Underlying Adsorption Mechanism Research Articles

Efficient Removal of Nickel from Wastewater Using Copper Sulfate-Ammonia Complex Modified Activated Carbon: Adsorption Performance and Mechanism.

The necessity to eliminate nickel (Ni) from wastewater stems from its environmental and health hazards. To enhance the Ni adsorption capacity, this research applied a copper sulfate-ammonia complex (tetraamminecopper (II) sulfate monohydrate, [Cu(NH3)4]SO4·H2O) as a modifying agent for a Phragmites australis-based activated carbon preparation. The physiochemical properties of powdered activated carbon (PAC) and a modified form ([Cu(NH3)4]-PAC) were examined by measuring their surface areas, analyzing their elemental composition, and using Boehm's titration method. Batch experiments were conducted to investigate the impact of various factors, such as Ni(II) concentration, contact time, pH, and ionic strength, on its substance adsorption capabilities. Additionally, the adsorption mechanisms of Ni(II) onto activated carbon were elucidated via Fourier-transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The findings indicated that modified activated carbon ([Cu(NH3)4]-PAC) exhibited a lower surface area and total volume than the original activated carbon (PAC). The modification of PAC enhanced its surface's relative oxygen and nitrogen content, indicating the incorporation of functional groups containing these elements. Furthermore, the modified activated carbon, [Cu(NH3)4]-PAC, exhibited superior adsorption capacity relative to unmodified PAC. Both adsorbents' adsorption behaviors conformed to the Langmuir model and the pseudo-second-order kinetics model. The Ni(II) removal efficiency of PAC and [Cu(NH3)4]-PAC diminished progressively with rising ionic strength. Modified activated carbon [Cu(NH3)4]-PAC demonstrated notable pH buffering and adaptability. The adsorption mechanism for Ni(II) on activated carbon involves surface complexation, cation exchange, and electrostatic interaction. This research presents a cost-efficient preparation technique for preparing activated carbon with enhanced Ni(II) removal capabilities from wastewater and elucidates its underlying adsorption mechanisms.

Enhanced Adsorption Response of pH-Sensitive Peptides: The Role of Membrane Acidity.

pH-sensitive peptides bind and traverse lipid membranes in response to changes in pH. They can be used to target tumors and other acidic tissues. We investigate the influence of acidic lipids on the pH-driven adsorption of recently synthesized peptides. Using a statistical-thermodynamic theory that takes into account the acid-base chemistry of peptides and lipids, we find that the presence of acidic lipids amplifies changes in peptide surface concentration when transitioning from high to low pH. We study cyclic and linear peptides, containing tryptophan, glutamic acid, and arginine residues, examining their behavior in both neutral and acidic membranes. Membrane binding consistently results from the shallow insertion of tryptophan residues with hydrophilic residues facing the aqueous solution. Regardless of the pH, the peptide's geometry predominantly determines the orientation and distribution of residues. Notably, we find that not only the extent of adsorption is pH-sensitive but also the underlying adsorption mechanism: it is barrier-free at low pH but hindered by a large free energy barrier at high pH. Hence, under more acidic conditions, pH-sensitive peptides show facilitated adsorption both kinetically and thermodynamically.

CoFe2O4/PANI/MWCNTs ternary hybrid composites. Synthesis, characterization, the effect of MWCNTs ratio and dye removal capability.

