A critical review of adsorption isotherm models for aqueous contaminants: Curve characteristics, site energy distribution and common controversies.

The quantitative description of the equilibrium data by the isotherm models is an indispensable link in adsorption studies. The previous review papers focus on the underlying assumptions, fitting methods, error functions and practical applications of the isotherm models, usually ignoring their curve characteristics, selection criteria and common controversies. The main contents of this review include: (i) effect of the model parameters on the isotherm curves; (ii) determination of the site energy distribution; (iii) selection criteria of the isotherm models; and (iv) elimination of some common controversies. It is of great significance to reveal the curve characteristics for selecting a proper isotherm model. The site energy distribution is conducive to understanding the physicochemical properties of the adsorbent surface. The complete isotherm is recommended to be correlated with the experimental data. The model parameter qmax should be cautiously adopted for comparison of the adsorbent performance. The residual plot can be used to diagnose the fitting quality of the isotherm models further. This review also addresses some common mistakes and controversies and thereby avoids their propagation in future publications.

Studies on competitive adsorption characteristics of bisphenol A and 17α-ethinylestradiol on thermoplastic polyurethane by site energy distribution theory.

Compound pollution of microplastics and estrogens is a growing ecotoxicological problem in aquatic environments. The adsorption isothermal properties of bisphenol A (BPA) and 17α-ethinyl estradiol (EE2) on polyamide (TPU) in monosolute and bisolute systems were studied. Under the same adsorption concentration (1-4 mg L-1), EE2 had a greater adsorption capacity than BPA in the monsolute system. Compared to the energy distribution features of the adsorption sites of EE2 and BPA, the BPA adsorption sites were located in the higher energy area and were more evenly distributed than those of EE2, while the quantity of BPA adsorption sites was less than that of EE2. In the bisolute system, the average site energy, site energy inhomogeneity, and adsorption site numbers of BPA increased by 1.674, -17.166, and 16.793%, respectively. In comparison, the average site energy, site energy inhomogeneity, and adsorption sites numbers of EE2 increased by 2.267, 4.416, and 8.585%, respectively. The results showed that BPA and EE2 had a cooperative effect on the competitive adsorption of TPU. XPS analysis showed that BPA and EE2 had electron transfer on TPU, although the chemisorption effects and hydrogen bonds between BPA and TPU were more significant. Comparing the changes in the relative functional group content of TPU in monosolute and bisolute systems, BPA and EE2 were synergistically absorbed on TPU. This study can provide a theoretical reference for the study of competitive adsorption between coexisting organic pollutants.

Adsorption of dissolved organic matter (DOM) on polystyrene microplastics in aquatic environments: Kinetic, isotherm and site energy distribution analysis.

Microplastics and dissolved organic matter (DOM) are ubiquitous in aquatic environments. The adsorption behavior of DOM on microplastics in aquatic environments is a prominent concern. In this study, the adsorption of two types of DOM, Suwannee River Humic Acid (HA) and Suwannee River Fulvic Acid (FA), on polystyrene microplastics (PSMPs, 10 µm) in aquatic environments was investigated. The adsorption of both HA and FA on PSMPs could be well described by using pseudo second-order and Freundlich models. The adsorption of HA and FA on PSMPs was low pH-dependent, particularly for FA adsorption. However, the elevated ionic strength slightly increased the adsorption of HA and FA on PSMPs. Based on Freundlich model, the site energy distribution of HA and FA adsorption on PSMPs under the experimental conditions were estimated. HA and FA first occupied the high-energy adsorption sites and then diffused to the low-energy adsorption sites on PSMPs. With higher site energies, HA demonstrated a much stronger adsorption affinity to PSMPs than FA. The adsorption site heterogeneity (σe*) on PSMPs under the experimental conditions were close. Hydrophobic interaction and π-π electron donor acceptor interaction acted simultaneously in the HA and FA adsorption on PSMPs. The results of this study suggested that the environmental behaviors of microplastics would be influenced by the amount and the type of DOM as well as solution chemistry.

Adsorption characteristics of nitrite on natural filter medium: Kinetic, equilibrium, and site energy distribution studies.

