Bacterial nanocellulose-clay film as an eco-friendly sorbent for superior pollutants removal from aqueous solutions.

The persistent water treatment and separation challenge necessitates innovative and sustainable advances to tackle conventional and emerging contaminants in the aquatic environment effectively. Therefore, a unique three-dimensional (3D) network composite film (BNC-KC) comprised of bacterial nanocellulose (BNC) incorporated nano-kaolinite clay particles (KC) was successfully synthesized via an in-situ approach. The microscopic characterization of BNC-KC revealed an effective integration of KC within the 3D matrix of BNC. The investigated mechanical properties of BNC-KC demonstrated a better performance compared to BNC. Thereafter, the sorption performance of BNC-KC films towards basic blue 9 dye (Bb9) and norfloxacin (NFX) antibiotic from water was investigated. The maximum sorption capacities of BNC-KC for Bb9 and NFX were 127.64 and 101.68 mg/g, respectively. Mechanistic studies showed that electrostatic interactions, multi-layered sorption, and 3D structure are pivotal in the NFX/Bb9 sorption process. The intricate architecture of BNC-KC effectively traps molecules within the interlayer spaces, significantly increasing sorption efficiency. The distinctive structural configuration of BNC-KC films effectively addressed the challenges of post-water treatment separation while concurrently mitigating waste generation. The environmental evaluation, engineering, and economic feasibility of BNC-KC are also discussed. The cost estimation assessment of BNC-KC revealed the potential to remove NFX and Bb9 from water at an economically viable cost.

Optimizing bone and biomass co-torrefaction parameters: High-performance arsenic removal from wastewater via co-torrefied bone char.

This study aimed to investigate bone char's physicochemical transformations through co-torrefaction and co-pyrolysis processes with biomass. Additionally, it aimed to analyze the carbon sequestration process during co-torrefaction of bone and biomass and optimize the process parameters of co-torrefaction. Finally, the study sought to evaluate the arsenic sorption capacity of both torrefied and co-torrefied bone char. Bone and biomass co-torrefaction was conducted at 175 °C-300 °C. An orthogonal array of Taguchi techniques and artificial neural networks (ANN) were employed to investigate the influence of various torrefaction parameters on carbon dioxide sequestration within torrefied bone char. A co-torrefied bone char, torrefied at a reaction temperature of 300 °C, a heating rate of 15 °C·min-1, and mixed with 5 g m of biomass (wood dust), was selected for the arsenic (III) sorption experiment due to its elevated carbonate content. The results revealed a higher carbonate fraction (21%) in co-torrefied bone char at 300 °C compared to co-pyrolyzed bone char (500-700 °C). Taguchi and artificial neural network (ANN) analyses indicated that the relative impact of process factors on carbonate substitution in bone char followed the order of co-torrefaction temperature (38.8%) > heating rate (31.06%) > addition of wood biomass (30.1%). Co-torrefied bone chars at 300 °C exhibited a sorption capacity of approximately 3 mg g-1, surpassing values observed for pyrolyzed bone chars at 900 °C in the literature. The findings suggest that co-torrefied bone char could serve effectively as a sorbent in filters for wastewater treatment and potentially fulfill roles such as a remediation agent, pH stabilizer, or valuable source of biofertilizer in agricultural applications.

Comparison of Adsorption Performance of Biochar Derived from Urban Biowaste Materials for Removal of Heavy Metals.

