Strength Of Solution Research Articles

Incorporation of Cu-TATAB metal-organic framework within polyurethane nanocomposite for enhanced thin film microextraction of some chlorinated pesticides

In this research, electrospun nanofibers based on copper-based metal organic framework (MOF)/polyurethane (PU) were prepared in order to achieve an applicable and superior extractive phase. The incorporation of MOF, in the synthesized nanocomposite contributed to the enhanced sorption efficiency. The prepared sorbent was implemented for the thin film microextraction (TFME) of target compounds with subsequent quantification using gas chromatography-mass spectrometry (GC–MS). To obtain the maximum efficiency of the synthesized sorbent, the influential parameters on extraction and desorption steps, including the MOF percentage in nanocomposite, desorption solvent type and its volume, desorption time, solution ionic strength and extraction time were optimized. After method development, the linear dynamic range (0.02–700 μg L−1), limits of detection (LODs) (0.005–0.1 μg L−1) and limits of quantification (LOQs))0.02–0.33 μg L−1(were calculated. The relative standard deviations values for intra-day and inter-day analysis were found to be in the range of 4.3–5.3 % and 6.2–8.1 %, respectively. The developed method was validated for the TFME of model organochlorine (OC) pesticide residues in fish, soil and water samples. the recovery values for the spiked samples at two concentration levels of 5 and 100 µg l-1 were found in the range of 72–110 %.

Spiky Magnetic Microparticles Synthesized from Microrod-Stabilized Pickering Emulsion.

Tailoring the microstructure of magnetic microparticles is of vital importance for their applications. Spiky magnetic particles, such as those made from sunflower pollens, have shown promise in single cell treatment and biofilm removal. Synthetic methods that can replicate or extend the functionality of such spiky particles would be advantageous for their widespread utilization. In this work, a wet-chemical method is introduced for spiky magnetic particles that are templated from microrod-stabilized Pickering emulsions. The spiky morphology is generated by the upright attachment of silica microrods at the oil-water interface of oil droplets. Spiky magnetic microparticles with control over the length of the spikes are obtained by dispersing hydrophobic magnetic nanoparticles in the oil phase and photopolymerizing the monomer. The spiky morphology dramatically enhances colloidal stability of these particles in high ionic strength solutions and physiologic media such as human saliva and saline-based biofilm suspension. To demonstrate their utility, the spiky magnetic particles are applied for magnetically controlled removal of oral biofilms and retrieval of bacteria for diagnostic sampling. This method expands the toolbox for engineering microparticle morphology and could promote the fabrication of functional magnetic microrobots.

Surface Modification of Graphene Oxide for Fast Removal of Per- and Polyfluoroalkyl Substances (PFAS) Mixtures from River Water.

Per- and polyfluoroalkyl substances (PFAS) make up a diverse group of industrially derived organic chemicals that are of significant concern due to their detrimental effects on human health and ecosystems. Although other technologies are available for removing PFAS, adsorption remains a viable and effective method. Accordingly, the current study reported a novel type of graphene oxide (GO)-based adsorbent and tested their removal performance toward removing PFAS from water. Among the eight adsorbents tested, GO modified by a cationic surfactant, cetyltrimethylammonium chloride (CTAC), GO-CTAC was found to be the best, showing an almost 100% removal for all 11 PFAS tested. The adsorption kinetics were best described by the pseudo-second-order model, indicating rapid adsorption. The isotherm data were well supported by the Toth model, suggesting that PFAS adsorption onto GO-CTAC involved complex interactions. Detailed characterization using scanning electron microscopy-energy dispersive X-ray spectroscopy, Fourier transform infrared, thermogravimetric analysis, X-ray diffraction, and X-ray photoelectron spectroscopy confirmed the proposed adsorption mechanisms, including electrostatic and hydrophobic interactions. Interestingly, the performance of GO-CTAC was not influenced by the solution pH, ionic strength, or natural organic matter. Furthermore, the removal efficiency of PFAS at almost 100% in river water demonstrated that GO-CTAC could be a suitable adsorbent for capturing PFAS in real surface water.

