adsorbent surface charge and the speciation of contaminants. It was reasonably suggested that the mechanisms of CIP adsorption on g-MoS₂-BC composites involved pore-filling effects, π-π EDA interaction, electrostatic interaction, and ion exchange interaction. These results are useful for the modification of biochar in exploiting the novel amendment for contaminated soils.     

A “Seawater-in-Sludge” approach for capacitive biochar production via the alkaline and alkaline earth metals activation

• Capacitive biochar was produced from sewage sludge. • Seawater was proved to be an alternative activation agent. • Minerals vaporization increased the surface area of biochar. • Molten salts acted as natural templates for the development of porous structure. Sewage sludge is a potential precursor for biochar production, but its effective utilization involves costly activation steps. To modify biochar properties while ensuring cost-effectiveness, we examined the feasibility of using seawater as an agent to activate biochar produced from sewage sludge. In our proof-of-concept study, seawater was proven to be an effective activation agent for biochar production, achieving a surface area of 480.3 m²/g with hierarchical porosity distribution. Benefited from our design, the catalytic effect of seawater increased not only the surface area but also the graphitization degree of biochar when comparing the pyrolysis of sewage sludge without seawater. This leads to seawater activated biochar electrodes with lower resistance, higher capacitance of 113.9 F/g comparing with control groups without seawater. Leveraging the global increase in the salinity of groundwater, especially in coastal areas, these findings provide an opportunity for recovering a valuable carbon resource from sludge.     

Crosslinking acrylamide with EDTA-intercalated layered double hydroxide for enhanced recovery of Cr(VI) and Congo red: Adsorptive and mechanistic study

• Functional groups of AM and EDTA in composite increased removal of Cr(VI) and CR. • Removal process reached equilibrium within 30 min and was minimally affected by pH. • Elimination of Cr(VI) was promoted by coexisting CR. • Adsorption process of CR was less influenced by the presence of Cr(VI). • Mechanisms were electrostatic attraction, surface complexation and anion exchange. We prepared ethylenediaminetetraacetic acid (EDTA)-intercalated MgAl-layered double hydroxide (LDH-EDTA), then grafted acrylamide (AM) to the LDH-EDTA by a cross-linking method to yield a LDH-EDTA-AM composite; we then evaluated its adsorptive ability for Congo red (CR) and hexavalent chromium (Cr(VI)) in single and binary adsorption systems. The adsorption process on LDH-EDTA-AM for CR and Cr(VI) achieved equilibrium quickly, and the removal efficiencies were minimally affected by initial pH. The maximum uptake quantities of CR and Cr(VI) on LDH-EDTA-AM were 632.9 and 48.47 mg/g, respectively. In mixed systems, chromate removal was stimulated by the presence of CR, while the adsorption efficiency of CR was almost not influenced by coexisting Cr(VI). The mechanisms involved electrostatic attraction, surface complexation, and anion exchange for the adsorption of both hazardous pollutants. In the Cr(VI) adsorption process, reduction also took place. The removal efficiencies in real contaminated water were all higher than those in the laboratory solutions.     

Ammonia and phosphorus removal from agricultural runoff using cash crop waste-derived biochars