This study investigated the adsorption performance of biochar produced from different types of urban biowaste material viz., sugarcane bagasse (SB), brinjal stem (BS), and citrus peel (CP) for removal of heavy metal ions (Pb, Cu, Cr, and Cd) from aqueous solution. The effects of biowaste material, dosage of biochar, solution pH, and initial concentration of heavy metal ions and isotherm models were performed to understand the possible adsorption mechanisms. The results showed that the biochar derived from BS and SB removes Cu (99.94%), Cr (99.57%), and Cd (99.77%) whereas biochar derived from CP removes Pb (99.59%) and Cu (99.90%) more efficiently from the aqueous solution. Biochar derived from BS showed maximum adsorption capacity for Cu (246.31 mg g-1), Pb (183.15 mg g-1), and Cr (71.89 mg g-1) while the biochar derived from CP showed highest for Cd (15.46 mg g-1). Moreover, biochar derived from BS and SB has more polar functional groups and less hydrophobicity than the biochar derived from CP. This study reveals that solution pH and biochar doses play a major role in removal of heavy metal ions from aqueous solution. The results of Langmuir model fitted well for Pb and Cu while the Freundlich model for Cr and Cd. Our study concludes that the biochar derived from different biowaste materials adsorbs heavy metal ions majorly through surface complexation and precipitation processes. The results of this study will be very useful in selecting the effective urban biowaste material for making biochar for heavy metal removal from the aqueous environment.

Rigidity and Flexibility: Unraveling the Role of Fulvic Acid in Uranyl Sorption on Graphene Oxide Using Molecular Dynamics Simulations.

Using molecular dynamics simulations, this work targets a molecular understanding on the rigidity and flexibility of fulvic acid (FA) in uranyl sorption on graphene oxide (GO). The simulations demonstrated that both rigid Wang's FA (WFA) and flexible Suwannee River FA (SRFA) can provide multiple sites to cooperate with GO for uranyl sorption and act as "bridges" to connect uranyl and GO to form GO-FA-U (type B) ternary surface complexes. The presence of flexible SRFA was more beneficial to uranyl sorption on GO. The interactions of WFA and SRFA with uranyl were primarily driven by electrostatics, and the electrostatic interaction of SRFA-uranyl was significantly stronger owing to the formation of more complexes. The flexible SRFA could markedly enhance the bonding strength of uranyl with GO by folding itself to provide more sites to coordinate with uranyl. The rigid WFAs tended to be adsorbed on the GO surface in parallel due to π-π interactions, whereas the flexible SRFAs took more slant configurations resulting from intermolecular hydrogen bonds. This work provides new insights into the sorption dynamics, structure, and mechanism and addresses the effect of molecular rigidity and flexibility, with great significance for FA-based remediation strategies of uranium-contaminated sites.

A systematic review on distribution, sources and sorption of perfluoroalkyl acids (PFAAs) in soil and their plant uptake.

Perfluoroalkyl acids (PFAAs) are ubiquitous in environment, which have attracted increasing concerns in recent years. This study collected the data on PFAAs concentrations in 1042 soil samples from 15 countries and comprehensively reviewed the spatial distribution, sources, sorption mechanisms of PFAAs in soil and their plant uptake. PFAAs are widely detected in soils from many countries worldwide and their distribution is related to the emission of the fluorine-containing organic industry. Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) are found to be the predominant PFAAs in soil. Industrial emission is the main source of PFAAs contributing 49.9% of the total concentrations of PFAAs (Æ© PFAAs) in soil, followed by activated sludge treated by wastewater treatment plants (WWTPs) (19.9%) and irrigation of effluents from WWTPs, usage of aqueous film-forming foam (AFFFs) and leaching of leachate from landfill (30.2%). The adsorption of PFAAs by soil is mainly influenced by soil pH, ionic strength, soil organic matter and minerals. The concentrations of perfluoroalkyl carboxylic acids (PFCAs) in soil are negatively correlated with the length of carbon chain, log Kow, and log Koc. The carbon chain lengths of PFAAs are negatively correlated with the root-soil concentration factors (RCFs) and shoot-soil concentration factors (SCFs). The uptake of PFAAs by plant is influenced by physicochemical properties of PFAAs, plant physiology and soil environment. Further studies should be conducted to make up the inadequacy of existing knowledge on the behavior and fate of PFAAs in soil-plant system.

Extended Rate Constants Distribution (RCD) Model for Sorption in Heterogeneous Systems: 4. Kinetics of Metal Ions Sorption in the Presence of Complexing Agents-Application to Cu(II) Sorption on Polyethyleneimine Cryogel from Acetate and Tartrate Solutions.