We have synthesized cobalt ferrite (CoFe2O4) using the sucrose auto-combustion method and subsequently employed the in situ polymerization technique to fabricate ternary composites comprising CoFe2O4, polyaniline (PANI), and multi-walled carbon nanotubes (MWCNTs). In this novel investigation, we explored the influence of varying MWCNTs ratios on these composites' structural, magnetic, thermal, and electrical properties. The crystal structures of the synthesized composites were analyzed using X-ray diffraction (XRD), while Fourier transform infrared (FT-IR) spectroscopy revealed changes in bonding patterns, including the disappearance of ferrite bonds and the emergence of new ones. Transmission electron microscopy (TEM) images illustrated a complete coating of PANI on both MWCNTs and CoFe2O4 particles, resulting in a substantial reduction in magnetization compared to pure CoFe2O4 ferrite due to PANI's nonmagnetic nature. Vibrating sample magnetometer (VSM) measurements confirmed this reduction, indicating a decrease to 7.3 emu.g-1. Thermal analysis demonstrated an enhancement in thermal stability with increasing MWCNTs content, as evidenced by an increase in the temperature equivalent for half decomposition (T50) from 486 to 522°C for composites with 40% MWCNTs. Moreover, the electrical conductivity showed a corresponding rise with MWCNTs content, increasing from 3.1 × 10-3 Ω-1.cm-1 to 2.2 × 10-2 Ω-1.cm-1, possibly indicating charge transfer from PANI to MWCNTs. To assess practical applications, we investigated the ability of the composite with 40% MWCNTs to remove phenol red (PR) dye from aqueous solutions. Through a systematic study of adsorption parameters and kinetics, we determined optimal conditions for effective dye removal and elucidated the underlying adsorption mechanism. Our results demonstrated the composite's efficiency in dye removal, with a 6.4mg·g-1 capacity for PR dye, highlighting its potential for environmental remediation efforts.

Decoration of phosphoric acid groups onto Ti3C2Tx MXene for enhanced uranium removal

The construction of novel MXene-based composites with superb abilities through functionalization is an effective strategy to enhance the potential of this emerging inorganic lamellar material for environmental adsorption applications. The present work systematically investigated the adsorption performance of Ti3C2Tx MXene modified with phosphate functional groups that facilitate the capture of uranyl ions. After introducing phosphate groups via a two-step modification of 3-aminopropyltriethoxysilane (APTES) and phytic acid (PA), the synthesized Ti3C2-APTES-PA is significantly superior to pristine Ti3C2Tx nanosheets in terms of adsorption capacity, adsorption selectivity and reusability for uranium. The maximum uptake capacity of Ti3C2-APTES-PA at pH = 5 reaches 323 mg/g, which is 2.5 times higher than that of unmodified MXene. Furthermore, the large selectivity coefficient (SU/M > 16.2) declares that Ti3C2-APTES-PA preferentially adsorbs uranium among substantial competing ions. Ti3C2-APTES-PA also shows good cycling performance that its adsorption capacity remained 92.3 % after 6 cycles. When it comes to treating simulated uranium tailings pond leachate and radioactive wastewater from mines, high U(VI) removal rates of 88.9 % and 96.8 % can be achieved by our ternary composite at a dosage of 0.05 g/L. The underlying adsorption mechanism was unraveled by spectroscopic analysis to be the formation of coordination complexes of uranyl ions with phosphate groups on PA and hydroxyl groups on Ti3C2Tx substrate, as well as the reduction of a small amount of adsorbed U(VI) to U(IV) by MXene. The overall results imply that Ti3C2-APTES-PA is an effective uranium chelating scavenger for the treatment of environmental radioactive wastewater.

Unlocking Agronutrient Resources: Sorption Strategies for sugar-energy industry waste

Vinasse and ash from sugarcane bagasse (SCB) are key byproducts in the sugar-energy industry. Vinasse is nutrient-rich but environmentally challenging, while sugarcane bagasse ash (SCBA) offers excellent adsorbent for treating effluents. This work aims to assess the effectiveness of SCBA in removing nitrogen (N) and potassium (K) nutrients from Vinasse. Simulated standard solutions of K2SO4 and (NH4)2HPO4 were used to mimic the nutrient concentrations in Vinasse and optimize experimental parameters such as adsorbent mass and contact time. Kinetic and isotherm models were also applied to elucidate the underlying adsorption mechanisms. Structural, morphological, and thermal analyses revealed the micro-mesoporous and heterogeneous nature of SCBA, primarily composed of SiO2 (quartz and cristobalite). The sorption assessment indicated the ideal conditions involved lower SCBA masses (2.5 g) and 6 h of contact time for the simulated standard solutions. The replicated conditions for Vinasse (at an adjusted sorption time of 24 h) demonstrated nutrient sorption and pH correction of the Vinasse, attributed to the alkaline nature of SCBA. Analysis of the sorption kinetic models for K+ and NH4+ revealed that SCBA interacts diffusively with the environment, not necessarily controlled by adsorption on active sites, indicating non-uniform characteristics. The sorption isotherms for K+ and NH4+ showed the non-linearized Freundlich model was the most suitable, indicating the adsorption sites with varying energy levels and a multilayer sorption process. In conclusion, we successfully demonstrated the sorption of nutrients from Vinasse by SCBA, enhancing the value of these residues and mitigating their environmental impact when used in agricultural applications.