Effect of grain size variation on strontium sorption to heterogeneous aquifer sediments

Strontium-90 (90Sr) is a major contaminant at nuclear legacy sites. The mobility of 90Sr is primarily governed by sorption reactions with sediments controlled by high surface area phases such as clay and iron oxides. Sr2+ adsorption was investigated in heterogeneous unconsolidated aquifer sediments, analogous to those underlying the UK Sellafield nuclear site, with grainsizes ranging from gravels to clays. Batch sorption tests showed that a linear Kd adsorption model was applicable to all grainsize fractions up to equilibrium [Sr] of 0.28 mmol L−1. Sr2+ sorption values (Kd; Langmuir qmax) correlated well with bulk sediment properties such as cation exchange capacity and surface area. Electron microscopy showed that heterogeneous sediments contained porous sandstone clasts with clay minerals (i.e. chlorite) providing an additional adsorption capacity. Therefore, gravel corrections that assumed that the > 2 mm fractions are inert were not appropriate and underestimated Kd(bulk) adsorption coefficients. However, Kd (<2 mm) values measured from sieved sediment fractions, were effectively adjusted to within error of Kd (bulk) using a surface area dependant gravel correction based on particle size distribution data. Amphoteric pH dependent Sr2+ sorption behaviour observed in batch experiments was consistent with cation exchange modelling between pH 2–7 derived from the measured cation exchange capacities. Above pH 7 model fits were improved by invoking a coupled cation exchange/surface complexation which allowed for addition sorption to iron oxide phases. The overall trends in Sr2+ sorption (at pH 6.5–7) produced by increasing solution ionic strength was also reproduced in cation exchange models. Overall, the results showed that Sr2+ sorption to heterogeneous sediment units could be estimated from Kd (<2 mm) data using appropriate gravel corrections, and effectively modelled using coupled cation exchange and surface complexation processes.

Multi-component ion equilibria and transport in ion-exchange membranes

At the interface between an ion-exchange membrane and a multi-electrolyte solution, charged species redistribute themselves to minimize the free energy of the system. In this paper, we explore the Donnan equilibrium of membranes with quaternary electrolyte (Na+/Mg2+/K+/Ca2+/Cl−) solutions, experimentally. The data was used to calculate the ion activity coefficients for six commercial cation-exchange membranes (CEMs). After setting one of the activity coefficients to an arbitrary value, we used the remaining (N-1) activity coefficients as fitting parameters to describe the equilibrium concentrations of (N) ionic species with a mean relative error of 3 %. At increasing solution ionic strengths, the equivalent ion fractions of monovalent counter-ions inside the membrane increased at the expense of the multivalent ones in alignment with the Donnan equilibrium theory. The fitted activity coefficients were employed in a transport model that simulated a Donnan dialysis experiment involving all four cations simultaneously. The arbitrary value assigned to one activity coefficient affects the calculated Donnan potential at the membrane interface. Nevertheless, this arbitrary value does not affect the prediction of the ion concentrations inside the membrane and consequently does not affect the modeled ion fluxes.

Electrochemical degradation of carbamazepine in water by a flow-through and pilot-scale reactor with carbon felt electrodes: Parametric study under realistic operational conditions