• Orange tree residuals biochar had a better ability to adsorb ammonia. • Modified tea tree residuals biochar had a stronger ability to remove phosphorus. • Partially-modified biochar could remove ammonia and phosphorus at the same time. • The real runoff experiment showed an ammonia nitrogen removal rate of about 80%. • The removal rate of total phosphorus in real runoff experiment was about 95%. Adsorption of biochars (BC) produced from cash crop residuals is an economical and practical technology for removing nutrients from agricultural runoff. In this study, BC made of orange tree trunks and tea tree twigs from the Laoguanhe Basin were produced and modified by aluminum chloride (Al-modified) and ferric sulfate solutions (Fe-modified) under various pyrolysis temperatures (200°C–600°C) and residence times (2–5 h). All produced and modified BC were further analyzed for their abilities to adsorb ammonia and phosphorus with initial concentrations of 10–40 mg/L and 4–12 mg/L, respectively. Fe-modified Tea Tree BC 2h/400°C showed the highest phosphorus adsorption capacity of 0.56 mg/g. Al-modified Orange Tree BC 3h/500°C showed the best performance for ammonia removal with an adsorption capacity of 1.72 mg/g. FTIR characterization showed that P = O bonds were formed after the adsorption of phosphorus by modified BC, N-H bonds were formed after ammonia adsorption. XPS analysis revealed that the key process of ammonia adsorption was the ion exchange between K⁺ and NH₄⁺. Phosphorus adsorption was related to oxidation and interaction between PO₄^3– and Fe³⁺. According to XRD results, ammonia was found in the form of potassium amide, while phosphorus was found in the form of iron hydrogen phosphates. The sorption isotherms showed that the Freundlich equation fits better for phosphorus adsorption, while the Langmuir equation fits better for ammonia adsorption. The simulated runoff infiltration experiment showed that 97.3% of ammonia was removed by Al-modified Orange tree BC 3h/500°C, and 92.9% of phosphorus was removed by Fe-modified Tea tree BC 2h/400°C.     

Wastewater treatment meets artificial photosynthesis: Solar to green fuel production,water remediation and carbon emission reduction

• Mitigating energy utilization and carbon emission is urgent for wastewater treatment. • MPEC integrates both solar energy storage and wastewater organics removal. • Energy self-sustaining MPEC allows to mitigate the fossil carbon emission. • MPEC is able to convert CO₂ into storable carbon fuel using renewable energy. • MPEC would inspire photoelectrochemistry by employing a novel oxidation reaction. Current wastewater treatment (WWT) is energy-intensive and leads to vast CO₂ emissions. Chinese pledge of “double carbon” target encourages a paradigm shift from fossil fuels use to renewable energy harvesting during WWT. In this context, hybrid microbial photoelectrochemical (MPEC) system integrating microbial electrochemical WWT with artificial photosynthesis (APS) emerges as a promising approach to tackle water-energy-carbon challenges simultaneously. Herein, we emphasized the significance to implement energy recovery during WWT for achieving the carbon neutrality goal. Then, we elucidated the working principle of MPEC and its advantages compared with conventional APS, and discussed its potential in fulfilling energy self-sustaining WWT, carbon capture and solar fuel production. Finally, we provided a strategy to judge the carbon profit by analysis of energy and carbon fluxes in a MPEC using several common organics in wastewater. Overall, MPEC provides an alternative of WWT approach to assist carbon-neutral goal, and simultaneously achieves solar harvesting, conversion and storage.     

Biotoxicity evaluation of zinc oxide nanoparticles on bacterial performance of activated sludge at COD,nitrogen, and phosphorus reduction

• ZnO-NP disrupted metabolic/catabolic balance of bacteria by affecting DHA activity. • ZnO-NPs toxicity was related to Zn²⁺ ion, interaction with cell and ROS generation. • Exposure to ZnO-NPs resulted in changed bacterial community structure at sludge. • The change in the EPS content was observed during exposure to ZnO-NPs. The unique properties and growing usage of zinc oxide nanoparticles increase their release in municipal wastewater treatment plants. Therefore, these nanoparticles, by interacting with microorganisms, can fail the suitable functioning of biological systems in treatment plants. For this reason, research into the toxicity of ZnO is urgent. In the present study, the toxicity mechanism of ZnO-NPs towards microbial communities central to granular activated sludge (GAS) performance was assessed over 120-day exposure. The results demonstrate that the biotoxicity of ZnO-NPs is dependent upon its dosage, exposure time, and the extent of reactive oxygen species (ROS) production. Furthermore, GAS performance and the extracellular polymeric substances (EPS) content were significantly reduced at 50 mg/L ZnO-NPs. This exposure led to decreases in the activity of ammonia monooxygenase (25.2%) and nitrate reductase (11.9%) activity. The Field emission scanning electron microscopy images confirmed that ZnO-NPs were able to disrupt the cell membrane integrity and lead to cell/bacterial death via intracellular ROS generation which was confirmed by the Confocal Laser Scanning Microscopy analysis. After exposure to the NPs, the bacterial community composition shifted to one dominated by Gram-positive bacteria. The results of this study could help to develop environmental standards and regulations for NPs applications and emissions.     

