High Removal Capability Research Articles

Metal–phenolic coating on membrane for ultrafast antibiotics adsorptive removal from water

Eliminating antibiotics from wastewater remains a critical challenge. This work introduces durable, high-performance adsorptive membranes formed by polymerizing tannic acid (TA) and Fe3+ ions on commercial substrates, known as TA-Fe, to enhance antibiotic removal. Using a filtration process, the TA-Fe modified membrane (MCM) demonstrated excellent ciprofloxacin hydrochloride removal efficiency, permeance, and reusability. The MCM achieved high removal capability for antibiotics, with a permeance of 3815 L m−2 h−1 bar−1 and 96.7% removal efficiency within 1.3 min—115 times faster than traditional methods. Furthermore, the MCM sustained an impressive adsorptive capacity of 99.4% even after 10 consecutive cycles. This work profoundly progresses the domain of adsorptive membrane technology, offering a promising avenue for the sustainable adsorption and separation of antibiotics from contaminated wastewater.

Two-response surface design optimization of carboxylated CNCs with super high thermal stability and dye removal capability

Discharging wastewater from industrial dyeing and printing processes poses a significant environmental threat, necessitating green and efficient adsorbents. Cellulose nanocrystals (CNCs) have emerged as a promising option for dye adsorbing. However, the industrial production and commercialization of CNCs still faced low yield, time-consuming, and uneco-friendly. In this study, we proposed a facile hydrochloric/maleic acid (HCl/C4H4O4) hydrolysis method to synthesize carboxylated CNCs using Box-Behnken design and dual response surface design, which can systematically investigate the effect of experimental factors (temperature, time and HCl/C4H4O volume ratio) on the final products. The rod-liked carboxylated CNCs gave the highest yield of 90.50 %, maximum carboxyl content of 1.29 mmol/g, and efficient dye removal ratio of 91.5 %. Furthermore, compared to CNCs obtained by commonly sulfuric acid hydrolysis way (CNCs-S) with a Tmax of 242.6 °C, the CNCs extracted at 5 h exhibited significantly improved thermal stability with Tmax reaching 351.2 °C. The enriched carboxyl content and excellent thermal stability show potential wastewater treatment applications under harsh conditions.

Calcium-Based Metal-Organic Framework: Detection and Idiosyncratic Removal of Copper by Nano-Particle Deposition.

A novel calcium-based metal-organic framework (CaMOF@LSB) was designed and synthesized, exhibiting dual functionality for both selective detection and removal of Cu2+ ions from aqueous solutions. The framework's stability, including solvent and pH variations, was established with notable thermal resilience. Colorimetric Cu2+ detection (≥5 ppm) with a high capture capacity of 484.2 mg g-1 by CaMOF@LSB places this material among the few that ensure efficient colorimetric detection and high removal capabilities of Cu2+ ions. Batch adsorption experiments revealed pH-dependent behavior and competitive interactions. Langmuir and pseudo-second-order kinetics models aptly described adsorption isotherms and kinetics, respectively. Thermodynamic assessments confirmed spontaneous and endothermic adsorption. Mechanistically, nanoparticle deposition contributes to the Cu2+ uptake. CaMOF@LSB also exhibited one of the best removal behaviour of Cu2+ by means of oxide formation on the surface. Regeneration of CaMOF@LSB was achieved by simple sonication in 0.1 M aqueous NaOH solution. The recyclability was also tested up to 5 cycles, and it exhibited a small decrease in adsorption capacity observed across the cycles. This research presents a promising avenue for addressing heavy metal pollution using metal-organic frameworks, thereby offering potential applications in water purification and environmental pollution monitoring and remediation.

