Ionizable Organic Compounds Research Articles

Sludge-derived hydrochar modulates complete nonradical electron transfer in peroxydisulfate activation via pyrrolic-N and carbon defect: Implication for degrading electron-rich ionizable anilines compounds

Nonradical electron transfer process (ETP) is a promising pathway for pollutant degradation in peroxydisulfate-based advanced oxidation processes (PDS-AOPs). However, there is a critical bottleneck to trigger ETP by sludge-derived hydrochar due to its negatively charged surface, inferior porosity and electrical conductivity. Herein, pyrrolic-N doped and carbon defected sludge-derived hydrochar (SDHC-N) was constructed for PDS activation to degrade anilines ionizable organic compounds (IOC) through complete nonradical ETP oxidation. Degradation of anilines IOC was not only affected by the electron-donating capacity but also proton concentration in solution because of the ionizable amino group (−NH2). Diverse effects including proton favor, insusceptible and inhibition were observed. Impressively, addition of HCO3 with strong proton binding capacity boosted aniline degradation nearly 10 times. Moreover, characterizations and theoretical calculations demonstrated that pyrrolic-N increased electron density and created positively charged surface, profoundly promoting generation of SDHC-N-S2O82−* complexes. More delocalized electrons around carbon defect could enhance electron mobility. This work guides a rational design of sludge-derived hydrochar to mediate nonradical ETP oxidation, and provides insights into the impacts of proton on anilines IOC degradation.

Comparative in vitro hepatic clearances of commonly used antidepressants, antipsychotics, and anti-inflammatory agents in rainbow trout liver S9 fractions

Residues of human pharmaceuticals are widely detected in surface waters and can be taken up by and bioaccumulate in aquatic organisms, especially fish. One of the key challenges in assessing the bioaccumulation potential of ionizable organic compounds, such as the pharmaceuticals, is the lack of empirical data for biotransformation. In the present study, we assessed the in vitro intrinsic clearances (CLINT) of twelve pharmaceuticals, individually and some additionally as mixtures, in rainbow trout (Oncorhynchus mykiss) liver S9 fractions (RT-S9) adhering to the OECD test guidance 319B. The test substances included four anti-inflammatory agents (diclofenac, ibuprofen, ketoprofen, naproxen), seven antidepressants/antipsychotics (citalopram, haloperidol, levomepromazine, mirtazapine, risperidone, sertraline, venlafaxine) and the O-desmethyl metabolite of venlafaxine. Quantifiable intrinsic clearances were detected for diclofenac, ibuprofen, naproxen, levomepromazine, and sertraline. Apart from diclofenac, the in vitro clearances of the other four pharmaceuticals were shown to be critically dependent on the cytochrome P450 (CYP) metabolism. Therefore, we also determined the half-maximal inhibitory concentrations (IC50) of the same twelve pharmaceuticals toward CYP1A-like (7-ethoxyresorufin-O-deethylation, EROD) and CYP3A-like (benzyloxy-4-trifluoromethylcoumarin-O-debenzyloxylation, BFCOD) activities in RT-S9 using IC50 shift assay. As a result, levomepromazine and sertraline were identified as the most potent inhibitors of both EROD and BFCOD activity (unbound IC50 < 10 µM each), followed by citalopram and haloperidol (10 µM < IC50 < 100 µM). Additionally, mirtazapine was a selective EROD inhibitor (IC50 ∼ 30 µM). The inhibitory impacts of haloperidol and sertraline were indicatively time dependent. Finally, we carried out intrinsic clearance assays with mixtures of diclofenac, ibuprofen, naproxen, levomepromazine, and sertraline to examine the impacts of EROD and BFCOD inhibitions on their in vitro CLINT in RT-S9. Our in vitro data suggests that the intrinsic clearances of ibuprofen, levomepromazine, and sertraline in rainbow trout can be significantly reduced as the result of P450 inhibition by pharmaceutical mixtures, whereas the clearances of diclofenac and naproxen are less impacted.