Bioinspired and biomimetic membranes for water purification and chemical separation: A review

•The history of biological and artificial water channels is reviewed. •A comprehensive channel characterization platform is introduced. •Rationale designs and fabrications of biomimetic membranes are summarized. •The advantages, limitations, and challenges of biomimetic membranes are discussed. •The prospect and scalable solutions of biomimetic membranes are discussed. Bioinspired and biomimetic membranes that contain biological transport channels or attain their structural designs from biological systems have been through a remarkable development over the last two decades. They take advantage of the exceptional transport properties of those channels, thus possess both high permeability and selectivity, and have emerged as a promising solution to existing membranes. Since the discovery of biological water channel proteins aquaporins (AQPs), extensive efforts have been made to utilize them to make separation membranes–AQP-based membranes, which have been commercialized. The exploration of AQPs’ unique structures and transport properties has resulted in the evolution of biomimetic separation materials from protein-based to artificial channel-based membranes. However, large-scale, defect-free biomimetic membranes are not available yet. This paper reviews the state-of-the-art biomimetic membranes and summarizes the latest research progress, platform, and methodology. Then it critically discusses the potential routes of this emerging area toward scalable applications. We conclude that an appropriate combination of bioinspired concepts and molecular engineering with mature polymer industry may lead to scalable polymeric membranes with intrinsic selective channels, which will gain the merit of both desired selectivity and scalability.     

Removal and recovery of toxic nanosized Cerium Oxide using eco-friendly Iron Oxide Nanoparticles

• Eco-friendly IONPs were synthesized through solvothermal method. • IONPs show very high removal efficiency for CeO₂ NPs i.e. 688 mg/g. • Removal was >90% in all synthetic and real water samples. • >80% recovery of CeO₂ NPs through sonication confirms reusability of IONPs. Increasing applications of metal oxide nanoparticles and their release in the natural environment is a serious concern due to their toxic nature. Therefore, it is essential to have eco-friendly solutions for the remediation of toxic metal oxides in an aqueous environment. In the present study, eco-friendly Iron Oxide Nanoparticles (IONPs) are synthesized using solvothermal technique and successfully characterized using scanning and transmission electron microscopy (SEM and TEM respectively) and powder X-Ray diffraction (PXRD). These IONPs were further utilized for the remediation of toxic metal oxide nanoparticle, i.e., CeO₂. Sorption experiments were also performed in complex aqueous solutions and real water samples to check its applicability in the natural environment. Reusability study was performed to show cost-effectiveness. Results show that these 200 nm-sized spherical IONPs, as revealed by SEM and TEM analysis, were magnetite (Fe₃O₄) and contained short-range crystallinity as confirmed from XRD spectra. Sorption experiments show that the composite follows the pseudo-second-order kinetic model. Further R²>0.99 for Langmuir sorption isotherm suggests chemisorption as probable removal mechanism with monolayer sorption of CeO₂ NPs on IONP. More than 80% recovery of adsorbed CeO₂ NPs through ultrasonication and magnetic separation of reaction precipitate confirms reusability of IONPs. Obtained removal % of CeO₂ in various synthetic and real water samples was>90% signifying that IONPs are candidate adsorbent for the removal and recovery of toxic metal oxide nanoparticles from contaminated environmental water samples.     

Size and shape effects of MnFe2O4 nanoparticles as catalysts for reductive degradation of dye pollutants