Here, we report a new version of the extended Rate Constants Distribution (RCD) model for metal ion sorption, which includes complex-formation equilibria. With the RCD-complex model, one can predict sorbent performance in the presence of complexing agents using data on metal ion sorption from ligand-free solutions and a set of coefficients for sorption rate constants of different ionic species. The RCD-complex model was applied to breakthrough curves of Cu(II) sorption from acetate and tartrate solutions on polyethyleneimine (PEI) monolith cryogel at different flow rates and ionic speciation. We have shown that, despite the lower stability of Cu(II)-acetate complex, at high flow rates, acetate has a more pronounced negative effect on sorption kinetics than tartrate. The RCD model was successfully used to predict the shape of the breakthrough curves at an arbitrary acetate concentration but failed to predict Cu(II) sorption from tartrate solutions in a broad range of ligand concentrations. Since a twofold increase in sorption capacity was observed at low tartrate concentrations, the latter fact was related to an alteration in the sorption mechanism of Cu(II)-ions, which depended on Cu(II) ionic speciation. The obtained results emphasize the importance of information about sorption kinetics of different ionic forms for the optimization of sorption filter performance in the presence of complexing agents.

Nano-hydroxyapatite modified biochar: Insights into the dynamic adsorption and performance of lead (II) removal from aqueous solution.

Adsorption of lead as Pb(II) using biochar is an environmentally sustainable approach to remediate this kind of pollution affecting wastewater. In this study, rice straw biochar (BC) was modified by combination with nano-hydroxy-apatite (HAP), resulting in a material designated as BC@nHAP, with enhanced adsorption performance. Based on Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses, it was evidenced that, after modification, HAP greatly enhanced surface functional groups (i.e., -COOH and/or -OH) of raw biochar's surface. Batch tests showed that the maximum sorption capacity of BC (63.03 mg g-1) was improved due to the modification, reaching 335.88 mg g-1 in BC@nHAP. Pseudo-second order (PSO) kinetics fitted well the adsorption data (R2 = 0.99), as well as the Langmuir isotherm model (showing an adsorption value of 335.88 mg g-1 for qe). The results of thermodynamic calculations showed that the adsorption was primarily governed by chemisorption process. FTIR spectroscopy and XPS spectrum after adsorption further confirmed that the adsorption mechanisms were ion exchange with Pb2+ and surface complexation by -OH and -COOH. In addition, BC@nHAP revealed a brilliant regeneration capability. The maximum adsorption capacity by BC@nHAP was higher than that of raw biochar or other previously reported adsorbents. Therefore, BC@nHAP could be seen as a new sorbent material with high potential for real-scale heavy metal removal from wastewater, and specifically as a capable candidate new sorbent for Pb(II) removal from wastewater, which has clear implications as regard preservation of environmental quality and public health.

Evaluation of Drug Sorption on Laboratory Materials with Abraham Solvation Parameters of Drugs and its Prevention.

PURPOSE: Undesired drug sorption on laboratory material surfaces reduces the performance of analytical methods and results in the generation of unreliable data. Hence, we characterized the sorption of drugs and evaluated the sorption extent using a linear free energy relationship (LFER) model with Abraham solvation parameters of drugs. Furthermore, to prevent sorption, the effects of additives, such as organic solvents and salts, were evaluated. METHODS: The sorption of fifteen model drugs (concentration: 2 µM), with various physicochemical properties, on materials in 0.2% dimethyl sulfoxide aqueous solutions was evaluated. Drug sorption extent on the materials was determined using high-performance liquid chromatography. The obtained results were analyzed using an LFER model with Abraham solvation parameters of the drugs. The effect of additives on the sorption of itraconazole, one of the most hydrophobic drugs among those tested in this study, was investigated. RESULTS: Sorption was dependent on the physicochemical properties of drugs, rather than the type of materials used, and additives altered the rate of drug sorption. Equations were developed to evaluate the sorption extent (nmol) of drugs to glass and polypropylene using the Abraham solvation parameters of the drugs. CONCLUSIONS: LFER modeling with Abraham solvation parameters of drugs enabled us to evaluate drug sorption on materials. All the additives altered the rate of drug sorption, and some organic solvents effectively prevented sorption. The developed LFER model would be useful for assessment of the sorption properties of compounds in in vitro evaluations in drug discovery research and various other biochemical fields.