Carbamazepine (CBZ) is one of the most stable pharmaceutical compounds that is commonly found in the effluents of wastewater treatment plants (WWTP). In this context, this contribution presents a comprehensive analysis of the different operating parameters of a flow-through and pilot-scale cylindrical reactor for hydrogen peroxide (H2O2) generation, in which the degradation of CBZ takes place. The electrochemical system was evaluated using 8 L of electrolytes prepared with tap water in the presence of methanol as dissolved organic matter or spiked tertiary WWTP effluent, at a volumetric flow of 7 L min−1. This reactor (i) improves the mass transport due to its flow-through configuration using fibrous quasi-three-dimensional carbon felt electrodes, (ii) operates without an external oxygen supply to promote the H2O2 electrosynthesis because it is incorporated by a jet aerator (iii) achieves the Fenton reaction at circumneutral pH due to Fe(II) disposition from a cation exchange resin. At first, the carbonaceous materials were electrochemically characterized by cyclic voltammetry measurements. Different operating parameters were evaluated by factorial design methodologies for H2O2 generation, energetic consumption and CBZ removal. The application of a current density of 1.4 mA cm−2, in a cathode-anode-cathode arrangement immersed in a 120 mM ionic strength solution, allowed to obtain up to 6.4 mg H2O2 L−1 after 40 min, consuming 0.44 kWh m−3. Later, the Fenton reaction was validated by a florescence study, and by the incorporation of 0.75 g of granular activated carbon and 5 g of Fe(II) loaded resin, CBZ abatement yields of 68 % and 32 % were obtained using a synthetic solution and a spiked tertiary WWTP effluent, respectively, and up to 28 % of the dissolved total organic carbon was removed. Finally, an analysis of the stability of the carbon felt electrodes was tackled using scanning electron microscopy and energy-dispersive X-ray spectroscopy.

Nanobubble transport in porous media: Towards agro- and environmental applications

Nanobubbles have been increasingly used in various applications involving porous media, such as groundwater remediation and irrigation. However, the fundamental scientific knowledge regarding the interactions between nanobubbles and the media is still limited. The interactions can be repulsive, attractive, or inert, and can involve reversible or irreversible attachment as well as destructive mechanisms. Specifically, the stability and mobility of nanobubbles in porous media is expected to be dependent on the dynamic conditions and the physicochemical properties of the porous media, solutions, and nanobubbles themselves. In this study, we investigated how changes in solution chemistry (pH, ionic strength, and valence) and media characteristics (size and wettability) affect the size and concentration of nanobubbles under dynamic conditions using column experiments. Quartz crystal microbalance with dissipation monitoring provided a deeper understanding of irreversible and elastic nanobubbles’ interactions with silica-coated surfaces. Our findings suggest that nanobubbles are less mobile in solutions of higher ionic strength and valence, acidic pH and smaller porous media sizes, while the wettability of porous media has a negligible influence on the retention of nanobubbles. Overall, our findings provide insights into the underlying mechanisms of nanobubble interactions and suggest potential strategies to optimize their delivery in various applications.

Bacterial transport mediated by micro-nanobubbles in porous media

Determining the role of micro-nanobubbles (MNBs) in controlling the risk posed by pathogens to soil and groundwater during reclaimed water irrigation requires clarification of the mechanism of how MNBs block pathogenic bacteria. In this study, real-time bioluminescence imaging was used to investigate the effects of MNBs on the transport and spatiotemporal distribution of bioluminescent Escherichia coli 652T7 strain in porous media. The presence of MNBs significantly increased the retention of bacteria in the porous media, decreasing the maximum relative effluent concentration (C/C0) by 78 % from 0.97 (without MNBs) to 0.21 (with MNBs). The results suggested that MNBs provided additional sites at the air-water interface (AWI) for bacterial attachment and acted as physical obstacles to reduce bacterial passage. These effects varied with environmental conditions such as solution ionic strength and pore water velocity. The results indicated that MNBs enhanced electrostatic attachment of bacteria at the AWI and their mechanical straining in pores. This study suggests that adding MNBs in pathogen-containing water is an effective measure for increasing filtration efficiency and reducing the risk of pathogenic contamination during agricultural irrigation.

Virus removal by microfiltration: Effects of electrostatic and hydrophobic interactions

Virus removal by membrane filtration is challenging due to the small size of these microorganisms. For microfiltration (MF) membranes, which have pore sizes above 100 nm (i.e., larger than most viruses), surface interactions are of critical importance in determining virus removal. The present study aims to evaluate the impact of surface interactions on virus removal by MF membranes wherein predictions by extended DLVO (XDLVO) modeling are compared with experimental data on virus clearance. The study employed four viruses (MS2, Qβ, phiX174, phi6), two MF cartridge membranes (nylon and PTFE), and several solution chemistry conditions to cover a range of virus-membrane surface interaction scenarios. For the hydrophilic nylon membrane, the highest log removal values (LRVs) were observed at the pH when the filter carried a slightly positive charge. For the hydrophobic PTFE membrane, higher LRVs were attained for high ionic strength solutions, wherein the electric double layer was compressed, even at pH values where the filter was negatively charged. We conclude that the electrostatic interaction determines whether viruses can approach the membrane and hydrophobic interactions are a critical factor in retaining viruses near the membrane surface, preventing viral leakage into the filtrate. The surface interactions have to be considered in virus membrane filtration.