Mechanistic insights to sorptive removal of four sulfonamide antibiotics from water using magnetite-functionalized biochar

Magnetite-functionalized biochar (MBC) is a promising engineered material for remediation of antibiotic-contaminated fields. However, sorption mechanisms of ionizable organic compounds such as sulfonamide antibiotics (SAs) on MBC are still unclear. This study employed four representative SAs including sulfamethazine (SMT), sulfamerazine (SMR), sulfadiazine (SDZ), and sulfamethoxazole (SMX), to compare the difference in sorption on MBC. Results showed that the sorption capacities and affinities of the four SAs varied with their substituents, hydrophobic properties, and dissociation constants (pKa). Synergistic effect during co-pyrolysis with Fe3+ enhanced the sorption performance of MBC towards SAs compared to original BC. Spectral methods confirmed structural changes of MBC such as the variance in oxygen-containing groups and defective/graphitized phases. Results of modeling pH-dependent sorption revealed that H-bonding or π-bond assisted H-bonding determined the sorption affinities and capacities of SAs. In particular, the SAs with lower pKa were thermodynamically favorable to form H-bonding with MBC via proton exchange with water molecules. Quantum calculation results quantified the contributions of H-bonding strengths and found that the energies of H-bonding were correlated with affinities of SAs. Moreover, contributions of oxygen-containing groups instead of minerals dominated the H-bonding energies. Mechanistic insights from this study can be valuable in exploring engineered BC composites for practical application in field remediation.Graphical

QSPR models for complexation performance of α-cyclodextrin and β-cyclodextrin complexes by norm indices

A generic method for predicting the complexation performance of cyclodextrins complexes is desirable. Two quantitative structure–property relationship models are established for the complexation performance of α- and β-cyclodextrins. The datasets consist of 229 α-cyclodextrin and 330 β-cyclodextrin complexes, including conventional organic molecules, ionic organic compounds, and drugs. Internal validation, indicated by the squared correlation coefficient (Q2) of 0.8949 and 0.8954 for α- and β-cyclodextrin models, demonstrates the stability and robustness of these models. For external validation, the squared correlation coefficients of test sets (R2test) are 0.9315 (α-cyclodextrin model) and 0.9171 (β-cyclodextrin model), confirming the predictive ability of both models. Furthermore, the complexation performances of two ionic liquids are measured using UV spectrometric titration for our models’ external prediction. The mean absolute error between measured and calculated values for β-cyclodextrin complexes is 0.20 M−1, indicating the satisfactory transferability of the model. For the α-cyclodextrin model, the mean absolute error of 1.25 M−1 is deemed acceptable. Both the model validations and experimental results underscore the robustness and predictive performance of these models. In conclusion, these developed models could effectively predict binding constants of several types of molecules with cyclodextrins, which can become valuable tools for cyclodextrin design.

Thermochemistry of hybrid materials.

This paper is based on a lecture Navrotsky gave honouring the memory of Paul McMillan. It summarizes our recent findings in the thermodynamics of hybrid materials including metal organic frameworks (MOFs), polymer-derived ceramics (PDCs) and ionic organic-inorganic compounds. This work describes the main structure types and their corresponding thermodynamic stability, obtained from calorimetric measurements in our laboratory. The effects of linker substituent and framework topology on the thermodynamic stability of isostructural zeolitic imidazolate frameworks and other MOFs are discussed. The paper documents the effects of interdomain interaction and bonding speciation on the thermodynamic stability of various PDC compositions, including SiC, SiOC and SiCN systems. The paper further describes effects of different cations on the thermodynamic stability of selected ionic organic-inorganic compounds. Similarities and differences among these materials are emphasized. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 2)'.

Efficient one-pot synthesis of magnetic MIL-100(Fe) using nitric acid without additional Fe ion addition and adsorption behavior of charged organic compounds

Metal organic frameworks (MOFs) are attracting attention as high-performance adsorbents because of their high specific surface area and porosity. In particular, magnetic MIL-100(Fe) has the both characteristics of Fe3O4 and MIL-100(Fe), which are magnetic characteristics, high specific surface area and open metal sites. However, multiple synthetic steps are required for synthesis of magnetic MOF, and there is limitation that the residual organic linker and unreacted Fe center ions can be discharged, and they cause water pollution. In this study, magnetic MIL-100(Fe) was synthesized within 4 h without the addition of Fe ions by using nitric acid for the surface modification of Fe3O4. Magnetic MIL-100(Fe) was confirmed through XRD, FTIR, and TEM surface analysis, and the optimal conditions for nitric acid addition were selected through magnetization measurements and BET analysis of synthesized magnetic MIL-100(Fe). Thereafter, adsorption evaluation was performed using MB and MO, which are representative cationic and anionic dyes, respectively. The pseudo-second-order Langmuir model showed a relatively high correlation compared to the other models. This shows that the adsorption mechanism depends on both the amount of adsorbent and adsorbate, and Fe3O4 modification with nitric acid does not cause any change in the adsorption mechanism. In the case of adsorption selectivity between the MB and MO, removal rates of 93.27% and 58.73% were obtained, respectively. The above results can contribute to the simplification of the manufacturing of magnetic metal organic frameworks for removing ionic organic compounds and the minimization of water pollution in the manufacturing process.