• Size and shape-dependent MnFe₂O₄ NPs were prepared via a facile method. • Ligand-exchange chemistry was used to prepare the hydrophilic MnFe₂O₄ NPs. • The catalytic properties of MnFe₂O₄ NPs toward dye degradation were fully studied. • The catalytic activities of MnFe₂O₄ NPs followed Michaelis–Menten behavior. • All the MnFe₂O₄ NPs exhibit selective degradation to different dyes. The magnetic nanoparticles that are easy to recycle have tremendous potential as a suitable catalyst for environmental toxic dye pollutant degradation. Rationally engineering shapes and tailoring the size of nanocatalysts are regarded as an effective manner for enhancing performances. Herein, we successfully synthesized three kinds of MnFe₂O₄ NPs with distinctive sizes and shapes as catalysts for reductive degradation of methylene blue, rhodamine 6G, rhodamine B, and methylene orange. It was found that the catalytic activities were dependent on the size and shape of the MnFe₂O₄ NPs and highly related to the surface-to-volume ratio and atom arrangements. Besides, all these nanocatalysts exhibit selectivity to different organic dyes, which is beneficial for their practical application in dye pollutant treatment. Furthermore, the MnFe₂O₄ NPs could be readily recovered by a magnet and reused more than ten times without appreciable loss of activity. The size and shape effects of MnFe₂O₄ nanoparticles demonstrated in this work not only accelerate further understanding the nature of nanocatalysts but also contribute to the precise design of nanoparticles catalyst for pollutant degradation.     

Co-pyrolysis of sludge and kaolin/zeolite in a rotary kiln: Analysis of stabilizing heavy metals

• Adding kaolin/zeolite promotes the formation of stable heavy metals. • The potential ecological risk index of co-pyrolysis biochar is extremely low. • Increasing the pyrolysis temperature reduces the leaching toxicity of heavy metals. • The toxicity of biochar reduces with the increasing content of stable heavy metals. Pyrolysis is a promising technique used for treating of sewage sludge. However, the application of pyrolysis products is limited due to the presence of heavy metals. In this study, sewage sludge mixed with kaolin/zeolite was pyrolyzed in a rotary kiln, aiming to improve the immobilization of heavy metals in pyrolytic carbon. The total concentrations, speciation distributions, leaching toxicities, and potential ecological risk indices of heavy metals in pyrolysis biochar were explored to examine the effects of kaolin/zeolite and pyrolytic temperature on immobilizing heavy metals. Further, mineral composition and surface morphology of biochar were characterized by X-ray diffraction and scanning electron microscopy to reveal the potential mechanism of immobilizing heavy metals. Increasing pyrolysis temperature facilitated the stabilization of heavy metals in pyrolysis biochar. The proportions of stable heavy metals in biochar obtained at 650℃ were 54.50% (Cu), 29.73% (Zn), 79.29% (Cd), 68.17% (Pb) and 86.70% (Cr). Compared to sewage sludge, the potential contamination risk index of pyrolysis biochar obtained at 650℃ was reduced to 17.01, indicating a low ecological risk. The addition of 7% kaolin/zeolite further reduced the risk index of co-pyrolysis biochar prepared at 650℃ to 10.86/15.28. The characterization of biochar revealed that increase in the pyrolysis temperature and incorporation of additives are conducive to the formation of stable heavy metal-inorganics. This study demonstrates that the formation of stable mineral compounds containing heavy metals is the key to stabilizing heavy metals in pyrolysis biochar.     

Dual-functional sites for synergistic adsorption of Cr(VI) and Sb(V) by polyaniline-TiO2 hydrate: Adsorption behaviors,sites and mechanisms

• PANI/Ti(OH)_n^(4–n)+ exhibited excellent adsorption capacity and reusability. • Adsorption sites of Cr(VI) were hydroxyl, amino/imino group and benzene rings. • Sb(V) was adsorbed mainly through hydrogen bonds and Ti-O-Sb. • The formation of Cr-O-Sb in dual system demonstrated the synergistic adsorption. • PANI/TiO₂ was a potential widely-applied adsorbent and worth further exploring. Removal of chromium (Cr) and antimony (Sb) from aquatic environments is crucial due to their bioaccumulation, high mobility and strong toxicity. In this work, a composite adsorbent consisting of Ti(OH)_n^(4–n)+ and polyaniline (PANI) was designed and successfully synthesized by a simple and eco-friendly method for the uptake of Cr(VI) and Sb(V). The synthetic PANI/TiO₂ composites exhibited excellent adsorption capacities for Cr(VI) and Sb(V) (394.43 mg/g for Cr(VI) and 48.54 mg/g for Sb(V)), wide pH applicability and remarkable reusability. The adsorption of Cr(VI) oxyanions mainly involved electrostatic attraction, hydrogen bonding and anion-π interactions. Based on X-ray photoelectron spectroscopy and FT-IR analysis, the adsorption sites were shown to be hydroxyl groups, amino/imino groups and benzene rings. Sb(V) was adsorbed mainly through hydrogen bonds and surface complexation to form Ti-O-Sb complexes. The formation of Cr-O-Sb in the dual system demonstrated the synergistic adsorption of Cr(VI) and Sb(V). More importantly, because of the different adsorption sites, the adsorption of Cr(VI) and Sb(V) occurred independently and was enhanced to some extent in the dual system. The results suggested that PANI/TiO₂ is a promising prospect for practical wastewater treatment in the removal of Cr(VI) and Sb(V) from wastewater owing to its availability, wide applicability and great reusability.     