Four-Component Statistical Copolymers by RAFT Polymerization.

This manuscript serves as the starting point for in-depth research of multicomponent, statistical, methacrylate-based copolymers that potentially mimic the behavior of proteins in aqueous solutions. These synthetic macromolecules are composed of specially chosen comonomers: methacrylic acid (MAA), oligoethylene glycol methyl ether methacrylate (OEGMA475), 2-(dimethylamino)ethyl methacrylate (DMAEMA) and benzyl methacrylate (BzMA). Monomer choice was based on factors such as the chemical nature of pendant functional groups, the polyelectrolyte/polyampholyte and amphiphilic character and the overall hydrophobic-hydrophilic balance (HLB) of the obtained quaterpolymers. Their synthesis was achieved via a one-pot reversible addition fragmentation chain transfer (RAFT) polymerization in two distinct compositions and molecular architectures, linear and hyperbranched, respectively, in order to explore the effects of macromolecular topology. The resulting statistical quaterpolymers were characterized via 1H-NMR and ATR-FTIR spectroscopies. Their behavior in aqueous solutions was studied by dynamic (DLS) and electrophoretic light scattering (ELS) and fluorescence spectroscopy (FS), producing vital information concerning their self-assembly and the structure of the formed aggregates. The physicochemical studies were extended by tuning parameters such as the solution pH and ionic strength. Finally, the quaterpolymer behavior in FBS/PBS solutions was investigated to test their colloid stability and biocompatibility in an in vivo-mimicking, biological fluid environment.

How does the diurnal biological clock influence electrokinetics in a living plant?

The existence of electrical potential in plant tissues has been studied for decades to understand its contribution toward the plants' health and developmental aspects. This potential is profoundly controlled and modulated by the electrokinetics involved in the flow navigated through the narrow conduits of a plant, which in turn is primarily governed by circadian rhythms. However, the interconnection between electrokinetics and the diurnal biological clock is yet to be understood. In this work, we unraveled the electrokinetics in response to the diurnal variations of a plant. Experiments conducted on water hyacinth stem indicate a cyclic variation of streaming potential synchronized with the changes introduced by circadian rhythm. In further efforts toward understanding the variation of streaming potential at different flow conditions, experiments were conducted on excised stem segments of Dracaena sanderiana, where the generated potential was studied against varying flow rates with different constitutive features of the flowing electrolyte. Notably, the resulting streaming potential from the flow of electrolytic solutions of different ionic strengths, species, and pH was found to align well with the fundamental premises of electrokinetics. These results are likely to expand our current knowledge of plant hydraulics by diligently examining the electrokinetics involved in the flow circuits of plants that undergo cyclic variations in close association with the circadian rhythms.

The suspension stability of nanoplastics in aquatic environments revealed using meta-analysis and machine learning

Nanoplastics (NPs) aggregation determines their bioavailability and risks in natural aquatic environments, which is driven by multiple environmental and polymer factors. The back propagation artificial neural network (BP-ANN) model in machine learning (R2 = 0.814) can fit the complex NPs aggregation, and the feature importance was in the order of surface charge of NPs > dissolved organic matter (DOM) > functional group of NPs > ionic strength and pH > concentration of NPs. Meta-analysis results specified low surface charge (0 ≤ |ζ| < 10 mV) of NPs, low concentration (< 1 mg/L) and low molecular weight (< 10 kg/mol) of DOM, NPs with amino groups, high ionic strength (IS > 700 mM) and acidic solution, and high concentration (≥ 20 mg/L) of NPs with smaller size (< 100 nm) contribute to NPs aggregation, which is consistent with the prediction in machine learning. Feature interaction synergistically (e.g., DOM and pH) or antagonistically (e.g., DOM and cation potential) changed NPs aggregation. Therefore, NPs were predicted to aggregate in the dry period and estuary of Poyang Lake. Research on aggregation of NPs with different particle size,shapes, and functional groups, heteroaggregation of NPs with coexisting particles and aging effects should be strengthened in the future. This study supports better assessments of the NPs fate and risks in environments.