Polymer Nanocomposites: A Comprehensive Review on Their Applications in Membranes and Adsorbents for Water Treatment and Gas Separation

Environmental challenges such as water scarcity and air pollution have become critical global issues, prompting the need for innovative solutions. Polymer nanocomposites have emerged as promising materials for addressing these challenges due to their unique properties and functionalities. This comprehensive review explores the effective utilization of polymer nanocomposites in membranes and adsorbents for water treatment and gas separation. The synthesis methods, properties, and mechanisms of polymer nanocomposite membranes are discussed, along with their applications in wastewater treatment and gas separation. Furthermore, the use of polymer nanocomposites as adsorbents for removing toxic metals ions and dyes from water is examined, including the underlying adsorption mechanisms. Additionally, the review highlights recent patents in the field, emphasizing the innovative applications of polymer nanocomposite membranes for environmental purposes

A Prussian blue analog-based copper-aluminum layered double hydroxide for cesium removal from water: fabrication, density functional theory-based molecular modeling, and the adsorption mechanism.

A new type of adsorbent, a Prussian blue analog-based copper-aluminum layered double hydroxide (PBA@CuAl-LDH), was successfully synthesized using a one-step method for the removal of radioactive Cs+ from wastewater. The adsorption performance, characteristics and the underlying adsorption mechanism of PBA@CuAl-LDH were systematically examined. The results showed that PBA@CuAl-LDH exhibited excellent adsorption performance, with a maximum adsorption capacity of 109.2 mg g-1. Over 85% of PBA@CuAl-LDH can be recycled, and the material exhibited only a 6.6% loss in adsorption performance. The adsorption process was well-fitted using the pseudo-second-order kinetic model and the Freundlich isotherm model, revealing the surface heterogeneity of the composite adsorbent. A molecular model of PBA@CuAl-LDH was constructed by combining density functional theory and multiple instrumental characterization techniques. Our results indicate that PBA crystals can be generated between layers and on the surface. Ion exchange was revealed as the main adsorption mechanism of Cs+ by PBA@CuAl-LDH. Specifically, the interstitial spaces of the PBA crystals generated between the layers and on the surface played an important role in ion exchange. These findings provide concrete theoretical support for radioactive pollution control and have significant value in directing the fabrication of cesium removal materials and their future engineering application.

Multi‐interactions driven continuous removal of organic dyes from water by lignocellulosic‐based fibers

AbstractWater polluted by organic dyes is normally present in industrial production, which seriously threatens environmental safety. Research on dye adsorption has recently been related to nanomaterials due to their large specific surface area. However, there are still some problems associated with their preparation, application, and recovery. In this study, we developed the one‐step synthesis of lignocellulosic‐Fe(OH)3 hybrid fibers by in situ growth of Fe(OH)3 nanoparticles on lignocellulosic, which could be used as effective adsorbents for dye removal. The formed Fe(OH)3 nanoparticles were dispersed homogeneously on the surface of lignocellulosic. The as‐prepared hybrid fibers featured a large absorption capacity for methylene blue, up to 150.9 mg/g. In a fixed‐bed column separation process, dye pollutants were successfully removed from the water even at a high speed of 5.0 mL/min, with the separation efficiency higher than 99.99%. Remarkably, 1.0 g of lignocellulosic‐Fe(OH)3 was capable of separating over 1200 mL of dye solution continuously and thoroughly. Notably, the underlying adsorption mechanism analyses suggested that multi‐interactions of hydrogen bonds, π–π interactions, and coordinate bonds contribute to the adsorption ability of lignocellulosic‐Fe(OH)3.