Ultrathin BiOCl-OV/CoAl-LDH S-scheme heterojunction for efficient photocatalytic peroxymonosulfate activation to boost Co (IV)=O generation

Sustainable and rapid production of high-valent cobalt-oxo (Co(IV)=O) species for efficiently removing organic pollutants is challenging in permoxymonosulfate (PMS) based advanced-oxidation-processes (AOPs) due to the limitation of the high 3d-orbital electronic occupancy of Co and slow conversion from Co(III) to Co(II). Herein, S-scheme BiOCl-OV/CoAl-LDH heterojunction were constructed by ultrathin BiOCl with the oxygen-vacancy (OV) self-assembled with ultrathin CoAl-LDH. OV promoted the formation of charge transfer channel (Bi-O-Co bonds) at the interface of the heterojunction and reduced electron occupation of the Co 3d-orbital to facilitate the generation of Co(IV)=O in the BiOCl-OV/CoAl-LDH/PMS/Visible-light system. S-scheme heterojunction accelerated the photogenerated electrons to allow rapid conversion of Co(III) to Co(II), promoting the fast two-electron transfer from Co(II) to Co(IV)=O. Consequently, the developed BiOCl-OV/CoAl-LDH/PMS/Visible-light system showed excellent degradation efficiency for most of organic pollutions, and exhibited very high removal capability for the actual industrial wastewater. This study provides a new insight into the evolution of Co(IV)=O and the coordinative mechanism for photocatalysis and PMS activation.

Impact of Nitrate on the Removal of Pollutants from Water in Reducing Gas-Based Membrane Biofilm Reactors: A Review.

The membrane biofilm reactor (MBfR) is a novel wastewater treatment technology, garnering attention due to its high gas utilization rate and effective pollutant removal capability. This paper outlines the working mechanism, advantages, and disadvantages of MBfR, and the denitrification pathways, assessing the efficacy of MBfR in removing oxidized pollutants (sulfate (SO4-), perchlorate (ClO4-)), heavy metal ions (chromates (Cr(VI)), selenates (Se(VI))), and organic pollutants (tetracycline (TC), p-chloronitrobenzene (p-CNB)), and delves into the role of related microorganisms. Specifically, through the addition of nitrates (NO3-), this paper analyzes its impact on the removal efficiency of other pollutants and explores the changes in microbial communities. The results of the study show that NO3- inhibits the removal of other pollutants (oxidizing pollutants, heavy metal ions and organic pollutants), etc., in the simultaneous removal of multiple pollutants by MBfR.

Effective adsorption of fluorescent congo red azo dye from aqueous solution by green synthesized nanosphere ZnO/CuO composite using propolis as bee byproduct extract.

The indirect dumping of massive volumes of toxic dyes into water has seriously affected the ecosystem. Owing to the many applications of the designed nanomaterials in the manufacturing process, there is a lot of research interest in synthesizing nanomaterials using green processes. In this research, the byproduct of bee was employed to synthesize nanoparticles (NPs) of ZnO, CuO, and biosynthesized ZnO/CuO (BZC) nanocomposite via utilizing a green and simple approach. To validate the effective fabrication of BZC nanocomposite, various characterization measurements were applied. FTIR analysis identified the functional groups in charge of producing nanoparticles and nanocomposites. Moreover, the existence of ZnO and CuO XRD peaks suggests that the nanocomposites were successfully biosynthesized. The high-resolution XPS spectrum of the BZC nanocomposite's Zn2p3, Cu2p3, and O1s were observed. Our findings indicate the successful engineering of the prepared nanomaterials and BZC nanocomposite. Our findings indicate the successful engineering of the prepared nanomaterials and BZC nanocomposite. For Congo red (CR) fluorescent stain azo dye elimination in water, all adsorption parameters were examined at room temperature. Moreover, the adsorption experiments revealed the removal capacity for uptake CR dye using BZC nanocomposite (90.14mgg-1). Our results show that the BZC nanocomposite exhibited high removal capability for the adsorption of CR dye. The nanosphere adsorbent offered a simple, low-cost, and green approach for water purification and industrial wastewater control.