Sorption of organochlorine pesticides on polyethylene microplastics in soil suspension.

As a new type of environmental pollutant, microplastics (MPs) can adsorb residual organochlorine pesticides (OCPs) in the soil and pose a severe threat to the soil ecosystems. To understand the interaction between soil MPs and OCPs, the sorption of two kinds of OCPs, including hexachlorocyclohexanes (HCHs) and dichlorodiphenyltrichloroethanes (DDTs), on polyethylene (PE) microplastics in soil suspension was studied through sorption kinetics and isotherm models. The effects of solution/soil ratio and MPs diameter on sorption were examined. The kinetic experiment results show that the sorption equilibrium was 12 h， and the sorption process of OCPs on MPs can be well described by a pseudo-second-order model. The Freundlich model (R2 = 0.942-0.997) provides a better fit to the sorption isotherm data than the Langmuir model (R2 = 0.062-0.634), indicating that the sorption process takes place on the nonuniform surface of MPs. The MPs had a good sorption effect on OCPs when the solution/soil ratio was from 75:1 to 100:1. As the diameter of MPs increases, the sorption capacity decreases. These results provide support for further research on microplastic pollution in soil.

Evaluation of the effect of the intrinsic chemical properties of pharmaceutically active compounds (PhACs) on sorption behaviour in soils and goethite.

The role of the chemical properties of Pharmaceutically Active Compounds (PhACs) in their sorption behaviour and consequently in their fate and mobility is of major environmental interest, but a comprehensive evaluation is still lacking. The sorption of nine PhAC molecules with distinct physico-chemical properties on soils and goethite was described using linear, Freundlich and Langmuir models and the relationship between the chemical structures of the compounds and the parameters of the adsorption was evaluated using redundancy analysis (RDA). The latter showed that the sorption of the pharmaceuticals was determined by the intrinsic chemical characteristics of the molecules, as shown by the 35% value of constrained variability. For the hydrophobic estrogens, E1, E2 and EE2, the logD value and the number of hydrogen bond sites were found to be the main controlling factors for adsorption, indicating that hydrophobic interaction and hydrogen bonding are the dominant sorption mechanisms. The π energy of the molecules also proved a very important parameter, governing the retention of PhACs in soils, especially in the case of carbamazepine, oxazepam and lamotrigine. The main controlling factor for ionic compounds, such as diclofenac sodium, tramadol or lidocaine, is the fraction of PhACs present as charged species, revealing the importance of Coulomb forces. The results of this study will allow semi-quantitative predictions to be made on how the molecular structure governs the sorption of PhACs and which sorption mechanism could be involved.

Comparative analysis of kinetics and mechanisms for Pb(II) sorption onto three kinds of microplastics.

Microplastics (MPs), a kind of novel contaminant, have potential to concentrate and transport heavy metals in the aquatic environment. This feature may affect the distribution and bioavailability of heavy metals. In order to determine the sorption behaviors of heavy metals onto the MPs, the sorption kinetics and mechanisms were investigated between the MPs (polyvinylchloride PVC, polyethylene PE, polystyrene PS) and Pb(II). The results suggested that the Pb(II) sorption onto the MPs were pH- and ionic strength-dependent. The sorption processes were best fitted by the pseudo-second-order model, and the rate-limiting steps were the intraparticle diffusion and final equilibrium process. The maximum sorption capacities of PVC, PE and PS were 483.1 µg/g, 416.7 µg/g and 128.5 µg/g under the condition of 0.01 M NaCl, pH 6.0, T = 298 K. The sorption rate constants were in the following order: PVC

Sorption Behavior and Mechanisms of Organic Contaminants to Nano and Microplastics.