Highly efficient removal of Aflatoxin B1 employing a flower-like covalent organic framework-based fiber membrane

Mycotoxin pollutants removal using adsorbents has been studied extensively in recent years, although the development of low-cost, recyclable, and highly efficient adsorbents remains a challenge to date. Covalent Organic Frameworks (COFs) represent a novel kind of porous crystalline material, which have been applied widely. In this work, a flower-like COF fiber membrane (PAN@COF FM) for adsorbing Aflatoxin B1 was fabricated using a simple approach. The COF was grown on the surface of polyacrylonitrile (PAN) skeleton using the in situ growth method. Then, the AFB1 adsorption performance of the prepared membrane and the underlying adsorption mechanism were studied. The results revealed that the activated PAN@COF FM reached adsorption equilibrium within 30 min. The used membranes were regenerated by washing with an alkaline solution and then tested for adsorption efficiency again. The PAN@COF FM could adsorb above 98% Aflatoxin B1 after 10 cycles, indicating its good reusability. The well adsorption performance of the membrane was attributed to the π-π stacking, hydrogen bonding, and hydrophobic interactions between PAN@COF FM and Aflatoxin B1. In summary, the as-prepared PAN@COF FM possesses the advantage of high reusability and good adsorption performance, and has the promising application in pollutant removal.

UiO-66-NH2/guanidine-functionalized chitosan: A new bio-based reusable bifunctional adsorbent for removal of methylene blue from aqueous media

Methylene Blue (MB) is a common pollutant found in industrial wastewater, and its removal is crucial to ensure environmental sustainability. Due to MOFs have high surface area, tunable pore size distribution, and excellent adsorption capacity, in the current study, Uio-66-NH2@Cs-ISo-Gu nanohybrid was prepared through soluthermal method and then was used to remove MB dye. The results displayed that dye optimal adsorption by Uio-66-NH2@Cs-ISo-Gu nanohybrid occurred in the first 40 min, pH = 8, and low dye concentrations. Also, with increasing temperature, the amount of adsorption has decreased, which indicated the adsorption process would be exothermic. Based on the results, the Uio-66-NH2@Cs-ISo-Gu nanohybrid has a surface area of 120.9 m2.g−1 and a type IV isotherm. Also, the Freundlich isotherm and pseudo-second order models had the best agreement with the experimental data. The maximum adsorption capacity for this nanohybrid was 178.571, 153.846, and 135.135 mg.g−1 at 25 °C, 45 °C, and 65 °C temperatures, respectively, which could be successfully used as an excellent adsorbent in treatment of wastewater. However, further research is needed to understand the underlying adsorption mechanism and optimize the process for efficient removal of MB from contaminated water sources.

Efficient oral delivery of resveratrol-loaded cyclodextrin-metal organic framework for alleviation of ulcerative colitis

Developing innovative strategies for the oral administration of phytochemicals presents a promising approach to addressing intestinal diseases. However, numerous challenges persist, including limited therapeutic efficacy, poor bioavailability, and inadequate biocompatibility. In this study, we employed a cross-linked cyclodextrin-metal organic framework (CDF) to encapsulate resveratrol (Res), generating Res-CDF, which was subsequently incorporated into natural polysaccharide hydrogel microspheres (Res-CDF in MPs) for targeted oral delivery to alleviate ulcerative colitis (UC). The underlying adsorption mechanism of Res by γ-CD elucidated by molecular dynamics simulations. Importantly, the Res-CDF in MPs formulation protected against gastric acid degradation while preserving the bioactivity of Res. Moreover, the design enabled specific release of Res-CDF in response to the mildly alkaline environment of the intestinal tract, followed by sustained Res release. In UC mice model, Res-CDF in MPs demonstrated potent anti-inflammatory effects by attenuating pro-inflammatory cytokine production and exhibited antioxidant properties. Additionally, Res-CDF in MPs enhanced the expression of tight junction proteins ZO-1, Occludin, and mucin-2 (Muc-2), thereby maintaining normal intestinal barrier function. This innovative oral delivery strategy capitalizes on the advantageous properties of polysaccharide hydrogel and CDF to augment bioavailability of phytochemicals, laying the groundwork for developing novel oral interventions employing natural phytochemicals to address intestinal-related diseases.