Valorization of agro-industrial fruit peel waste to fluorescent nanocarbon sensor: Ultrasensitive detection of potentially hazardous tropane alkaloid

• Transformation of agro-industrial waste to value-added material via green chemistry. • Orange peel is valorized into fluorescent nanodiamond-like carbon (fNDC) sensor. • fNDC detects potentially hazardous drug atropine sulfate (AS). • fNDC recognizes AS in biological fluids and pharmaceuticals. • fNDC assures applications in clinical and forensic toxicology. Millions of tonnes of agro-industrial waste are generated each year globally, with the vast majority of it going untreated, underutilized, and disposed of by burning or landfilling, causing severe environmental distress and economic downturn. A practical solution to this global issue is to use green chemistry to convert this waste into value-added products. Accordingly, in the present study, agro-industrial orange peel waste was valorized into fluorescent nanodiamond-like carbon sensor via a green route involving hydrothermal treatment of microwave carbonized orange peel waste. The developed sensor, used for the fluorescence detection of potentially hazardous drug atropine sulfate, exhibits unique dual linearity over concentration ranges of 300 nM to 1 M and from 1 M to 10 M, as well as ultra-low sensitivity of 34.42 nM and 356.46 nM, respectively. Additionally, the sensor demonstrates excellent reproducibility, high stability, and satisfactory recovery when used to identify and quantify atropine sulfate in biological samples and commercially available pharmaceuticals, indicating promising multidisciplinary applications.     

Solvent-free mechanochemical mild oxidation method to enhance adsorption properties of chitosan

• Solvent-free chitosan oxidation is obtained by rapid mechanochemical reaction. • Different oxidants induce very diverse physicochemical changes on chitosan. • Oxidized chitosan with persulfate or percarbonate has improved adsorption capacity. • Uptake on oxidized chitosan with persulfate is 125-fold faster than on pristine one. Oxidation has been profitably utilized to improve some properties of chitosan. However, only solvent-based oxidation procedures have been proposed so far, which are hardly feasible at industrial scale in an economic way because of product recovery cost. In this study, a solvent-free, rapid, and effective oxidation method is proposed. It is based on direct solid-state reaction between chitosan and oxidant powder in a mechanochemical reactor. Results prove that by short high energy ball milling (<3 h) it is possible to achieve diverse physicochemical modifications employing different reagents. Apart from polysaccharidic chain shortening, persulfate provokes high amorphization and induces formation of ketonic groups; percarbonate heightens deacetylation degree, preserving in part crystallinity; calcium peroxide merely deprotonates amino groups and increases amorphization degree. Adsorption tests with the azo-dye reactive red 2 show that adsorption capacity of chitosan co-milled with persulfate (974 mg/g milled product), which is the best performing adsorbent, is twice that of pristine chitosan, while adsorption rate is outstandingly boosted (125 times).     