Nitrite is one of the world's major contaminants in drinking water resources, and granular anthracite is often used as filter medium in water treatment. In this study, the adsorption characteristics of nitrite on granular anthracite under various temperatures were investigated through adsorption kinetic, isotherm models, and site energy distribution theory. The adsorption of nitrite on granular anthracite was an endothermic reaction, while intraparticle diffusion was not the only rate control step. The adsorption could be well described by using pseudo-second-order and Langmuir-Freundlich equations. The adsorption capacity was 402.51 mg NO2--N kg-1 at 298 K, which could be significantly improved to 1380.1 mg NO2--N kg-1 when the temperature reached 308 K. Furthermore, nitrite ions first occupied the high-energy adsorption sites and then diffused to the low-energy adsorption sites on granular anthracite. There were more sites, including high-energy sites and low-energy sites, for nitrite adsorption at 308 K. Besides, the thickness of the boundary layer increased with the adsorption capacity improved at a higher temperature, and nitrite ions were adsorbed mainly through chemical mechanisms. Moreover, the neutral pH was helpful for the adsorption. The presence of co-existing ions could limit the adsorption and the effect followed the order of PO43- > CO32- > SO42- > NO3- > Cl-. The saturated anthracite could be effectively regenerated by 0.2 mol L-1 HCl solution. Therefore, the granular anthracite used as filter medium also has a possible application as a nitrite scavenger at the same time.

Interpretation of Ocular Melanin Drug Binding Assays. Alternatives to the Model of Multiple Classes of Independent Sites.

Melanin has a high binding affinity for a wide range of drugs. The determination of the melanin binding capacity and its binding affinity are important, e.g., in the determination of the ocular drug distribution, the prediction of drug effects in the eye, and the trans-scleral drug delivery. The binding parameters estimated from a given data set vary significantly when using different isotherms or different nonlinear fitting methods. In this work, the commonly used bi-Langmuir isotherm, which assumes two classes of independent sites, is confronted with the Sips isotherm. Direct, log-log, and Scatchard plots are used, and the interpretation of the binding curves in the latter is critically analyzed. In addition to the goodness of fit, the emphasis is placed on the physical meaning of the binding parameters. The bi-Langmuir model imposes a bimodal distribution of binding energies for the sites on the melanin granules, but the actual distribution is most likely continuous and unimodal, as assumed by the Sips isotherm. Hence, the latter describes more accurately the distribution of binding energies and also the experimental results of melanin binding to drugs and metal ions. Simulations are used to show that the existence of two classes of sites cannot be confirmed on the sole basis of the shape of the binding curve in the Scatchard plot, and that serious doubts may appear on the meaning of the binding parameters of the bi-Langmuir model. Experimental results of melanin binding to chloroquine and metoprolol are used to illustrate the importance of the choice of the binding isotherm and of the method used to evaluate the binding parameters.

Biochar supported nanoscale zerovalent iron-calcium alginate composite for simultaneous removal of Mn(II) and Cr(VI) from wastewater: Sorption performance and mechanisms.

Heavy metal pollution in water caused by industrial activities has become a global environmental issue. Among them, manganese mining and smelting activities have caused the combined pollution of Cr(VI) and Mn(II) in water, posing a serious ecotoxicological risk to ecological environments and human health. To efficiently remove Cr(VI) and Mn(II) from wastewater, a novel biochar supported nanoscale zerovalent iron-calcium alginate composite (CA/nZVI/RSBC) was synthesized by liquid-phase reduction and calcium alginate embedding methods. The adsorption performance and mechanisms of Cr(VI) and Mn(II) by CA/nZVI/RSBC were investigated. The maximum adsorption capacities of Cr(VI) and Mn(II) onto CA/nZVI/RSBC fitted by the Langmuir model were 5.38 and 39.78 mg/g, respectively, which were much higher than the pristine biochar. The iron release from CA/nZVI/RSBC was comparatively lower than that of nZVI/RSBC. Mn(II) presence enhanced the reduction of Cr(VI) by CA/nZVI/RSBC. The results of XRD, XPS, and site energy distribution analysis indicated that redox was the predominant mechanism of Cr(VI) adsorption, while electrostatic attraction dominated Mn(II) adsorption. This study provides a novel alternative way for the simultaneous removal of Cr(VI) and Mn(II) in wastewater.

Guideline for modeling solid-liquid adsorption: Kinetics, isotherm, fixed bed, and thermodynamics.