Zeolitic imidazolate framework biocomposite as a visible light-assisted photocatalyst: Synthesis (in-situ and blending), regeneration, and decolorization of Malachite Green

To overcome the limitations of current water treatment technologies, it is essential to develop non-toxic materials with high removal capabilities. Herein, novel green biocomposite beads, CS/ZIF-8/TiO2 (CZT), based on chitosan modified with zeolitic imidazolate framework (ZIF-8) and titania (TiO2) was introduced. The interesting and noteworthy features of this new biocomposite are its green synthesis, biocompatibility, and easy separation ability. The composite beads effectively decolorize Malachite Green (MG) dye solution using visible LED light. In the present study, the efficiency of three components of CZT biocomposite, which were synthesized by two different methods (in situ and blending), was compared to investigate the effect of the synthesis method, as well as the synthesis with two different amounts of TiO2 (0.2 g, and 0.4 g) to investigate the effect of TiO2. The prepared materials through the XRD, SEM, EDS, FTIR, DRS, TGA, and RAMAN analyses were characterized. The synergistic effect of ZIF-8, TiO2, and chitosan in the biocomposite increased the photo-decolorization ability of the MG dye under visible-light irradiation. The decolorization at the optimum pH (pH = 6.5) after 180 min reached 94.5% and at the natural pH (pH = 3.93) after 300 min reached 98.2%. The photocatalytic decolorization reaction of the biocomposite followed zero-order kinetics.

English

Immobilization is an efficient method in the remediation of heavy metal-polluted soils. A greenhouse experiment was conducted to investigate the influence of fish scale powder, chitin, and chitosan on the growth and chemical composition of rice grown on a soil contaminated with Zn, Pb, Cd, and Ni. Results showed that the application of fish scale powder, chitin, and chitosan significantly increased root and shoot dry matter yield of rice, but decreased Pb phytoextraction efficiency. Further, the translocation factor of Ni decreased following the application of fish scale powder and chitosan. Application of fish scale powder decreased Ni, Cd, Zn, and Pb bioavailability in soil. The addition of chitosan caused 56% decrease in shoots Ni concentration as compared to control. Among different amendments, only the application of chitosan had a significant effect on the reduction of Zn content in rice root by 70% as compared to control. Considering that the translocation factors were less than one in all treatments, it can be concluded that biostabilization of the studied metals has occurred. Based on the obtained results, fish scale derivatives including fish scale powder and chitosan play an important role in the removal of heavy metals due to having suitable functional groups. Therefore, it can be deduced that due to the economic feasibility, environmentally friendly, and high metal removal capability of chitosan and fish scale powder, these two amendments are highly recommendable to be applied in multi-metal polluted soils for increasing metals removal and hence decreasing their phytotoxicity.

Polysulfone-based mixed matrix membranes loaded with a multifunctional hierarchical porous Ag-Cu dendrites@SiO2 core-shell nanostructure for wastewater treatment

Eliminating pollutants from wastewater is a crucial approach to securing the global water supply. It is well known that membrane purification technologies are remarkably attractive due to their high efficacy and low energy consumption. The neat polysulfone (PSF) polymer membranes, though, are prone to be fouled by organic pollutants, causing pore blockage and waned separation performance. We herein report and describe the rational design of a hierarchical porous Ag-Cu dendrites@SiO2 core-shell nanostructure/PSF mixed matrix membranes (MMMs) by coupling heterogeneous dendritic Ag-Cu@SiO2 core-shell nanostructure with PSF polymer matrix using facile phase inversion method for efficient separation of the protein (Bovine Serum Albumin; BSA) and Rose Bengal (RB) dye removal. Besides, for the first time, a theoretical mapping of molecular electrostatic potential (MESP) maps for chemical structure has been used for studying the interaction between the compounds (membrane moieties and pollutants). Practically, the SiO2 nanoparticles provide excellent hydrophilicity causing a sequential efficient, antifouling protein and dye separation with an outstanding rejection rate of over 96 % for both BSA and RB. In addition, the porous hierarchical scaffold formed from the hydrophilic Ag-Cu nanosheets embedded with SiO2 nanoparticles greatly assists the rapid permeation of water with a high flux rate of up to 50 L m−2 h−1 bar−1 for pure water. Furthermore, the hydrophilic nature of Ag and Cu nanoparticles also renders this membrane with a high removal capability for dye blocking enabling it to remove soluble pollutants in molecular dimensions as well. This design strategy not only provides an outstanding membrane for water purification but also sheds light on the design of multi-purpose functional membranes for a variety of energy and environment-related applications.