Transport and retention of positively charged zinc oxide nanoparticles in saturated porous media: Effects of metal oxides and clays

The effects of metal oxides and clays on the transport of zinc oxide nanoparticles (ZnO-NPs) in saturated porous media were investigated under different ionic strength (IS) conditions. We studied the transport and retention behavior of ZnO-NPs for different types of porous media (untreated, acid treated, and acid–salt treated sand). The selected untreated sand was used as a representative sand, coated with both metal oxide and clay. The acid treated and acid–salt-treated sands were used and compared to investigate the effects of clays on the surface of the sand. In addition, the effects of clay particles in bulk solutions on the mobility and retention of ZnO-NPs were observed using bentonite as a representative clay particle. We found that the increased mobility of positively charged ZnO-NPs can be attributed to increasing charge heterogeneity of silica sand with metal oxides (mainly, iron oxide) and clays in untreated sand. No breakthrough of ZnO-NP was observed for acid-treated (presence of clays and absence of metal oxides) and acid–salt-treated sand (absence of both metal oxide and clays). Most of the injected ZnO-NPs were deposited on the surface of the sand near the column inlet. The transport of bentonite-facilitated ZnO-NPs was improved at the lowest IS (0.1 mM) (∼20%), whereas there was no difference in the mobility of ZnO-NPs at high IS solutions (1 mM and 10 mM). In particular, the breakthrough amount improved with increasing bentonite concentration. Classical Derjaguin–Landau–Verwey–Overbeek interactions help explain observed interactions between ZnO-NPs and sand as well as bentonite and sand.

Using solid waste to treat wastewater: Preparation of flowerlike calcium silicate hydrate from coal fly ash for cadmium removal

Efficient utilization of Coal fly ash (CFA) and ingenious treatment of cadmium (Cd (II)) in the water environment are interesting topics. In this paper, a mesoporous floral calcium silicate hydrate (MCSH) for removal of Cd (II) was prepared by low temperature hydrothermal synthesis using CFA desilication solution. Different synthesis parameters (molar ratio of Ca to Si (Ca/Si), temperature, time) of MCSH were investigated and optimized. All synthesized MCSH showed good adsorption properties for Cd (II), and MCSH synthesized at Ca/Si molar ratio of 1.0, temperature of 363 K and time of 120 min had the optimum Cd (II) adsorption capacity of 357.43 mg/g. The effects of solution pH, MCSH dosage, coexisting cations and ionic strength on the Cd (II) adsorption performance by MCSH were further considered systematically. The adsorption process was a spontaneous and endothermic process, conformed to the pseudo-second-order kinetic and Langmuir isothermal model. The main mechanism of Cd (II) removal by MCSH was the precipitation between Cd (II) and OH– released by MCSH, accompanied by ion exchange, surface complexation and electrostatic adsorption. The mesoporous flowery MCSH prepared from CFA provides an satisfactory solution for the utilization of solid waste resources and the purification of heavy metal wastewater.

Solution Ionic Strength Can Modulate Functional Loop Conformations in E. coli Dihydrofolate Reductase.