Tissue-specific accumulation, depuration, and effects of perfluorooctanoic acid on fish: Influences of aqueous pH and sex

Perfluorooctanoic acid (PFOA) is widely distributed in nature, particularly in aquatic environments. Its bioaccumulation and toxicity in aquatic organisms can be affected by both the chemical status of PFOA in water and the physiology of the organism. However, research on the patterns of these effects is scarce. In this study, we investigated the influence of aqueous pH (pH 6, acidic; pH 7.5, neutral; pH 9, basic) and fish sex on PFOA uptake, clearance, and biochemical effects in crucian carp (C. auratus) using flow-through exposure. In the 17-d kinetic experiment, PFOA bioaccumulation adhered to a uniform first-order model in which PFOA uptake rates from water to blood and liver in acidic conditions were faster than those in other conditions, indicating possible acidic pH influence on PFOA uptake. PFOA clearance rates in these compartments of males were slower than in females, which was attributed to the notably stronger expression of Oat2 (organic anion transporter 2, responsible for reabsorption) in the kidneys of males. Similar responses were observed for peroxisome proliferation-related biomarkers at different pH levels and in different sexes. These biochemical responses were driven by the internal concentrations of PFOA. The inhibition acetylcholinesterase activity in the fish brain was closely linked to changes in P-glycoprotein content, demonstrating a protective relationship. Collectively, an aqueous pH lower than 7.5 might affect the uptake of PFOA by fish. The clearance discrepancies between the sexes highlight the importance of anion carriers for ionizable organic compounds in aquatic organisms.

Improved ionic organic pollutant degradation under visible light by Ag SPR-promoted phosphorus-doped g-C3N4/AgBr/Bi2WO6 with excellent charge transfer capacity and high surface area

Graphite carbon nitride (g-C3N4) has a strong photocatalytic capability to degrade ionic organic compounds due to its unique electrical structure with numerous marginal amino groups. A photocatalyst was fabricated via a facile in-situ sedimentation–calcine–hydrothermal method by anchoring AgBr and Bi2WO6 onto the framework of phosphorus-doped g-C3N4 (PCAB). The photocatalyst has been proven to have good photocatalytic degradation effect on different ionic organic pollutants. The removal rate of tetracycline, the target pollutant, can reach 99.2%, which was 1.83 times higher than that of g-C3N4 within 60 min under visible light. Moreover, the degradation rates of dyes containing azo bonds and -SO3H can reach 100% within 20 min, as determined by the electrical relationship between the catalyst and the dye. The excellent performance can be attributed to the synergistic effect of the formation of mid-gap in g-C3N4 after phosphorus doping, improvements in charge carrier transfer and the low recombination rate based on the construction of dual Z-scheme heterojunction and Ag bridge. In addition, cycling experiments and characterizations illustrated the high stability and reusability of PCAB. The main active species during photocatalytic process was·O2−, whereas h+ and·OH played a minimal role. Ultimately, a dual Z-scheme mechanism was proposed to explain the photocatalytic reaction.

Effect of pH-Dependent Homo/Heteronuclear CAHB on Adsorption and Desorption Behaviors of Ionizable Organic Compounds on Carbonaceous Materials.