Effective Removal of Methyl Orange Dyes Using an Adsorbent Prepared from Porous Starch Aerogel and Organoclay

Intending to provide efficient and compact wastewater remediation, the present work is exploiting and introducing a novel composite prepared from porous starch aerogel (PSA) and organically modified Ca-montmorillonite (OMMT) for the removal of dyes from aqueous samples. First, potato starch components were used as a hydrolysis precursor to obtain PSA. The organoclay samples were prepared by co-intercalation of octadecylamine (ODA) into Ca-MMT using a low-temperature melting procedure. Composites with different starch-to-organoclay ratios of 10:1, 1:1, and 1:10 were then prepared by a blending process in distilled water and used for methyl orange (MO) uptake. The removal of methyl orange dyes increased with the amount of organoclay in the PSA matrix. Characterization revealed that organoclay synergy improved the PSA surface chemistry, while an important improvement in textural properties and thermal stability was also observed. The composite’s efficiency was demonstrated by high removal capabilities towards MO in most experimental runs, with a maximum adsorption capacity beyond 344.7 mg/g. The fitting result showed that MO adsorption follows a monolayer adsorption model, and chemisorption was the rate-controlling step. Nonetheless, this study proved the great potential of PSA/OMMT in dyeing wastewater treatment. Furthermore, starch modification is proven as an effective approach to enhancing the performance of starch-derived adsorbents.

Design of ion-imprinted cellulose-based microspheres for selective recovery of uranyl ions

Herein, cellulose was selected as the raw material for the production of sorbent microspheres for the selective separation of uranyl (UO22+) ions by ion-imprinting technique due to their low cost, biodegradability, and renewability. To begin, an amidoxime cellulosic derivative (AOCE) is synthesized by a Michael addition followed by an amidoximation reaction, both of which are homogeneous reactions. In the end, microspheres of ion-imprinted U-AOCE sorbent were made by mixing the developed AOCE derivative with UO22+, crosslinking the UO22+ polymer complex with glyoxal, and eluting the coordinated ions with H+/EDTA. U-AOCE smartly recognized the target ions for fitting the cavities generated during the UO22+-imprinting process, resulting in a much greater adsorption capacity of 382 ± 1 mg/g and enhanced adsorption selectivity for UO22+. A pseudo-second-order model fit the data well in terms of kinetics, while the Langmuir model adequately explained the isotherms, indicating chemisorption and adsorption via UO22+ chelation. The coordination between UO22+ and both the -NH2 and -OH groups of the amidoxime units is the primary adsorption process, as shown by NMR, XPS, and FTIR studies. For UO22+ biosorption from aqueous effluents, the results of this study deliver new guidance for the design of biosorbents with high removal capability and excellent selectivity.

Effect of Process Parameters on the Graphite Expansion Produced by a Green Modification of the Hummers Method.

Adsorption stand out among other standard techniques used for water treatment because of its remarkable simplicity, easy operation, and high removal capability. Expanded graphite has been selected as a promising agent for oil spill adsorption, but its production involves the generation of corrosive remnants and massive amounts of contaminated washing waters. Although the advantageous use of the H2O2-H2SO4 mixture was described in 1978, reported works using this method are scarce. This work deals with the urgent necessity for the development of alternative chemical routes decreasing their environmental impact (based on green chemistry concepts), presenting a process for expanded graphite production using only two intercalation chemicals, reducing the consumption of sulfuric acid to only 10% and avoiding the use of strong oxidant salts (both environmentally detrimental). Three process parameters were evaluated: milling effect, peroxide concentration, and microwave expansion. Some remarkable results were obtained following this route: high specific volumes elevated oil adsorption rate exhibiting a high oil-water selectivity and rapid adsorption. Furthermore, the recycling capability was checked using up to six adsorption cycles. Results showed that milling time reduces the specimen's expansion rate and oil adsorption capacity due to poor intercalant insertion and generation of small particle sizes.

A Simple and Efficient Solar Interfacial Evaporation Device Based on Carbonized Cattail and Agarose Hydrogel for Water Evaporation and Purification.