The observation of multiple conformations of a functional loop (termed M20) in the Escherichia coli dihydrofolate reductase (ecDHFR) enzyme triggered the proposition that large-scale motions of protein structural elements contribute to enzyme catalysis. The transition of the M20 loop from a closed conformation to an occluded conformation was thought to aid the rate-limiting release of the products. However, the influence of charged species in the solution environment on the observed M20 loop conformations, independent of charged ligands bound to the enzyme, had not been considered. Molecular dynamics simulations of ecDHFR in model CaCl2 solutions of varying molar ionic strengths IM reveal a substantial free energy barrier between occluded and closed M20 loop states at IM exceeding the E. coli threshold (∼0.24 M). This barrier may facilitate crystallization of ecDHFR in the occluded state, consistent with ecDHFR structures obtained at IM exceeding 0.3 M. At lower IM (≤0.15 M), the M20 loop can explore the occluded state, but prefers an open/partially closed conformation, again consistent with ecDHFR structures. Our findings caution against using ecDHFR structures obtained at nonphysiological ionic strengths in interpreting catalytic events or in structure-based drug design.

Plasmid size determines adsorption to clay and breakthrough in a saturated sand column

Horizontal gene transfer (HGT) is a major factor in the spread of antibiotic resistant genes (ARG). Transformation, one mode of HGT, involves the acquisition and expression of extracellular DNA (eDNA). eDNA in soils is degraded rapidly by extracellular nucleases. However, if bound to a clay particle, eDNA can persist for long periods of time without losing its transformation ability. To better understand the mechanism of eDNA persistence in soil, this experiment assessed the effects of 1) clay mineralogy, 2) mixed salt solution, 3) plasmid size on DNA adsorption to clay and 4) breakthrough behavior of three differently sized plasmids in an environmentally relevant solution. Batch test methods were used to determine adsorption trends of three differently sized DNA plasmids, pUC19, pBR322, and pTYB21, to several pure clay minerals, goethite (α-FeOOH), illite, and kaolinite, and one environmental soil sample. Results show not all sorbents have equal adsorption capacity based on surface area with adsorption capacities decreasing from goethite > illite = kaolinite > bulk soil, and low ionic strength solutions will likely not significantly alter sorption trends. Additionally, plasmid DNA size (i.e., length) was shown to be a significant predictor of adsorption efficiency and that size affects DNA breakthrough, with breakthroughs occurring later with larger plasmids. Given that DNA persistence is linked to its adsorption to soil constituents and breakthrough, eDNA size is likely an important contributor to the spread of ARG within natural microbial communities.

Quantification of Residual Water in Pharmaceutical Frozen Solutions Via 1H Solid-State NMR

Freezing is essential for the stability of biological drug substances and products, particularly in frozen solution formulations and during the primary drying of lyophilized preparations. However, the unfrozen segment within the frozen matrix can alter solute concentration, ionic strength, and stabilizer crystallization, posing risks of increased biophysical instability and faster chemical degradation. While quantifying the unfrozen water content is important for designing stable biopharmaceuticals, there is a lack of analytical techniques for in situ quantitative measurements. In this study, we introduce a 1H magic angle spinning NMR technique to identify the freezing point (Tice) and quantify mobile water content in frozen biologics, applying this method to analyze the freezing of a commercial high-concentration drug product, Dupixent®. Our results demonstrate that water freezing is influenced by buffer salt properties and formulation composition, including the presence of sugar cryoprotectants and protein concentration. Additionally, the 1H chemical shift can probe pH in the unfrozen phase, potentially predicting the microenvironmental acidity in the frozen state. Our proposed methodology provides fresh insights into the analysis of freeze-concentrated solutions, enhancing our understanding of the stability of frozen and lyophilized biopharmaceuticals.

Removal of Anionic Methyl Orange Dye from Water by Poly[2-methyl-1H-indole] Derivatives: Investigation of Kinetics and Isotherms of Adsorption.

The adsorption properties toward methyl orange (MO) were evaluated for poly[2-methyl-1H-indole] and its derivatives. The influence of pH, ionic strength of solution, composition, and amount of sorbent on the adsorption of MO dye was investigated; the kinetics of dye adsorption was studied. The adsorption isotherms were analyzed using different models of sorption equilibrium. The presence of chemical interaction between polyindoles and dye was proved by IR and UV spectroscopy methods. The sorption of MO with polymers is realized mainly due to the formation of electrostatic interactions between the sulfogroup of the dye and the imino group of the sorbent. Microphotographs demonstrate the change in the morphology of polyindoles after adsorption, which further confirms the structural changes in the polymers. It was found that the main factors affecting the sorption capacity of the studied materials are the position and nature of substituents in the polymers and the sorption conditions. For example, polyindoles containing a methoxy group in their structure (o-OMePIn and m-OMePIn) have the best sorption activity. These polymers are effective in adsorbing dyes, which means that they can be used in wastewater treatment.