Herein, the adsorption/desorption behaviors of benzoic acid (BA) and phthalic acid (PA) on three functionalized carbon nanotubes (CNTs) at various pH were investigated, and the charge-assisted H-bond (CAHB) was verified by DFT and FTIR analyses to play a key role. The results indicated that the adsorption order of BA and PA on CNTs was different from Kow of that at pH 2.0, 4.0, and 7.0 caused by the CAHB interaction. The strength of homonuclear CAHB (≥78.96 kJ·mol−1) formed by BA/PA on oxidized CNTs is stronger than that of heteronuclear CAHB formed between BA/PA and amino-functionalized CNTs (≤51.66 kJ·mol−1). Compared with the heteronuclear CAHB (Hysteresis index, HI ≥ 1.47), the stronger homonuclear CAHB leads to clearly desorption hysteresis (HI ≥ 3.51). Additionally, the contribution of homonuclear CAHB (≥52.70%) was also greater than that of heteronuclear CAHB (≤45.79%) at pH 7.0. These conclusions were further confirmed by FTIR and DFT calculation, and the crucial evidence of CAHB formation in FTIR was found. The highlight of this work is the identification of the importance and difference of pH-dependent homonuclear/heteronuclear CAHB on the adsorption and desorption behaviors of ionizable organic compounds on carbonaceous materials, which can provide a deeper understanding for the removal of ionizable organic compounds by designed carbonaceous materials.

Human Apparent Volume of Distribution Predicts Bioaccumulation of Ionizable Organic Chemicals in Zebrafish Embryos.

Chemicals with elevated bioaccumulation profiles present potential hazards to public health and the environment. Ionizable organic compounds (IOCs) increasingly represent a large proportion of commercial chemicals; however, historical approaches for bioaccumulation determinations are mainly developed for neutral chemicals, which were not appropriate for IOCs. Herein, we employed the zebrafish embryo, a common vertebrate model in environmental and biomedical studies, to elucidate toxicokinetics and bioconcentration of eight IOCs with diverse physicochemical properties and pharmacokinetic parameters. At an environmentally relevant pH (7.5), most IOCs exhibited rapid uptake and depuration in zebrafish, suggesting the ionized forms of IOCs are readily bioavailable. Bioconcentration factors (BCF) of these IOCs ranged from 0.0530 to 250 L·kg-1 wet weight. The human pharmacokinetic proportionality factor, apparent volume of distribution (VD), better predicted the BCF of selected IOCs than more commonly used hydrophobicity-based parameters (e.g., pH-dependent octanol-water distribution ratio, Dow). Predictive bioaccumulation models for IOCs were constructed and validated using VD alone or with Dow. Significant relationships between fish BCF and human VD, which is readily available for pharmaceuticals, highlighted the utility of biologically based "read-across" approaches for predicting bioaccumulative potential of IOCs. Our novel findings thus provided an understanding of the partitioning behavior and improved predictive bioconcentration modeling for IOCs.

Recovery of L-glutamic acid from ammonium glutamate by Donnan dialysis: Membrane characteristic and operation parameters

A proof-of-concept study using Donnan dialysis with cation-exchange membranes (CEMs) to recover glutamic acid (GA) from ammonium glutamate was herein developed for cleaner production without directly adding sulfate acid to the fermentation broth. Different commercial CEMs were compared and the operation conditions, including flow velocity, temperature and acid concentration, were investigated focusing on GA conversion and recovery in the feed solution as well as NH4+ transport performance. The results showed that the cation-exchange membranes with low water content and large thickness benefited for GA recovery; And the ones allowing for superior ion transport flux were those possessing relatively high fixed charge density combined with low thickness. Under the optimized condition, the GA conversion rate could reach over 83% and ammonium removal rate over 93% at initial concentration ratio of H+ to NH4+ of 1.6. Meanwhile, over 96% of GA was recovered, avoiding wastewater containing high content of ammonium sulfate. This work indicated that Donnan dialysis could be a promising option toward GA cleaner production and provides important knowledge for better understanding of transport phenomena in the system with ionic organic compounds.