Biogenic palladium prepared by activated sludge microbes for the hexavalent chromium catalytic reduction: Impact of relative biomass

• Pd nanoparticles could be reduced and supported by activated sludge microbes. • The effect of biomass on Pd adsorption by microbes is greater than Pd reduction. • More biomass reduces Pd particle size, which is more dispersed on the cell surface. • When the biomass/Pd add to 6, the catalytic reduction rate of Cr(VI) reaches stable. Palladium, a kind of platinum group metal, owns catalytic capacity for a variety of hydrogenations. In this study, Pd nanoparticles (PdNPs) were generated through enzymatic recovery by microbes of activated sludge at various biomass/Pd, and further used for the Cr(VI) reduction. The results show that biomass had a strong adsorption capacity for Pd(II), which was 17.25 mg Pd/g sludge. The XRD and TEM-EDX results confirmed the existence of PdNPs associated with microbes (bio-Pd). The increase of biomass had little effect on the reduction rate of Pd(II), but it could cause decreasing particle size and shifting location of Pd(0) with the better dispersion degree on the cell surface. In the Cr(VI) reduction experiments, Cr(VI) was first adsorbed on bio-Pd with hydrogen and then reduced using active hydrogen as electron donor. Biomass improved the catalytic activity of PdNPs. When the biomass/Pd (w/w) ratio increased to six or higher, Cr(VI) reduction achieved maximum rate that 50 mg/L of Cr(VI) could be rapidly reduced in one minute.     

TiO2@palygorskite composite for the efficient remediation of oil spills via a dispersion-photodegradation synergy

• A novel and multi-functional clay-based oil spill remediation system was constructed. • TiO₂@PAL functions as a particulate dispersant to break oil slick into tiny droplets. • Effective dispersion leads to the direct contact of TiO₂ with oil pollutes directly. • TiO₂ loaded on PAL exhibits efficient photodegradation for oil pollutants. • TiO₂@PAL shows a typical dispersion-photocatalysis synergistic remediation. Removing spilled oil from the water surface is critically important given that oil spill accidents are a common occurrence. In this study, TiO₂@Palygorskite composite prepared by a simple coprecipitation method was used for oil spill remediation via a dispersion-photodegradation synergy. Diesel could be efficiently dispersed into small oil droplets by TiO₂@Palygorskite. These dispersed droplets had an average diameter of 20–30 mm and exhibited good time stability. The tight adsorption of TiO₂@Palygorskite on the surface of the droplets was observed in fluorescence and SEM images. As a particulate dispersant, the direct contact of TiO₂@Palygorskite with oil pollutants effectively enhanced the photodegradation efficiency of TiO₂ for oil. During the photodegradation process, •O₂⁻and •OH were detected by ESR and radical trapping experiments. The photodegradation efficiency of diesel by TiO₂@Palygorskite was enhanced by about 5 times compared with pure TiO₂ under simulated sunlight irradiation. The establishment of this new dispersion-photodegradation synergistic remediation system provides a new direction for the development of marine oil spill remediation.     

Enhanced 4-chlorophenol biodegradation by integrating Fe2O3 nanoparticles into an anaerobic reactor: Long-term performance and underlying mechanism

• 4-chlorophenol biodegradation could be enhanced in Fe₂O₃ coupled anaerobic system. • Metabolic activity and electron transport could be improved by Fe₂O₃ nanoparticles. • Functional microbial communities could be enriched in coupled anaerobic system. • Possible synergistic mechanism involved in enhanced dechlorination was proposed. Fe₂O₃ nanoparticles have been reported to enhance the dechlorination performance of anaerobic systems, but the underlying mechanism has not been clarified. This study evaluated the technical feasibility, system stability, microbial biodiversity and the underlying mechanism involved in a Fe₂O₃ nanoparticle-coupled anaerobic system treating 4-chlorophenol (4-CP) wastewater. The results demonstrated that the 4-CP and total organic carbon (TOC) removal efficiencies in the Fe₂O₃-coupled up-flow anaerobic sludge blanket (UASB) were always higher than 97% and 90% during long-term operation, verifying the long-term stability of the Fe₂O₃-coupled UASB. The 4-CP and TOC removal efficiencies in the coupled UASB increased by 42.9±0.4% and 27.5±0.7% compared to the control UASB system. Adding Fe₂O₃ nanoparticles promoted the enrichment of species involved in dechlorination, fermentation, electron transfer and acetoclastic methanogenesis, and significantly enhanced the extracellular electron transfer ability, electron transport activity and conductivity of anaerobic sludge, leading to enhanced 4-CP biodegradation performance. A possible synergistic mechanism involved in enhanced anaerobic 4-CP biodegradation by Fe₂O₃ nanoparticles was proposed.