Heavy Metal Removal from Aqueous Solutions Using a Customized Bipolar Membrane Electrodialysis Process.

Lack of safe water availability and access to clean water cause a higher risk of infectious diseases and other diseases as well. Heavy metals (HMs) are inorganic pollutants that cause severe threats to humans, animals, and the environment. Therefore, an effective HM removal technology is urgently needed. In the present study, a customized bipolar membrane electrodialysis process was used to remove HMs from aqueous solutions. The impacts of the feed ionic strength, applied electrical potential, and the type and concentration of HMs (Cd2+, Co2+, Cr3+, Cu2+, and Ni2+) on the process performance were investigated. The results showed that feed solution pH changes occurred in four stages: it first decreased linearly before stabilizing in the acidic pH range, followed by an increase and stabilization in the basic range of the pH scale. HM speciation in the basic pH range revealed the presence of anionic HM species. The presence of HMs on anion exchange membranes confirmed the contribution of these membranes for HM removal in the base channels of the process. While no clear trend was seen in the ionic strength solution, the maximum HM removal was observed when 1.5 g/L NaCl was used. The initial HM concentration showed a linear increase in HMs removal of up to 30 mg/L. A similar trend was seen with an increase in the applied electrical potential of up to 15 V. In general, the amount of HMs removed increased in the following order: Cd2+ ˃ Ni2+ ˃ Co2+ ˃ Cu2+ ˃ Cr3+. Under some operational conditions, however, the removed amount of Cu2+, Co2+, and Ni2+ was similar. The mass balance and SEM-EDX results revealed that the removed HMs were sorbed onto the membranes. In conclusion, this process efficiently separates HMs from aqueous solutions. It showed the features of diluate pH adjustment, reduction in the overall stack electrical resistance, and contribution of anion exchange membranes in multivalent cation removal. The mechanisms involved in HMs removal were diffusion and migration from the bulk solution, followed by their sorption on both cation and anion exchange membranes.

Transport and retention of ciprofloxacin with presence of multi-walled carbon nanotubes in the saturated porous media: impacts of ionic strength and cation types.

The environmental fate and risks of ciprofloxacin (CIP) in the subsurface have raised intensive concerns. Herein, the transport behaviors of CIP in both saturated quartz sand and sand/multi-walled carbon nanotubes (MWCNTs) mixtures under different solution ionic strength of the solution and coexisting cation types were investigated. Batch adsorption experiments highlighted growing adsorptive capacity for CIP with the increasing content of MWCNTs in the MWCNTs-quartz sand mixtures (from 0.5% to 1.5%, w/w). Breakthrough curves (BTCs) of CIP in the MWCNTs-quartz sand mixtures were well fitted by the two-site chemical nonequilibrium model (R2 > 0.833). The estimated retardation factors for CIP increased from 9.68 to 282 with growing content of MWCNTs in the sand column, suggesting the presence of MWCNTs significantly inhibited the transport of CIP in saturated porous media. Moreover, the values of retardation factors are negatively correlated with the ionic strength and higher ionic strength could facilitate the transport of CIP in the saturated porous media. Compared with monovalent cations (Na+), the presence of divalent cations (Ca2+) significantly facilitated the transport of CIP in the columns due to the complexation between CIP and Ca2+ as well as deposition of MWCNTs aggregates on the sand surface. Results regarding CIP retention in columns indicated that MWCNTs could enhance the accumulation of CIP in the layers close to the influent of sand columns, while they could hinder upward transport of CIP to the effluent. This study improves our understanding for transport behaviors and environmental risk assessments of CIP in the saturated porous media with MWCNTs.