Electro-assisted removal of polar and ionic organic compounds from water using activated carbon felts

Highly water-soluble, persistent, and mobile organic compounds (PMOCs) are more and more often detected in surface and groundwater, evoking potential threats to the environment and human health. Traditional water treatment strategies, including adsorption by activated carbon materials, fail to efficiently remove PMOCs due to their hydrophilic nature. Electro-assisted sorption processes offer a clean, facile, and promising solution to remove PMOCs on activated carbon-based electrodes and potentially allow an easy on-site sorbent regeneration (trap&release). In this work, the electrosorption of five selected PMOCs, that is, tetrapropylammonium (TPA+), benzyltrimethylammonium (BTMA+), p-tosylate (p-TsO-), p-toluenesulfonamide (p-TSA), and methyl-tert-butyl ether (MTBE), were investigated on two comprehensively characterized activated carbon felt (ACF) types carrying different surface functionalities. Significant enrichment factors in ranges of 102 to 103 for charged PMOCs were expected by our first estimation for electro-assisted trap&release on ACFs in flow systems applying potentials in the range of −0.1 V/+0.6 V vs. SHE for ad-/desorption, respectively. Defunctionalized ACF carrying larger density in surface π-systems and lower O-content promises a higher capability in electrosorption processes than the pristine material in terms of better material stability (tested for 5 cycles over 500 h) and better removal efficiency of ionic PMOCs. To improve ACFs adsorption performance for cationic and anionic PMOCs, permanent chemical surface modification and reversible electric polarization as alternative strategies are compared. Our findings explore future electrode and process design of electrosorption for applications to treat water contaminated by emerging PMOCs.

Sorption and Mobility of Charged Organic Compounds: How to Confront and Overcome Limitations in Their Assessment.

Permanently charged and ionizable organic compounds (IOC) are a large and diverse group of compounds belonging to many contaminant classes, including pharmaceuticals, pesticides, industrial chemicals, and natural toxins. Sorption and mobility of IOCs are distinctively different from those of neutral compounds. Due to electrostatic interactions with natural sorbents, existing concepts for describing neutral organic contaminant sorption, and by extension mobility, are inadequate for IOC. Predictive models developed for neutral compounds are based on octanol–water partitioning of compounds (Kow) and organic-carbon content of soil/sediment, which is used to normalize sorption measurements (KOC). We revisit those concepts and their translation to IOC (Dow and DOC) and discuss compound and soil properties determining sorption of IOC under water saturated conditions. Highlighting possible complementary and/or alternative approaches to better assess IOC mobility, we discuss implications on their regulation and risk assessment. The development of better models for IOC mobility needs consistent and reliable sorption measurements at well-defined chemical conditions in natural porewater, better IOC-, as well as sorbent characterization. Such models should be complemented by monitoring data from the natural environment. The state of knowledge presented here may guide urgently needed future investigations in this field for researchers, engineers, and regulators.

Adsorption of polar and ionic organic compounds on activated carbon: Surface chemistry matters

Persistent and mobile organic compounds (PMOCs) are often detected micropollutants in the water cycle, thereby challenging the conventional wastewater and drinking water treatment techniques. Carbon-based adsorbents are often less effective or even unable to remove this class of pollutants. Understanding of PMOC adsorption mechanisms is urgently needed for advanced treatment of PMOC-contaminated water. Here, we investigated the effect of surface modifications of activated carbon felts (ACFs) on the adsorption of six selected PMOCs carrying polar or ionic groups. Among three ACFs, defunctionalized ACF bearing net positive surface charge at neutral pH provides the most versatile sorption efficiency for all studied PMOC types representing neutral, anionic and cationic compounds. Ion exchange capacity giving quantitative information of sorbent surface charges at specified pH is recognized as a frequently underestimated key property for evaluating adsorbents aiming at PMOC adsorption. A most recently developed prediction tool for Freundlich parameters in PMOC adsorption was applied and the prediction results are compared to the experimental data. The comparison demonstrates the so far underestimated importance of the sorbent surface chemistry for PMOC adsorption affinity and capacity. PMOC adsorption mechanisms were additionally investigated by adsorption experiments at various temperatures, pH values and electrolyte concentrations. Exothermic sorption was observed for all sorbate-sorbent pairs. Adsorption is improved for ionic PMOCs on AC carrying sites of the same charge (positive or negative) at increased electrolyte concentration, while not affected for neutral PMOCs unless strong electron donor-acceptor yet weak non-Coulombic interactions exist. Our findings will allow for better design and targeted application of activated carbon-based sorbents in water treatment facilities.

Translocation versus ion trapping in the root uptake of 2,4-dichlorophenol by wheat seedlings.