During the years, adsorption has garnered considerable attention being one of the most cost-effective and efficient methods for separating contaminants out of liquid phase. A comprehensive understanding of adsorption mechanisms entails several crucial steps, including adsorbent characterization, batch and column adsorption tests, fitting of predefined kinetic and isotherm models, and meticulous thermodynamic analysis. These combined efforts serve to provide clarity and insights into the intricate workings of adsorption phenomena. However, the vast amount of literature published in the field each year is riddled with ill-considered model selections and incorrect parameter analyses. Therefore, the aim of this paper is to establish guidelines for the proper employment of these numerous kinetic, isotherm, and fixed-bed models in various applications. A thorough review has been undertaken, encompassing more than 45 kinetic models, 70 isotherm models, and 45 fixed bed models available hitherto, with their classification determined based on the adsorption mechanisms expounded within each of them. Moreover, five general approaches for modifying fixed-bed models were provided. The physical meanings, assumptions, and interconversion relationships of the models were discussed in detail, along with the information criterion used to evaluate their validity. In addition to commonly used activation energy and Gibbs energy analysis, the methods for calculating site energy distribution were also summarized.

Competitive adsorption of sulfamethoxazole and bisphenol A on magnetic biochar: Mechanism and site energy distribution.

Competitive adsorption and complementary adsorption between emerging pollutants has been observed in multiple studies. Investigation of the preference of pollutants for different types of adsorption sites can provide a supplementary perspective for understanding complementary adsorption. In this study, the simultaneous adsorption of two typical emerging pollutants, sulfamethoxazole (SMX) and bisphenol A (BPA), on magnetic biochar (MBC-1) was investigated. The results showed that the modification with ferric chloride optimized the surface properties of biochar (aromaticity, hydrophobicity, and oxygen-containing functional groups, etc.), and helped to remove SMX and BPA through various interactions. The equilibrium adsorption capacity of the two adsorbents was inhibited by competitive adsorption in the mixed solute systems, which was due to the same adsorption mechanism. When pH = 7, the SMX and BPA adsorption mainly involved pore filling, hydrophobic effect, π-π EDA, and hydrogen bonding. In addition, electrostatic force, surface coordination, and ion exchange have also been proven to be related to the adsorption of SMX and BPA. In the co-adsorption system, BPA's competitive advantage might be due to its superior hydrophobicity, charge property, and molecular diameter. In the competitive adsorption experiment, the total adsorption capacity (Qi) of the competitive solute exceeded the adsorption inhibition (△Qi) of the main solute, indicating that the two solutes occupied their preferred adsorption sites, which confirmed the complementary adsorption phenomenon. Complementary adsorption can be explained by the preference of SMX and BPA for different types of adsorption sites. BPA preferentially occupied high-energy sites in the co-adsorption system, such as π-π EDA interaction, ion exchange, and surface coordination. At the same time, SMX tended to be removed by hydrophobic interaction and hydrogen bonding.

π-π stack driven competitive /complementary adsorption of aromatic compounds on MIL-53(Al).

In this study, the selective adsorption of aromatic compounds on mesoporous MIL-53(Al) was investigated, and followed the order: Biphenyl (Biph) > Triclosan (TCS) > Bisphenol A (BPA) > Pyrogallol (Pyro) > Catechol (Cate) > Phenol (Phen), and exhibited high selectivity toward TCS in binary compounds. In addition to hydrophobicity and hydrogen bonding, π-π interaction/stacking predominated, and more evidently with double benzene rings. TCS-containing halogens could increase π interaction on the benzene rings via forming Cl-π stacking with MIL-53(Al). Moreover, site energy distribution confirmed that complementary adsorption mainly occurred in the Phen/TCS system, as evidenced by ΔQpri (the decreased solid-phase TCS concentration of the primary adsorbate) < Qsec (the solid-phase concentrations of the competitor (Phen)). In contrast, competitive sorption occurred in the BPA/TCS and Biph/TCS systems within 30 min due to ΔQpri = Qsec, followed by substitution adsorption in the BPA/TCS system, but not for the Biph/TCS system, likely attributed to the magnitude of energy gaps (Eg) and bond energy of TCS (1.80 eV, 362 kJ/mol) fallen between BPA (1.74 eV, 332 kJ/mol) and Biph (1.99 eV, 518 kJ/mol) according to the density-functional theory of Gaussian models. Biph with a more stable electronic homeostasis than TCS lead to the occurrence of substitution adsorption in the TCS/BPA system, but not in the TCS/Biph system. This study provides insight into the mechanisms of different aromatic compounds on MIL-53(Al).