Nano and microplastics (NPs/MPs) have received widespread attention in recent years. Because of their large specific surface area and hydrophobicity, NPs/MPs can adsorb various organic contaminants. This article gives a brief review of the sorption behavior of organic contaminants to NPs/MPs, summarizes the possible sorption mechanisms, and analyzes the influencing factors in the environment on the sorption behavior and mechanisms of NPs/MPs. The main mechanisms of sorption of organic contaminants to NPs/MPs are partitioning, surface sorption (hydrogen bonding, π-π interaction, electrostatic interaction, and van der Waals force), and pore filling. The sorption behavior of organic contaminants to NPs/MPs is not only affected by the properties of the NPs/MPs and the organic contaminants, but also by the solution chemistry, such as the pH, ionic strength, and dissolved organic matter.

Characteristics and applications of biochar for remediating Cr(VI)-contaminated soils and wastewater.

Chromium (Cr) is a common environmental contaminant due to industrial processes and anthropogenic activities such as mining of chrome ore, electroplating, timber treatment, leather tanning, fertilizer and pesticide, etc. Cr exists mainly in both hexavalent [Cr(VI)] and trivalent [Cr(III)] form, being Cr(VI) with non-degradability and potential to be hidden, thereby affecting surrounding environment and being toxic to human health. Therefore, researches on remediation of Cr pollution in the environment have received much attention. Biochar is a low-cost adsorbent, which has been identified as a suitable material for Cr(VI) immobilization and removal from soil and wastewater. This review incorporates existing literature to provide a detailed examination into the (1) Cr chemistry, the source and current status of Cr pollution, and Cr toxicity and health; (2) feedstock and characterization of biochar; (3) processes and mechanisms of immobilization and removal of Cr by biochar, including oxidation-reduction, electrostatic interactions, complexation, ion exchange, and precipitation; (4) applications of biochar for Cr(VI) remediation and the modification of biochar to improve its performance; (5) factors affecting removal efficiency of Cr(VI) with respect to its physico-chemical conditions, including pH, temperature, initial concentration, reaction time, biochar characteristics, and coexisting contaminants. Finally, we identify current issues, challenges, and put forward recommendations as well as proposed directions for future research. This review provides a thorough understanding of using biochar as an emerging biomaterial adsorbent in Cr(VI)-contaminated soils and wastewater.

Interaction of arsenic(III) and arsenic(V) on manganese dioxide: XPS and electrochemical investigations.

Manganese dioxide (MnO2) synthesized by solid-state reaction was characterized and sorption of As(III) and As(V) on it was studied in batch mode using 76As radiotracer. Arsenic removal efficiency was ∼98 % in the pH range of 3-9. Solvent extraction study indicated that >95% of arsenic is present as As(V) after sorption. A new electrochemical method was developed for explaining the arsenic-manganese interactions. Cyclic voltammetry and chronopotentiometry measurements were carried out which indicated the difference in the interaction of As(III) and As(V) with MnO2. X-ray Photoelectron Spectroscopy (XPS) was carried out in which the 3p3/2 binding energy peak of As(III) and As(V) standards was compared with the binding energy peaks observed for arsenic sorbed on manganese dioxide. The binding energy peaks of arsenic on MnO2 were matching with that of As(V), irrespective of the oxidation state of arsenic taken for sorption. The study confirmed that irrespective of the initial oxidation state, arsenic was sorbed on MnO2 as As(V); during the oxidation of As(III) by MnO2, manganese was reduced to Mn(II) and the Mn(II) formed during sorption was sorbed on the surface creating fresh surface promoting further sorption. Based on the observations, a mechanism of sorption has been proposed.

Arsenic adsorption on Fe-Mn modified granular activated carbon (GAC-FeMn): batch and fixed-bed column studies.