One of the main trends in the development of solar interface evaporation technology is the simple, efficient, and environmentally friendly bio-based evaporation device. However, the development of bio-based evaporators with high water evaporation rates and good pollution removal capability is a significant challenge. Here, we present a carbonized cattail-agarose hydrogel (CCAH) membrane with numerous microchannels resembling bamboo knots, exceptional hydrophilicity, outstanding light absorption capability, and potent adsorption. Under one solar irradiation, its evaporation rate and efficiency reached 1.93 kg m-2 h-1 and 95.8%, respectively. More importantly, the CCAH membrane produces steam water that is almost totally free of salts (Na+, K+, Mg2+, and Ca2+), heavy metal ions (Pb2+, Cd2+, and Cr2+), and organic dyes (Rhodamine B, methylene blue, and methyl orange). The CCAH membrane is highly promising for the use of saltwater desalination and wastewater recovery to help people in impoverished areas with water scarcity problems.

Mechanically stable core-shell cellulose nanofibril/sodium alginate hydrogel beads with superior cu(II) removal capacity

Nanocellulose hydrogels are promising sustainable biosorbents for removing heavy metal ions for wastewater treatment. However, the nanocellulose hydrogels reported thus far typically suffer from inferior adsorption performance and/or poor mechanical stability, thus limiting their industrial applications. Achieving the goals of mechanical stability and high removal capability remains a crucial technical challenge, which may be addressed, as presented in this study, by developing novel core-shell carboxymethylated cellulose nanofibril (CMCNF)/sodium alginate (SA) hydrogel beads (CAbs). By immobilizing CMCNFs (shell) on the surface of the SA hydrogel bead (core) via electrostatic attractions and hydrogen bonding, a mechanically stable hydrogel bead with a core-shell configuration was constructed, which shows a Cu(II) removal capacity of up to 221 mg/g that exceeds that of CMCNFs and most other nanocellulose structural adsorbents. Furthermore, both the formation principle of the core-shell structure and the Cu(II) removal mechanism were explored in detail. Finally, we demonstrated a potential application of core-shell CAbs to treat drinking water with a low concentration of Cu(II) using a homemade column adsorption device. This work brings sustainable nanocellulose adsorbents a step closer to industrial applications for Cu(II) wastewater treatment.

Facile encapsulation of nano zero-valent iron with calcium carbonate: synthesis, characterization and application for iron remediation.

In this study, CaCO3 was used as a modifier for nano zero-valent iron (nZVI) surface to prevent rapid aggregation and effectively utilized for iron remediation from aqueous solution. Surface chemistry and morphology of CaCO3 encapsulated nZVI (CaCO3-nZVI) before and after treatment of contaminant iron solution were characterized by scanning electron microscopy-energy dispersive X-ray (SEM-EDX), X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). The mechanisms of surface modification as well as iron remediation were well depicted with the help of these characterisation tools. Iron removal efficacy of 96.4% was achieved with 0.25g/L adsorbent dose for an influent iron of 0.5mg/L at pH 10 after a 3h treatment process. When the influent concentration was increased to 10mg/L, the removal capacity decreased to 92.1%. The study demonstrates that CaCO3 and nZVI in the encapsulated nanoparticle have a significant synergistic effect. The pseudo-second- order reaction kinetics and Freundlich isotherm model correctly portrayed the experimental data for iron removal by CaCO3-nZVI. The CaCO3-nZVI is a viable option for iron removal from various aqueous media due to its facile preparation, high iron removal capability, and reusability.