Enhanced removal of organophosphate esters by iron-modified biochar with developed mesoporous: Performance and mechanism based on site energy distribution theory.

Removing the widely concerned pollutant of organophosphate esters (OPEs) by agriculture waste biochar is an effective way to address the waste and pollutant problem simultaneously. In this work, an iron-modified coconut shell biochar (MCSB) was prepared by co-pyrolysis method and used to adsorb tris(2-chloroethyl) phosphate (TCEP) and tris(1-chloro-2-propyl) phosphate (TCPP), which were two typical OPEs. The attention was focused on comprehensively investigating the adsorption behaviors to study the adsorption mechanisms of TCEP and TCPP onto MCSB. With the development of mesoporous and formation of γ-Fe2O3 in MCSB, the adsorption equilibrium was quickly reached in 60 min with the Langmuir maximum adsorption capacities of 211.3 mg/g for TCEP and 223.7 mg/g for TCPP, respectively. Results of adsorption kinetics and isotherm showed the heterogeneous and multilayer of the adsorption process. Pore-filling interaction, the Lewis acid-base interaction, and the hydrophobic interaction were considered to drive the adsorption. And the site energy distribution theory was introduced to further reveal that the physisorption was the main adsorption mechanism, while the Lewis acid-base interaction was responsible for the differences in adsorption of TCEP and TCPP onto MCSB. Additionally, the excellent adsorption performances of MCSB in various circumstances and fixed-bed column experiments suggested that the MCSB would be a promising adsorbent for OPEs removal.

Synthesis of co-pyrolyzed biochar using red mud and peanut shell for removing phosphate from pickling wastewater: Performance and mechanism.

Iron (Fe)/iron oxide-modified biochar has practicable adsorption capability for phosphorus (P), but it is expensive. In this study, we synthesized novel low-cost and eco-friendly adsorbents co-pyrolyzed biochars using Fe-rich red mud (RM) and peanut shell (PS) wastes via a one-step pyrolysis process for removing P from pickling wastewater. The preparation conditions (heating rate, pyrolysis temperature, and feedstock ratio) and P adsorption behaviors were systematically investigated. In addition, a series of characterization and approximate site energy distribution (ASED) analyses were conducted to understand the P adsorption mechanisms. The magnetic biochar (BR7P3) with m (RM):m (PS) of 7:3 prepared at 900°C and 10 °C/min had a high surface area (164.43 m2/g) and different abundant ions (including Fe3+, and Al3+). In addition, BR7P3 exhibited the best P removal capability (142.6 mg/g). The Fe2O3 from RM was successfully reduced to Fe0, which was easily oxidized as Fe3+ to precipitate with H2PO4-. The electrostatic effect, Fe-O-P bonding, and surface precipitation were the main mechanisms of P removal. ASED analyses revealed that high distribution frequency and solution temperature led to a high P adsorption rate of the adsorbent. Therefore, this study provides new insight into the waste-to-wealth strategy by transforming PS and RM into mineral-biomass biochar with excellent P adsorption capability and environmental adaptability.

[Sorption Mechanism and Site Energy Distribution of Acetaminophen on Straw-derived Biochar].

As one of the large dosages of pharmaceutical and personal care products (PPCPs), acetaminophen is widely present in the water environment and presents potential environmental risks. Therefore, it is necessary to study the removal mechanism of acetaminophen from the environment. Based on the high-value conversion demand of agricultural straw resources in China, straw-derived biochar prepared by pyrolysis has a good application prospect for the sorption and purification of acetaminophen in water. However, the sorption process and mechanism of straw-derived biochar for acetaminophen remain unclear. Four types of straw (rice, wheat, maize, and bean straw) were chosen as raw materials, and straw-derived biochars were prepared through the pyrolysis method at 400℃ and 500℃. The batch sorption experiments were used to study the sorption of acetaminophen to different sources and different pyrolysis temperature biochars. The effect of humic acid and pH on the sorption process was also studied. The results showed that:based on the Freundlich and site energy distribution models, the sorption of acetaminophen on biochar at 500℃ biochar was significantly higher than that at 400℃ biochar (the sorption coefficient KF was 1.16-2.53 times higher), and 500℃ biochar had more high-energy sorption sites. For high-temperature pyrolysis biochar, the primary sorption mechanism was pore sorption and π-π effect; for low-temperature pyrolysis biochar, the primary sorption mechanism for removing acetaminophen was H-bonding. The presence of humic acid enhanced the sorption of acetaminophen, which was attributed to the strong interaction between the humic acid selected in the experiment and acetaminophen, thus promoting adsorption. The decrease in sorption capacity of biochar caused by the increasing pH was mainly attributed to the pore blockage resulting from the aggregation of acetaminophen molecules. The pore sorption and π-π interaction of acetaminophen on straw-derived biochar could be promoted by increasing pyrolysis temperature. These experiments on humic acid and pH show that straw-derived biochar is not affected by humic acid and has good sorption performance in a low pH environment.