Granular activated carbon (GAC) was modified with Fe-Mn binary oxide to produce a novel effective hybrid adsorbent (GAC-FeMn) for simultaneous removal of As(III) and As(V) from water. After characterization (including BET, SEM/EDS and XRD analyses) of the raw and modified GAC, FTIR analysis before and after As removal showed that ligand exchange was the major mechanism for As removal on GAC-FeMn. Sorption kinetics followed pseudo-second order kinetics for both As(III) and As(V) and were not controlled by intraparticle diffusion. Batch equilibrium experiments yielded adsorption capacities for As(III) and As(V) of 2.87 and 2.30 mg/g, and demonstrated that better sorption was achieved at low pH. Of the competitive anions investigated (PO43-, SiO32-, CO32-, SO42-, NO3-, Cl-), phosphate had the greatest negative effect on As(III) and As(V) adsorption. Three sorption/desorption cycles were conducted in continuous column tests with a real arsenic contaminated groundwater, with subsequent TCLP leaching tests confirming the stability of the spent sorbent. In the column tests, breakthrough curves were also obtained for phosphates, which were present at a relatively high concentration (1.33 mg/L) in the investigated groundwater. The phosphates limited the effective operational bed life of GAC-FeMn for arsenic removal. Nonetheless, the maximum arsenic adsorption capacities for GAC-FeMn obtained by the Thomas model during the three sorption cycles were high, ranging from 18.8 to 29.8 mg/g, demonstrating that even under high phosphate loads, with further process improvements, GAC-FeMn may provide an excellent solution for the economic removal of arsenic from real groundwaters.

Charge Control in Two Isostructural Anionic/Cationic CoII Coordination Frameworks for Enhanced Acetylene Capture.

Two isostructural CoII -based metal-organic frameworks (MOFs) with the opposite framework charges have been constructed, which can be simply controlled by changing the tetrazolyl or triazolyl terminal in two bifunctional ligands. Notably, the cationic MOF 2 can adsorb much more C2 H2 than the anionic MOF 1 with an increase of 88 % for C2 H2 uptake at 298 K in spite of more active nitrogen sites in 1. Theoretical calculations indicate that both nitrate and triazolyl play vital roles in C2 H2 binding and the C2 H2 adsorption isotherm confirms that the enhanced C2 H2 uptake for 2 (225 and 163 cm3 g-1 at 273 and 298 K) is exceptionally high for MOF materials without open metal sites or uncoordinated polar atom groups on the frameworks.

General facile approach to transition-metal oxides with highly uniform mesoporosity and their application as adsorbents for heavy-metal-ion sequestration.

Mesoporous powders of transition-metal oxides, TiO2, ZrO2, HfO2, Nb2O5, and Ta2O5, pure from organic impurities were produced by a rapid single-step thermohydrolytic approach. The obtained materials display an impressively large active surface area and sharp pore-size distribution, being composed of partially coalesced uniform nanoparticles with crystalline cores and amorphous shells. They reveal extremely high adsorption capacity in removal of Cr(VI) anions from solutions (25.8 for TiO2, 73.0 for ZrO2, and 74.7 mg g(-1) for Nb2O5 in relation to the Cr2O7(2-) anion), making them very attractive as adsorbents in water remediation applications. The difference in adsorption capacities for the studied oxides may be explained by variation in surface hydration and surface-charge distribution.

The synergistic effect of typical chiral organic acids and solution chemistry conditions on the transport of 2-arylpropionic acid chiral derivatives in porous media.