Species transformation and removal mechanism of various iodine species at the Bi2O3@MnO2 interface

Long-term exposure to excessive iodine via drinking water significantly increases the risk of thyroid diseases. Further, the mechanisms and feasible technologies for iodine removal are far from being well elucidated. In this study, we constructed a heterogeneous Bi2O3@MnO2 interface with oxidation and adsorption efficiency toward iodide (I−), and investigated the performance and mechanisms involved in iodine removal. Bi2O3@MnO2 at the optimized Bi/Mn ratio of 0.05:1 had a maximum adsorption capacity of 1.19, 1.21, and 1.06 mg/g toward I−, iodine elemental (I2), and iodate (IO3−), respectively. According to the density functional theory (DFT) calculation, Bi2O3@MnO2 had an adsorption energy of -2.34, -2.11, and -3.89 eV for I−, I2, and IO3−, and exhibited a better band structure and state density character for iodine removal. Based on the results of XPS, HPLC, and LC-ICP-MS characterization, Bi2O3 plays an important role in adsorbing and capturing I− whereas MnO2 dominates the moderate oxidation of I− and the adsorption of I− and I2. The adsorbed I− and I2 concentrations on the Bi2O3@MnO2 surfaces were 146.3 μg/L and 18.3 μg/L. Notably, IO3− was not detected owing to its moderate oxidation effect. The coexisting ions of chloride (Cl−) and bromide (Br−) tended to occupy the Bi2O3 lattice and form insoluble BiOCl and BiOBr. Further, reductive species, such as sulphite (SO32−), may reduce MnO2 to Mn(III) and Mn(II). The synergistic effect between moderate oxidation and adsorption led to Bi2O3@MnO2 with high iodine removal capability. Overall, this study proposes a strategy for designing suitable interfaces and adsorbents for iodine removal; however, further studies are necessary to advance its application in practice.

Construction of 3D Ni2+-Al3+-LDH/γ-Fe2O3-Cd2+-Ni2+-Fe3+-LDH structures and multistage recycling treatment of dye and fluoride-containing wastewater

The construction of three-dimensional (3D) Ni2+-Al3+-LDH/γ-Fe2O3-Cd2+-Ni2+-Fe3+-layered double hydroxide (LDH) structures (S1–S6) with magnetic properties and different (γ-Fe2O3-Cd2+-Ni2+-Fe3+-LDH)/(Ni2+-Al3+-LDH) ratios were successfully prepared. The effects of these ratios in these 3D LDH constructions on physicochemical properties were investigated using XRD, SEM, VSM, UV–vis, and BET analyses. The specific surface area and band gap of these materials decreased with increased ratio, while the saturation magnetization increased. The synergistic combination of saturation magnetization, adsorption characteristics, and band gap of six sample types were evaluated. S3 samples were used in a multistage recycling treatment study of dye wastewater and fluoride ion (F−)-containing wastewater, effectively degrading methyl orange (MO) due to its high photocatalytic activity. After this, the memory effect of the calcined product (S3, 300 °C) significantly enhanced the migration and diffusion of F−, resulting in a F− adsorption capacity of 49.25 mg/g. The recycling properties of this composite material for photocatalytic degradation and adsorption capabilities for F− removal were evaluated, showing a reduction in efficiency of only 1 % and 8.6 % for degradation of MO and F− removal respectively, with no significant loss of efficiency after 10 cycles. Adsorption experiments and subsequent sample characterization showed that the F− adsorption mechanism of S3 involved ion exchange mechanism and sorption sites (interlayer, basal, edges and junction sites). The existence of oxygen vacancies and formation of S-scheme heterojunction between γ-Fe2O3-Cd2+-Ni2+-Fe3+-LDH and Ni2+-Al3+-LDH, resulted in the improvement of the photocatalytic activity. The results obtained in this study demonstrated that Ni2+-Al3+-LDH/γ-Fe2O3-Cd2+-Ni2+-Fe3+-LDH composites were a promising adsorbent for degradation of MO and F− removal in practical multilevel utilization due to its simple synthesis, low-cost, recyclability, and high removal capability.

SEM and XRD for removal of heavy metals from industrial wastewater and characterization of chicken eggshell.