Adsorption of fulvic acid onto polyamide 6 microplastics: Influencing factors, kinetics modeling, site energy distribution and interaction mechanisms.

Information on the interactions of microplastics (MPs) with dissolved organic matter (DOM) is essential for understanding their environmental impacts. This study selected fulvic acid (FA) as a typical DOM to investigate the influence of contact time, temperature, dosage, solution pH, salinity, and coexisting metal ions on the adsorption of FA onto polyamide 6 (PA6) MPs. The adsorption kinetic and isotherm can be successfully described by mixed-order (MO) and Freundlich models. The adsorption site energy distribution based on the Freundlich equation was applied to analyze the interaction between FA and PA6-MPs and the adsorption site heterogeneity. Thermodynamic analysis demonstrated that the values of parameters (ΔGads°, ΔSads°, ΔHads°) were significantly affected by initial solution concentrations and the adsorption process was spontaneous, endothermic, and randomness-increased. Fourier transform-infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) revealed the importance of amide functional groups of PA6-MPs in controlling FA adsorption. Hydrogen bonds, hydrophobic, electrostatic, and n-π electron donor-acceptor (n-π EDA) interactions played different roles on adsorption of FA under different conditions of solution chemistry. These findings are beneficial to provide new insights involving the adsorption behavior and interaction mechanisms of FA onto PA6-MPs for the environmental risk assessment of MPs.

Manganese ferrite modified biochar from vinasse for enhanced adsorption of levofloxacin: Effects and mechanisms.

The primitive biochar (BC) and NiFe2O4/biochar composites (NFBC), biological adsorbents prepared from vinasse wastes, possess the environmental application in levofloxacin (LEV) removal. In this study, the efficient adsorption of LEV onto biochar synthesized by pyrolysis of vinasse wastes from aqueous environment was investigated. The influencing factors (i.e., pH, reaction time, and temperature) of adsorption process were also well studied. The results indicated that the maximum adsorption capacities of both BC and NFBC were occurred in mildly acidic condition (pH 6). In addition, the biochar adsorption capacities were obviously increased in higher temperature (25-45 °C). The chemistry adsorption and monolayer homogeneous dominated adsorption process of LEV onto BC and NFBC. The adsorption process was spontaneous and endothermic by thermodynamic analysis. The SEDA (site energy distribution analysis) explained that the adsorption effectivity increased by increasing site energy of biochar surface. The SEDA revealed the more energy heterogeneity in NFBC, fitting the characterization result of Fourier-transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The electron-donor-acceptor (EDA) interactions and hydrogen bonds is suggested as the major adsorption mechanism. And as for the adsorption of the various biowaste recycled synthetic, this study can be referred in discussion of performance analysis and optimal condition.

A mechanistic study on removal efficiency of four antibiotics by animal and plant origin precursors-derived biochars.

Extensive research has been performed on the utilization of biochar for pollutant removal via sorption. Additionally, the relationship between sorption strength of organic pollutants by organic matter and nanomaterials and their sorption site energy distribution has been studied. However, the linkage between removal efficiency of organic pollutants and the sorption site energy distribution on biochars is unknown. As a first attempt to address this knowledge gap, three biochars were derived from two plant-origin precursors (corn straw-CS; birch sawdust-BS) and one animal-origin precursor (meat and bone meal-MBM) at 500 °C (CS-500, BS-500, and MBM-500). In addition, two biochars were prepared with CS at 300 and 800 °C (CS-300 and CS-800) to examine the relationship between their site energy distribution and removal efficiency of antibiotics including sulfadiazine (SDZ), sulfamethoxazole (SMX), tetracycline (TC) and ciprofloxacin (CFX) by these materials. Our findings showed that the antibiotic-biochar interactions can be well interpreted with site energy distribution and XPS analysis results. Polar interactions between CS-300, CS-500, and CS-800 and SDZ and SMX occurring at the high-energy sites dominated their removal. However, TC and CFX removal by these biochars was driven by their polar interactions occurring at high-energy sites and π-π interactions at low-energy sites. The π-π stacking mechanism tended to dominate their removal with increasing charring temperature. Abundance of polar functionalities on CS-500, BS-500, and MBM-500 and TC removal efficiency of these materials consistently followed an order of MBM-500 > CS-500 > BS-500, highlighting importance of precursors for making biochars and polar interactions in its removal.