The hazards of man-made chiral compounds are of great public concern, with reports of worrying stereoselective compounds and an urgent need to assess their transport. This study evaluated the transport of 2-arylpropionic acid derivatives enantiomers (2-APA) in porous media under a variety of solution chemistry conditions via column packing assays. The results revealed the introduction of Malic acid (MA) enantiomers enhanced the mobility of 2-APA enantiomers, but the enhancement effect was different for different 2-APA enantiomers. Batch sorption experiments confirmed that the MA enantiomers occupied the sorption site of the quartz sand, thus reducing the deposition of the 2-APA enantiomer. Homo- or heterochirality between 2-APA and MA dominates the transport of 2-APA enantiomers, with homochirality between them triggering stronger retention and vice versa. Further evaluating the effect of solution chemistry conditions on the transport of 2-APA enantiomers, increased ionic strength attenuated the mobility of 2-APA enantiomers, whereas introduced coexisting cations enhanced the retention of 2-APA enantiomers in the column. The redundancy analyses corroborated these solution chemistry conditions were negatively correlated with the transport of 2-APA enantiomers. The coupling of pH and these conditions reveals electrostatic forces dominate the transport behavior and stereoselective interactions of 2-APA enantiomers. Distinguishing the transport of enantiomeric pair helps to understand the difference in stereoselectivity of enantiomers and promises to remove the more hazardous one.

A comprehensive study of artificial neural network for sensitivity analysis and hazardous elements sorption predictions via bone char for wastewater treatment.

Using bone char for contaminated wastewater treatment and soil remediation is an intriguing approach to environmental management and an environmentally friendly way of recycling waste. The bone char remediation strategy for heavy metal-polluted wastewater was primarily affected by bone char characteristics, factors of solution, and heavy metal (HM) chemistry. Therefore, the optimal parameters of HM sorption by bone char depend on the research being performed. Regarding enhancing HM immobilization by bone char, a generic strategy for determining optimal parameters and predicting outcomes is crucial. The primary objective of this research was to employ artificial neural network (ANN) technology to determine the optimal parameters via sensitivity analysis and to predict objective function through simulation. Sensitivity analysis found that for multi-metals sorption (Cd, Ni, and Zn), the order of significance for pyrolysis parameters was reaction temperature > heating rate > residence time. The primary variables for single metal sorption were solution pH, HM concentration, and pyrolysis temperature. Regarding binary sorption, the incubation parameters were evaluated in the following order: HM concentrations > solution pH > bone char mass > incubation duration. This approach can be used for further experiment design and improve the immobilization of HM by bone char for water remediation.

Using the benzenepolycarboxylic acid (BPCA) method to assess activated biochars and their PFAS sorption abilities.

Activated carbon (AC) has important industrial and environmental applications as it has excellent abilities to sorb contaminants such as per- and polyfluoroalkyl substances (PFAS). Current research aims to develop activated biochars (AB) from renewable biomass to replace AC that is produced from fossil feedstock. Both AC and AB are primarily comprised of condensed aromatic carbon (ConAC), the component that is the focus of this study. ConAC is characterized to determine its relationship with biochar activation conditions and PFAS sorption, which are understudied at present. Benzenepolycarboxylic acid (BPCA) markers for ConAC were quantified in steam-activated biochars (AB-Steam) and carbon dioxide-activated biochars (AB-CO2) prepared from waste timber at different temperatures (800, 850, 900 °C) and molar ratios of feedstock-carbon:steam (0.50 - 1.25). A non-activated biochar was also included as a reference. ConAC relative to total organic carbon content was higher in AB-Steam than in AB-CO2 (92 ± 2 % vs. 81 ± 11%). The ratio of benzenehexa- (B6CA) to benzenepentacarboxylic (B5CA) acids revealed that AB-Steam also had larger ConAC clusters than AB-CO2. These findings provide novel evidence that steam activation is more effective than CO2 activation in creating ConAC. To assess how ConAC impacts AB sorption abilities, AB-Steam were used to remediate PFAS from contaminated soils. The observed strong correlations between ConAC content and sorption of long-chain PFAS suggest the importance of hydrophobic interactions between PFAS tails and ConAC. Poor correlations for short-chain PFAS, on the other hand, indicated the existence of electrostatic repulsion interactions between PFAS head groups and ConAC. Collectively, these results explain the great ability of AB-Steam to sorb PFAS from contaminated soils (up to 100% remediation). More broadly, this work demonstrates that the BPCA method can be a valuable tool to assess the quality of biochars and other carbonaceous sorbents in relation to their production conditions or contaminant sorption abilities.