Novel Method for the Arsenic Removal Experiment and Mechanism Analysis.

This study focuses on the hydrothermal synthesis of magnetically activated carbon and its efficacy in As(III) adsorption. The successful incorporation of magnetite nanoparticles within the porous carbon structure was confirmed, enriching the adsorbent's properties. Comprehensive characterization was performed to analyze the pore size distribution, zeta potential at varying pH levels, and thermostability using thermogravimetric analysis. These adsorbents exhibited high As(III) removal efficiency with a uniform pore distribution. The zeta potentials were observed to decrease with an increase in pH, suggesting a relationship between adsorbent charge and pH. Adsorption dynamics were rigorously modeled using pseudo-first-order, pseudo-second-order, Elovich, and intraparticle diffusion models for different adsorbents labeled as a,b,c, and d. Each adsorbent displayed unique fitted parameters, revealing varied adsorption capabilities. The study further explored the adsorption kinetics and found that the pseudo-second-order kinetics model and the Langmuir model were most appropriate for describing the adsorption process. Adsorption thermodynamics was also fitted to elucidate the underlying adsorption mechanisms. For the a,b,c, and d adsorbents, the pseudo-first-order model, the qe(cal) values for the four adsorbents were 434.2, 418.4, 283.5, and 279.5 μg/g, respectively. Take adsorbent a as an example; the qm values for 298, 303, 308, and 313 K were 702, 673, 605, and 589 μg/g, respectively, and KL values of these temperatures were 0.021, 0.031, 0.018, and 0.009 L/μg, respectively. For the Langmuir model, the R2 values at the four temperatures were 0.999, 0.978, 0.985, and 0.993, respectively, which indicated that the Langmuir model showed higher fitness. For the Freundlich model, the KL values (L/μg) at the parameters of these temperatures are 432, 409, 328, and 294, respectively. For the Freundlich model, the 1/n values at temperatures of 298, 303, 308, and 313 K are 0.049, 0.045, 0.052, and 0.035, respectively. For the Freundlich model, the R2 values at parameters of 298, 303, 308, and 313 K are 0.986, 0.989, 0.982, and 0.872, respectively. For the Temkin model, the B values (in J/mol) are 30.93, 0.894, 0.824, and 0.782 at these temperatures, respectively. The KT values (in L/μg) are 1.02 × 106, 0.07 × 106, 0.003 × 106, and 0.002 × 106, respectively. The R2 values are 0.973, 0.958, 0.972, and 0.894, respectively. In the end, the ΔH, ΔS, and ΔG values for different adsorbents were calculated. Collectively, these findings contribute significant insights into the design and application of magnetically activated carbon adsorbents for effective As(III) removal.

Natural phosphorus-ferromanganese ore-based composites for the simultaneous remediation of arsenic- and lead-co-contaminated groundwater: synergistic effectiveness, kinetics, and mechanisms.