Microcystin-LR sorption and desorption by diverse biochars: Capabilities, and elucidating mechanisms from novel insights of sorption domains and site energy distribution.

This study accurately assessed microcystin-LR (MCLR)-trapping capabilities of diverse biochars based on sorption and sequential desorption (SDE), and elucidated MCLR sorption-desorption mechanisms from novel views of sorption domains and site energy distribution along sorption-SDE process. Results showed that maize straw biochar (MSB) and chicken manure biochar (CMB) excelled in trapping MCLR (91.0%-97.4% and 85.7%-96.4%, respectively, at 60-600 µg/L of initial MCLR amount), followed by their respective HCl-treated ones (HCMB, HSMB), while HCl-treated bamboo biochar and pine sawdust biochar poorly trapped MCLR (48.9%-77.8% for HBB, 22.6%-67.2% for HPSB). Non-partition sorption domains (NPSD) contributed more than partition sorption domain (PSD) to MCLR sorption by each biochar. Higher NPSD contribution to MCLR sorption in CMBs and MSBs than other biochars resulted from their higher pHPZC and mesoporosity, which provided stronger electrostatic and pore-filling interaction for MCLR. Desorption hysteresis was weaken with rising aqueous MCLR amount for most biochars. Along SDE process, remaining MCLR in PSD of MSBs, HPSB and HBB could transfer to NPSD, thus desorption ratio continuously decreased with increasing desorption cycle. Differently, remaining MCLR in NPSD of CMBs converted into PSD during 1st-3rd desorption, causing fluctuated desorption ratio without obvious decrease as desorption cycle increased. These implied that MCLR in PSD was more easily desorbed than NPSD for each biochar. Site energy distribution dynamics supported the results of PSD and NPSD contribution changes along SDE. This study was greatly implicated in cost-efficient emergent MCLR-pollution remediation and deeply understanding MCLR sorption-desorption mechanisms of diverse biochars.

Contrasting microcystin-LR sorption and desorption capability of different farmland soils amended with biochar: Effects of biochar dose and aging time.

This study explored biochar (BC) amendment effects on microcystin-LR (MCLR) concentration-dependent sorption and sequential desorption (SDE) by diverse soils to assess MCLR-trapping by BC-amended soils. Soil properties varied with rising BC dose and aging time. As aging proceeded, BC-amended soils shared a generally similar 'firstly increase and then decrease' trend of MCLR sorption and 'firstly decrease and then increase' trend of desorption at most cases. It appeared that MCLR sorption by BC-amended soils was most positively correlated with mesoporosity and surface basic functionality. BC-amendment increased MCLR-trapping for most soils, especially 4% BC at 3 month-aging maximized trapping ratio of GZ, SY and SX to 86.59%-95.43%, 80.01%-87.20% and 78.73%-90.85%, respectively, at 50-500 µg/L MCLR by largely increasing sorption and decreasing desorption. BC-amendment best matched GZ soil because MCLR-trapping of BC-amended GZ exceeded other amended soils at the same BC dose and aging time, but failed to obviously increase MCLR-trapping of HS soil at most cases, except only case with 2% BC at 3 month-aging. Site energy distribution verified that maximally enhanced MCLR-trapping of most soils was due to greatly enhanced sorption affinity during sorption and 1st desorption cycle, making closer MCLR-binding that more resistant to desorption. Contrarily, BC-amendment did not enhance sorption affinity of HS along sorption-SDE to compromise MCLR-trapping increase at most cases. This study validated 3 months as suitable BC-aging time to maximize MCLR-trapping in diverse soils, and elucidated influencing factors and mechanisms from view of site energy distribution, which shed novel insights on MCLR sorption-desorption by BC-amended soils, and guided to optimize BC-amendment strategy for efficient MCLR-immobilization and eco-risk elimination in diverse soils.

Immobilization of Cr(VI) on engineered silicate nanoparticles: Microscopic mechanisms and site energy distribution.