Heavy metal toxicity due to industrial wastewater has been a threat to the environment for the past many decades, especially in developing countries. Electroplating Industry wastewater containing heavy metals can become a serious environmental pollutant if not treated appropriately. Present study investigated the removal of nickel and chromium ions from electroplating wastewater using calcined hen eggshells because of it high removal capability, little cost and easy approachability. Characterization of the adsorbent such as proximate analysis, surface charge, X-ray diffraction, and surface area was done prior to adsorption process. Batch adsorption experiment was performed to study the effect of different parameters such as adsorbent dose, contact time, temperature, and pH for adsorbent. Removal percentage of both heavy metals was checked by using calcined eggshell as adsorbent. Comparison was made between nickel and chromium to identify the most effective removal efficacy. It was concluded that utilization of natural waste was found suitable, easier, cost operative and environmental approachable for removal of heavy metals from industrial wastewater. RESEARCH HIGHLIGHTS: To use ecofriendly approach for the treatment of industrial wastewater. To used calcined eggshell as adsorbents for removing metal concentration from industrial wastewater. To find the metal removal potential of calcined eggshell under various environmental conditions like dosage, contact time, temperature, and pH. To checking the efficacy of calcined eggshell.

Cubosomic Supramolecular Solvents: Synthesis, Characterization, and Potential for High-Throughput Multiclass Testing of Banned Substances in Urine.

This paper was intended to efficiently extract multiclass prohibited substances in human sport drug testing by using supramolecular solvents (SUPRASs) made up of cubosomes. These SUPRASs, here first reported, are synthesized by the salt-induced coacervation of 1,2-hexanediol in urine. The formation of square and rounded cubosomes with a size range of 140-240 nm was confirmed by electron microscopy. These nanostructures consisted of 1,2-hexanediol, salt, and a high water content (36-61%, w/w). Their applicability in multiclass determinations was investigated by the extraction of 92 prohibited substances (log P from 2.4 to 9.2) belonging to the 10 categories of the World Anti-Doping Agency's (WADA) list. Variables influencing both recoveries and matrix effects were optimized. Cubosomic SUPRASs showed high extraction efficiency and interference removal capability, which was attributed to their large hydrophilicity and surface area. Both features were superior to those of the other 11 SUPRASs that were based on sponge droplets and inverted hexagonal aggregates and to those of conventional organic solvents. A sport drug-testing method based on cubosomic SUPRAS-LC-ESI-MS/MS was proposed and validated. Around 82-95% of drugs were efficiently extracted (recoveries 70-120%) in urine samples, and 81-92% did not present matrix effects. The method detection limits (0.001-4.2 ng mL-1) were all far below WADA's limits. The proposed SUPRAS-based sample treatment is as simple as QuEChERS, but the distinctive features of cubosomes confer them high capability in multiclass determinations.

Algae-derived metal-free boron-doped biochar as an efficient bioremediation pretreatment for persistent organic pollutants in marine sediments

Aquatic systems are important sinks of persistent organic pollutants (POPs), such as polycyclic aromatic hydrocarbons (PAHs). In this study, boron-doped biochar (B-BAB) was prepared from pristine brown algae (Sargassum duplicatum) and boric acid using a facile pyrolysis method. The B-BAB was then used as catalyst for the activation of peroxymonosulfate (PMS) for bioremediation-based sediment decontamination. The effect of catalyst dosage and initial pH of the B-BAB/PMS system on PAH removal were studied. At an initial pH of 3.0, 93% of the PAH was degraded within 12 h in the presence of 1.0 g/L of B-BAB and 1 × 10−4 M of PMS, while the removal of 2-, 3-, 4-, 5-, and 6-ring PAHs was 53, 86, 81, 83, and 91%, respectively. Results demonstrated that B-BAB has superior catalytic capacity for PMS activation and significantly improved the efficacy of PAH removal. Interaction between boric and nitrogen species on the graphitized carbon framework, through the primary radical (SO4•– and HO•) and nonradical (1O2) reactions in the B-BAB/PMS system was key to efficient PAHs removal. High PAH removal capability and favorable changes in benthic bacterial communities of the B-BAB/PMS process suggested that PMS-advanced oxidation process (AOP) treatment enhanced the biological richness and microbiota diversity of the sediments, which were initially dominated by Proteobacteria and Epsilonbacteraeota, including genera related to Woeseia and Sulfurovum. Overall, the present study significantly expanded knowledge on the metal-free nature of carbocatalysis-boosting B-BAB/PMS removal of POPs. The B-BAB/PMS system may be useful to realizing the application of green technologies for future water environment bioremediation campaigns.