Natural phosphorus-ferromanganese ore (NPO-NFMO) based composites by mechanical ball milling method, applying for the simultaneous remediation of arsenic (As) and lead (Pb) co-contaminated groundwater. Kinetic behavior adopted pseudo-second-order adsorption mechanism attaining equilibrium in 120min over a wide pH range (2.0-6.0). NPO-NFMO realized higher adsorption capacity for As(III) (6.8mgg-1) and Pb(II) (26.5mgg-1) than those of single NPO (1.7 and 7.8mgg-1) and NFMO (2.9 and 5.1mgg-1), indicating that synergistic effects of NPO and NFMO considerably enhanced the adsorption capacity in mixed adsorption system. Fresh and used NPO-NFMO were characterized, and indicated that NPO-NFMO formed stable minerals of PbAs2O6 and PbFe2(AsO4)2(OH)2. The underlying adsorption mechanism indicated that As(III) and Pb(II) removal was involved with multiple mechanisms, including electrostatic adsorption, oxidation, complexation, and coprecipitation. The effects of key reaction parameters including mass ratios of NPO and NFMO, initial metal ion concentration, dosage, solution pH, and co-existing anions in groundwater were systematically investigated. The novel designed NPO-NFMO-based composites can be deemed as a promising amendment for simultaneous immobilization of As(III) and Pb(II) in co-contaminated soil and groundwater.

A computational investigation on the roles of binding affinity and pore size on CO2/N2 overall adsorption process performance of MOFs through modifying MIL-101 structure

To develop an appropriate metal-organic framework to capture CO2 from dry flue gas, understanding the roles of structural modifications, location of primary adsorption sites and underlying adsorption mechanisms is crucial. Herein, effects of type, position and concentration of nitrogen-containing functional groups and C/N-substituted ligands are investigated on overall CO2/N2 adsorption process performance and mechanism of pristine and metal-substituted MIL-101 MOFs. In this investigation, density functional theory computations, grand-canonical Monte-Carlo, and molecular dynamics simulations are applied. Taguchi-based overall evaluation criteria objective function is also used to assess the overall adsorption performances of these MIL-101 MOFs in terms of CO2 uptake capacity, CO2/N2 selectivity, isosteric heat of adsorption and mass transfer resistance. The PBE/DZVP computations resulted in the CO2-framework binding energies ranging from −3.85 to −21.01 kJ/mol implying an acid-base type of physisorption. A correlation is introduced to estimate the CO2 uptake capacity from binding affinity and pore diameter of these MIL-101 MOFs. Mechanistic investigations show that to enhance CO2 uptake capacity and CO2/N2 selectivity, functionalization of the linker ligands is more successful than functionalization of the open metal sites having strong interactions with CO2 molecules. Results also showed that the best possible scenario to improve the overall adsorption process performance of MIL-101 is to substitute the C atom(s) of the BDC ligands with the N atom(s), regardless of the central metal atom type. The comprehensive molecular design approach introduced in this work can be used as a methodology by scientists for the development of new MOFs for practical CO2 capture applications.

Characteristics and mechanism of phosphate removal by lanthanum modified bentonite in the presence of dissolved organic matter

Lanthanum modified bentonite (LMB) is a widely used adsorbent for removing inorganic phosphorus from polluted water to prevent eutrophication. However, its efficiency can be affected by various environmental factors, including dissolved organic matter (DOM), which is still unclear. In this study, we systematically explored the influence of model DOMs, including HA, bovine serum albumin (BSA), and sodium alginate (SA), on phosphate adsorption by LMB, as well as to elucidate the underlying adsorption mechanisms. Our results showed that only HA had a significant effect on phosphate adsorption by LMB, causing inhibition. When three DOMs were mixed with phosphate in different proportions and DOM was mainly HA, the performance of phosphate adsorption on LMB became worse, while BSA can slightly offset this impact. The kinetics of HA and phosphate adsorption on LMB followed the pseudo-second-order kinetic model, and isotherms fitted the Langmuir model, with a maximum adsorption capacity of 5.7 mg g−1 for P and 12 mg g−1 for HA. However, when HA and phosphate were mixed based on their Qm, a C/P molar ratio of 5.35, LMB preferentially adsorbed phosphate. HA invasion was also disadvantageous for phosphate removal by LMB, in which P adsorption was less efficient at low-concentrations. However, during co-adsorption the adsorption capacity for HA was higher. With a secondary addition of higher levels of P, both pollutants were adsorbed more effectively. In the natural water experiment, phosphate concentration decreased with increasing shaking time, while the UV254 value showed a downward trend, indicating that LMB also adsorbed HA. Characterization results showed that La and phosphate formed LaPO4 precipitation, forming La–O–P inner-sphere complexes as the main mechanism of phosphate removal by LMB. La and HA formed La-HA complexes, with O–CO bonds from HA competing for lanthanum with phosphate. Despite HA obstructing pores from adsorbent, LMB still maintained a good binding ability with phosphate. It may form La–P-HA ternary complexes during adsorption to keep HA adsorption amount.