Understanding of the plant uptake of ionizable organic compounds is critical to the evaluation of crop contamination, plant protection, and phytoremediation. This study investigated the time-dependent uptake of 2,4-dichlorophenol (DCP) by intact wheat seedling roots and subsequent translocation to shoots at pH 5.0 and 8.0. Sorption of DCP by cut roots and shoots at these two pHs was conducted to provide the uptake limits and the Donnan charge. For comparison, sorption was also conducted for 1,3-dichlorobenzene (DCB), a nonionizable compound having a structure similar to that of DCP. The DCB sorption isotherms were linear and independent of pH, yielding a consistent log Klip of 3.56 with both roots and shoots, reflective of the essential dominant role of lipids in plant partition uptake. Whereas the DCP sorption also showed a linear isotherm at pH 5.0 with log Klip = 2.88, the sorption at pH 8.0 was nonlinear with a concave downward shape, especially at low concentrations. With live wheat seedlings, the DCB uptake by roots and the DCB translocation to shoots rapidly approached a steady state, showing no obvious pH effect. On the DCP uptake by live plants, there was a rapid attainment of a steady state in roots at pH 5.0 coupled with a retarded transport to shoots due presumably to the polarity of DCP. At pH 8.0, the root uptake of DCP was comparatively slower and the translocation to shoots was completely inhibited due presumably to DCP ionization. At high pH, DCP was supposedly accumulated in an ionized form in root cells via an ion-trapping mechanism.

Per- and polyfluoroalkyl substances (PFASs) in the soil-plant system: Sorption, root uptake, and translocation.

Per- and polyfluoroalkyl substances (PFASs) are ubiquitous in the environment but pose potential risks to ecosystems and human health. The soil-plant system plays an important role in the bioaccumulation of PFASs. Because most PFASs in the natural environment are anionic and amphiphilic (both lipophilic and hydrophilic), their sorption and accumulation behaviors differ from those of neutral organic and common ionic compounds. In this review, we discuss processes affecting the availability of PFASs in soil after analyzing the potential mechanisms underlying the sorption and uptake of PFASs in the soil-plant system. We also summarize the current knowledge on root uptake and translocation of PFASs in plants. We found that the root concentration factor of PFASs for plants grown in soil was not significantly correlated with hydrophobicity, whereas the translocation factor was significantly and negatively correlated with PFAS hydrophobicity regardless of whether plants were grown hydroponically or in soil. Further research on the cationic, neutral, and zwitterionic forms of diverse PFASs is urgently needed to comprehensively understand the environmental fates of PFASs in the soil-plant system. Additional research directions are suggested, including the development of more accurate models and techniques to evaluate the bioavailability of PFASs, the effects of root exudates and rhizosphere microbiota on the bioavailability and plant uptake of PFASs, and the roles of different plant organelles, lipids, and proteins in the accumulation of PFASs by plants.

Disentangling Mechanisms in Natural Toxin Sorption to Soil Organic Carbon.

Natural toxins are multifunctional, often ionizable organic compounds increasingly detected in the environment. Surprisingly little is known about their interactions with soil organic carbon, although sorption largely controls transport, bioavailability, and dissipation. For a set of 117 natural toxins from 36 compound classes the pH-dependent organic carbon-water distribution coefficient (Doc) was quantified using a soil column chromatography approach under changing conditions with regards to pH, ionic strength, and the major inorganic cation in solution. Natural toxins could be assigned to groups with either hydrophobic partitioning or specific interactions (complexation reactions, cation exchange) as dominating sorption mechanisms. The complex interplay of interactions in the sorption of natural toxins was equally influenced by sorbate, sorbent, and solution specific characteristics. High variability in sorption was particularly observed in the presence of Ca2+ resulting in Doc being enhanced by a factor of 10 when the pH was increased from 4.5 to 6. Sorbates following this trend contain either functional groups able to form ternary complexes via Ca2+ or aromatic moieties adjacent to protonated N presumably stabilizing cation exchange reactions. Although sorption was often stronger than predicted, investigated natural toxins were highly mobile under all considered conditions.