Engineered nanoparticles-mediated contaminant transport has been recognized as a significant process governing the mobility of metals and radionuclides in groundwater. Engineered silicate nanoparticles (ESNPs) are attractive materials for the sequestration or extraction of Cr(VI) and other metals and radionuclides from groundwater. While great efforts have been devoted toward the application of these materials for Cr(VI) sequestration, the underlying interface adsorption mechanism is not thoroughly elucidated. This study investigates the immobilization mechanisms of Cr(VI) on a representative ESNPs, NH2-MCM-41, over a range of water chemistry conditions. By combining batch adsorption experiments with an array of complementary characterizations, we provided spectroscopic and microscopic evidence that the electrostatic interactions between the positively charged NH2-MCM-41 surface derived from amino functionality and the negatively charged Cr(VI) species was the dominant mechanism responsible for Cr(VI) immobilization. In addition, the weak hydrogen bonding interactions may also contribute to adsorption to a degree. Furthermore, thermodynamic studies suggested a favorable, spontaneous, and exothermic adsorption process. Site energy analysis illustrated that the distribution of energy binding sites on NH2-MCM-41 is Cr(VI) loading dependent. The new insights provided here can advance understanding of the transport of Cr(VI) associated NH2-MCM-41 that benefits the application of ESNPs-based technologies for metals immobilization in groundwater.

Evaluation of the performance of zirconia-multiwalled carbon nanotube nanoheterostructures in adsorbing As(III) from potable water from the perspective of physical chemistry and chemical physics with a special emphasis on approximate site energy distribution.

In this study, the performance of zirconia-multiwalled carbon-nanotube nanoheterostructure in adsorbing the highly toxic water-contaminant As(III) from water has been probed from the perspective of physical chemistry and chemical physics. The adsorbent found extremely efficient in adsorbing As(III) from potable water. Moreover, its ability to oxidize As(III) to As(V) in the aqueous solution has been evinced by the XPS studies. The values of the maximum adsorption capacities (qm) depend on the isotherm studied and in this study, no wonder different values of qm are obtained for different adsorption isotherms. The thermodynamic studies advocate the exothermic and spontaneous nature of the adsorption process. Calculation on density functional theory (DFT) also suggested the exothermic nature of the adsorption process. DFT calculation further revealed the role of the Zr-O and Zr-OH bridges in binding As(III) species on the zirconia surface. However, this study finds an adverse effect of visible light-irradiation on the adsorption process. Furthermore, this study propounds an approach to estimate the maximum solubility of As(III) in water combining the Cerofolini's condensation-approximation and Polanyi adsorption potential. Detailed analysis on the approximate adsorption site energy distribution (f(E*)) further finds an inconsistency in the formula used to estimate qm using f(E*), which underestimates qm. The inconsistency, for the very first time, has successfully been resolved by modifying the heterogeneity related parameter in f(E*).

Effect of dissolved organic matter on adsorption of sediments to Oxytetracycline: An insight from zeta potential and DLVO theory.

To reveal the adsorption mechanism of sediment to antibiotics with the presence of dissolved organic matter (DOM), batch experiments were carried out by oxytetracycline (OTC) on sediments with decayed plants (PDOM) and composted chicken manure (MDOM), and the zeta potential in the system before and after adsorption was measured. Results showed that the PDOM promoted the adsorption process, while the MDOM inhibited the adsorption. Adding PDOM, the change of zeta potential (Δζ) increased by 40.08% for first terrace sediments (FT) and 63.98% for riverbed sediments (RB), respectively; meanwhile, MDOM decreased by 20.04% for FT and 28.39% for RB, respectively. The results of kinetic fitting models of replacing the adsorption amount with Δζ were consistent with the initial. It indicated that there was a positive correlation between the adsorption amount and Δζ, and the zeta potential can be used to quickly judge the degree of adsorption process. The Derjaguin-Landau-Verwey-Overbeek (DLVO) theory describes the interactions of sediment particles. In terms of adsorption amount, zeta potential (absolute value) and total interaction energy all followed the order: RB > FT, RB-PDOM > FT-PDOM, and RB-MDOM > FT-MDOM. The more negative the zeta potential is, the better the dispersion of the particles is. Stronger repulsion is more conducive to adsorbing positively charged OTC. The site energy distribution theory further explained that the distribution of adsorption site in the various states of sediments increased while adding the PDOM and decreased while adding the MDOM.