Tunable Fluorine-Functionalized Scholl-Coupled Microporous Polymer for the Selective Adsorption and Ultrasensitive Analysis of Environmental Liquid-Crystal Monomers.

Liquid-crystal monomers (LCMs), especially fluorinated biphenyls and analogues (FBAs), are identified to be an emerging generation of persistent organic pollutants. However, there is a dearth of information about their occurrence and distribution in environmental water and lacustrine soil samples. Herein, a series of fluorine-functionalized Scholl-coupled microporous polymers (FSMP-X, X = 1-3) were designed and synthesized for the highly efficient and selective enrichment of FABs. Their hydrophobicity, porosity, chemical stability, and adsorption performance (capacity, rate, and selectivity) were regulated preciously. The best-performing material (FSMP-2) was employed as the on-line fluorous solid-phase extraction (on-line FSPE) adsorbent owing to its high adsorption capacity (313.68 mg g-1), fast adsorption rate (1.05 g h-1), and specific selectivity for FBAs. Notably, an enrichment factor of up to 590.2 was obtained for FSMP-2, outperforming commercial C18 (12.6-fold). Also, the underlying adsorption mechanism was uncovered by density functional theory calculations and experiments. Based on this, a novel and automated on-line FSPE-high-performance liquid chromatography method was developed for ultrasensitive (detection limits: 0.0004-0.0150 ng mL-1) and low matrix effect (73.79-113.3%) determination of LCMs in lake water and lacustrine soils. This study offers new insight into the highly selective quantification of LCMs and the first evidence for their occurrence and distribution in these environmental samples.

Efficient nitrous oxide capture by cationic forms of FAU and CHA zeolites

Nitrous oxide is a strong greenhouse gas contributing over 300 times global warming potential higher than carbon dioxide. The capture of nitrous oxide from industrial emission source represents an efficient and promising strategy for its further treatment or recycling, which receives less attention in the past decades. Herein, a comprehensive study on nitrous oxide capture by alkali and alkaline-earth metal ions (Li, Na, K, Mg, Ca and Ba) exchanged FAU and CHA zeolites was conducted, with focuses on the underlying adsorption mechanism and the structure-performance relationship. Under ambient conditions, Ba-FAU and Na-CHA show remarkable nitrous oxide dynamic uptakes of 2.25 and 2.41 mmol/g, respectively, at high concentration of 50000 ppm, and Ba-FAU shows good dynamic uptake of 0.35 mmol/g at extremely low concentration of 1000 ppm. The dynamic nitrous oxide uptakes by zeolites at high concentrations are related to the surface area and the adsorption strength controlled by local electrostatic field, while the diffusion resistance shows serious negative impacts at low concentrations. The intrinsic stability of zeolite and the perfect recyclability make Ba-FAU an eligible industrial adsorbent for nitrous oxide capture. In situ Fourier transform infrared spectroscopy and Grand Canonical Monte Carlo simulations reveal that nitrous oxide molecules prefer to anchor to extraframework cations via terminal-oxygen atoms and meanwhile stabilized by framework oxygen through electrostatic interaction via central nitrogen atoms. The explicit structure-performance relationship and the underlying mechanism are very important for the understanding of nitrous oxide capture by zeolites and most helpful for the rational design of robust adsorbents.