Comparative study on tartaric acid production by two-chamber and three-chamber electro-electrodialysis

Acidification is an essential step in organic acid production. In this work, an environmentally friendly electro-electrodialysis (EED) process was carried out to transform potassium tartrate (K2Tar) to tartaric acid (H2Tar) without additional waste salt generation. The characteristics of ions migration in the two-chamber EED and three-chamber EED processes were investigated, and the conversion ratio of tartaric acid and specific energy consumption of the two configurations were also compared. The competitive migration of K+ ions and H+ ions through cation exchange membrane was the key factor affecting the extent of acidification in the two-chamber EED process, while the selective transport of tartrate ions (Tar2−) and H+ ions through the anion exchange membrane influenced the three-chamber EED process significantly. The three-chamber process generated pure H2Tar solution with higher concentration than the two-chamber process and reached a conversion ratio of 99% after 120 min’s operation running at 7 mA/cm2. Owing to the lower resistance of the two-chamber membrane stack, the specific energy consumption in the two-chamber EED process was lower than that of three-chamber EED process. This work provides important knowledge for assessing the application of EED in the production of tartaric acid (H2Tar) from potassium tartrate (K2Tar) and a better understanding of the transport phenomena in the system with ionic organic compounds.

Underwater suspended bifunctionalized polyethyleneimine-based sponge for selective removal of anionic pollutants from aqueous solution

Highly selective and efficient removal of ionic pollutants, including ionic organic compounds and heavy metal ions from water, is still a huge challenge due to the complex nature of polluted water. To meet this challenge, we presented the synthesis of bifunctionalized polyethyleneimine-based sponges through cryo-polymerization via BDDE as the crosslinker followed by bifunctional modification with glycidyl trimethylammonium chloride (GTAC) and phenyl glycidyl ether (PGE), which simultaneously afford quaternary ammonium cation (strongly basic and hydrophilic) and phenyl (hydrophobic) functionalities, respectively. As a result, a hybrid hydrophilic-hydrophobic sponge is generated that could stably be suspended underwater due to the co-operative effect of the water-absorbing hydrophilic domain and the hydrophobic domain generating buoyancy. The quaternized and phenyl-functionalized PEI-based sponge (SQP-PEI) demonstrated highly selective and efficient removal of anionic pollutants from water, including diclofenac sodium (DIC), methyl orange (MO) and chromium (Cr(VI)) with co-existing interferences. The Langmuir isotherms revealed the maximum adsorption capacities of 342.7 mg/g, 491.9 mg/g, and 242.7 mg/g for DIC, MO, and Cr(VI), respectively. The studies of adsorption mechanism suggested that the bifunctional SQP-PEI sponge indeed afford both strong anion-exchange interaction and π–π interaction toward organic pollutants DIC and MO, and the strong anion-exchange interaction can be the dominated adsorption mechanism for anionic DIC, MO and Cr(VI) species. The suspended SQP-PEI also demonstrated excellent reusability, which shows the potential of SQP-PEI for real applications.

Sorption of anthracene (C14H10) and 9-anthroic acid (C15H10O2) onto biochar-amended soils as affected by field aging treatments

There is a lack of information on how aging affects the sorption of ionizable organic compounds on biochar-amended soils. To that end, this study investigates the sorption of two hydrophobic solutes (anthracene (ANT) and 9-anthroic acid (9-ANCA)) onto biochar-amended (5%, w/w) soils as a function of aging period (0, 6, and 12 months), electrolyte (5 mM CaCl2 and 10 mM KCl), and aqueous pH. The isotherm plot of both solutes was fairly linear (r2 > 0.998) and the linear sorption coefficient (Kd, L kg−1) was obtained from this. In CaCl2 solution at pH 5, the log Kd of ANT tended to decrease (from 3.90 to 3.72) with an increasing aging period, which was attributed to clogged pore surface, whereas the differences in 9-ANCA sorption (from 2.56 to 2.51) were not significant (α = 0.05). The increased ANT sorption at acidic pH (<4) could be attributed to π-π interaction. Aqueous Ca2+ ions played an important role in 9-ANCA sorption by forming a Ca-bridge between anionic solute and negatively charged adsorbent surface, thus accounting for up to 35% of its sorption at alkaline pH (>8). The spectroscopic data and isoelectric point measurement results indicated that the number of oxygen-containing functional groups and the content of elemental oxygen were both higher in aged samples, resulting in a more polar (negatively charged) surface. The formation of surface polar groups and the associated deformation altered the adsorbent nature of the tested biochar, thereby fortifying the hydrophilic retention propensity for ionizable organic solutes.