Utilization of low-cost watermelon rind for efficient removal of Cd(II) from aqueous solutions: Adsorption performance and mechanism elucidation

Recycling of agricultural waste as adsorbents for pollutant removal realizes “Waste to Resource”. This study utilized an abundant fruit waste material, watermelon rind (WR), to remove Cd(II) from aqueous solutions (Cd(II) solution in distilled deionized water) in a batch mode, and the underlying adsorption mechanism was deciphered by complementary methods. The Cd(II) adsorption process rapidly reached equilibrium in 60 min, with 90% of adsorption finished in 10 min (50 mg/L Cd(II), 0.5 g/L WR). The maximum Cd(II) adsorption capacity of WR was 102.0 ± 0.1 mg/g at pH 7.0 (25–500 mg/L Cd(II), 1.0 g/L WR), and the Dubinin-Radushkevich isotherm and pseudo-second-order kinetic models provided the best description to the adsorption process. Spectroscopic analysis using Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) showed hydroxyl, carboxyl, ether, and amine groups as the binding sites, probably via complexation. Physicochemical analysis such as zeta potential measurement and scanning electron microscopy coupled with electron dispersive X-ray spectroscopy (SEM-EDS) revealed the occurrence of electrostatic interaction and microprecipitation. Moreover, ion exchange of Cd(II) with Mg2+and Ca2+ bound to WR contributed to 83% of the Cd(II) adsorption. The findings indicate the great potential of WR for Cd(II) removal from wastewater. The mechanism elucidation uncovered the interactions between Cd(II) and the WR surface, providing insights to the development and optimization of biosorbents derived from agricultural waste.

Adsorption of fulvic acid on mesopore-rich activated carbon with high surface area.

The loss of dissolved organic matter (DOM), especially fulvic acid (FA), from soil by rainfall and runoff will reduce soil fertility and result in water pollution of DOM. Carbon materials including biochars (BCs) and activated carbons (ACs) are widely suggested for soil remediation and carbon immobilization. However, these suggested carbon materials are dominated by micropores, and largely limiting the adsorption capacity for FA. Therefore, a mesopore-rich activated carbon (KAC) with high surface area was prepared from bamboo chips to investigate the adsorption of FA. This KAC can adsorb FA more than ACs and BCs investigated in this study and reported in previous studies not only because of the high surface area (3108 m2/g), but also the higher mesopore volume proportion (57%). The negative pH effect on adsorption performance of KAC was weaker than that on AC and BC, because of the less polarity of KAC. Moreover, KAC was favorable to adsorb FA fractions with various molecular weights, higher aromaticity and higher polarity. This study indicated that KAC was a promising adsorbent for FA, and revealed the underlying adsorption mechanism of FA on KAC, which are helpful for the carbon immobilization and pollution control in soil.

Charge-modulated calcite surface for anionic surfactant adsorption from molecular dynamics simulations

Since surfactant adsorption on reservoir rock means the loss of a valuable component, it makes surfactant flooding economically less feasible. In this work, adsorption behaviors of anionic surfactant on calcite surface were investigated with different charge states for the first time using molecular dynamic (MD) simulations. To reveal the underlying adsorption mechanism, adsorption processes were systematically analyzed with the adsorption energy, mean square displacement (MSD), relative concentration distribution (RCD), and radial distribution function (RDF). The results showed that sodium dodecyl sulfate had the strongest adsorption on the surface of calcite. When calcite surface was modelled with a charge state up to 80 e (8.24 × 1014 e/cm2), sodium dodecyl benzene sulfonate (SDBS) was found to be most stable on 10 e (1.03 × 1014 e/cm2) positively charge surface, with the maximum adsorption energy and the minimum diffusion coefficient. Increasing the carbon chain length of surfactant tail, the adsorption energy of SDBS became weaker, which can be attributed to the van der Waals interactions (long-range dispersion interactions) among surfactants. A monolayer or bilayer of surfactants can be derived based on the RCD. RDF curves revealed that hydrogen bonds played an important role in interactions among calcite surface, water molecules, and head groups of surfactants. The obtained results offer important insights into charge-modulated anionic surfactant adsorption on calcite surface at molecular scale and a guide to optimal flooding conditions with reduced surfactant loss.