Bed Volume Research Articles

Alleviation of the necessity for supernatant prefiltering in the protein a recovery of Monoclonal antibodies from Chinese hamster ovary cell cultures

Protein A (ProA) chromatography is a mainstay in the analytical and preparative scale isolation/purification of monoclonal antibodies (mAbs). One area of interest is continuous processing or continuous chromatography, where ProA chromatography is used in the large-scale purification of mAbs. However, filtration is required prior to all ProA isolations to remove large particulates in cell culture supernatant, consisting of a mixture of cell debris, host cell contaminants, media components, etc. Currently, in-line filters are used to remove particles in the supernatant, requiring replacement over time due to fouling; regardless of the scale. Here we demonstrate the ProA isolation of unfiltered Chinese hamster ovary (CHO) cell media using capillary-channel polymer (C-CP) fiber stationary phases modified with S. aureus Protein A (rSPA). The base polymer of the analytical scale C-CP columns costs ∼$5 per 30 cm column, and when modified with ProA, the base cost is ∼$25 per 30 cm column, a cost-effective option in comparison to analytical-scale commercial columns. To directly sample unfiltered media, a 5 cm gap was created at the head of the C-CP column, where the large particulates are trapped, while molecular solutes flow through the capillary channels without sacrifice in analytical performance, mAb loading capacity, or backpressure increases. The binding capacity of the gap ProA C-CP column was ∼ 2 mg mL−1 of IgG per bed volume. The same analytical column could be operated after processing a total of ∼ 56 column bed volumes of supernatant (>25 analytical cycles) without the need for caustic clean-in-place processing.

Process design for removal of pharmaceuticals in wastewater treatment plants based on predicted no effect concentration (PNEC)

Increasing concern on water contamination by micropollutants like pharmaceuticals fuels the development and implementation of technologies to remove micropollutants from municipal wastewater treatment plants (WWTP). However, often the targets and criteria for process design of such technologies are not clarified. This study was conducted to test whether predicted no-effect concentrations (PNEC) can be used as a design parameter for advanced treatment technologies to achieve pharmaceutical levels in WWTP effluents. This goal is consistent with environmental requirements, currently being discussed both by the Danish authorities and the European goals on zero emissions as documented in the draft of the Urban Wastewater Directive. The effluent of a conventional activated sludge WWTP was treated by ozonation and granular activated carbon (GAC) and monitored for 50 pharmaceuticals and iodinated X-ray contrast media, as well as 23 transformation products. Treatment with GAC alone initially achieved concentrations below PNEC for all targeted compounds, but after treating 3,000 – 5,000 bed volumes, the removal for several compounds decreased and the effluent concentrations for clarithromycin and venlafaxine were no longer below PNEC. Ozonation alone effectively reduced the concentrations of most of the compounds with standard ozone dosing of 0.5 mg O3/mg DOC. However, ozonation was unable to remove bicalutamide and oxazepam to reach target concentrations. The operation of both technologies in combination achieved concentrations of all measured pharmaceuticals below the PNEC (even with ozone concentrations of below 0.5 mg O3/mg DOC). Nonetheless, this study suggests that proper steering of WWTP design via the PNEC values alone is obstructed by lack of reliable primal PNEC data and absence of PNEC references for emerging pollutants and potential biologically active transformation products.

Amorphous Fe–Mn binary oxides nanoparticles decorating waste bamboo biomass-based monolith for efficient arsenic removal with column adsorption

The removal of naturally occurring arsenic from aqueous media remains a challenging endeavor for the protection of public health and ecosystems. Herein, we devised a workable fresh-biomass-based monolith adsorbent by in situ generation of amorphous Fe–Mn binary oxides nanoparticles (Fe–Mn–O) on a waste bamboo biomass (MB) via a simple procedure of pre-oxidation plus co-precipitation. In the pre-oxidation process of MB, the surface underwent roughening and the manganese ions permeated deeply inside the biomass, both of which facilitated the loading of Fe–Mn–O (25.06 wt%). As a result, the Fe–Mn–O/MB had outstanding adsorption capacities of 33.41 and 36.88 mg g−1 for As(III) and As(V), respectively. XRD and FTIR analyses show that the amorphous structure of Fe–Mn–O with low-coordinated active centers provides numerous hydroxyl functional groups that enhance arsenic adsorption, moreover, oxidation of As(III) was realized. In different water matrix, the Fe–Mn–O/MB composite exhibited a retention of 87.33 % and 89.53 % of its original adsorption capacity for As(III) and As(V) after five cycles of reuse as well as enabled continuous operation in a fixed-bed system with a bed volume of around 1150. Therefore, this work provides a promising approach for efficient abatement of inorganic arsenic-caused water pollution.

Nitrogen doped residual carbon from gasification slag to enhance trifluoroacetate adsorption in groundwater: Experiments and calculations

In this work, a nitrogen doped residual carbon (RCN) from gasification slag was prepared to adsorb trifluoroacetate (TFA) from groundwater. The physicochemical properties of the residual carbon variants were characterized using BET, SEM, XPS and Boehm titration techniques, which determines the porous structure and basic surface property of RCN. For all residual carbon variants, the TFA adsorption kinetics conform the pseudo-second-order model and isotherm data followed the Langmuir model. The RCN exhibited the highest TFA monolayer adsorption capacity of 24.8 mg/g. Thermodynamics study indicated that TFA adsorption onto these adsorbents was spontaneous and the increasing temperature is not conductive to TFA adsorption. During the rapid small scale column tests, the RCN offered 1390 bed volumes (BV) to 3 μg/L breakthrough which was >4 times higher than did the pristine residual carbon (290 BV). Moreover, the DFT calculations obtained the adsorption strength sequence of sulfate > TFA > nitrate onto nitrogen doped carbon, which manifested most unfavorable effect of sulfate on TFA adsorption. This research offers a theoretical and practice reference for the simultaneous gasification slag utilization and perfluorochemicals purification.

The treatment of As(III)-contaminated water by using granular Fe-Mn-Cu composite oxide: Removing As(III) via the oxidation-adsorption process and handling the release of manganese ions

It is a challenge to obtain an outstanding removal performance for the treatment of As(III)-contaminated water without the risk of secondary pollution. In this study, a novel granular adsorbent of Fe-Mn-Cu composite oxide (GFMCO) was fabricated by the redox-precipitation method. Batch adsorption experiments were conducted to investigate the adsorption behavior of As(III) onto GFMCO, including adsorption isotherms, adsorption kinetics, the influences of pH and competing anions, and reuse performance. The adsorption equilibrium of As by GFMCO could be achieved within 12 h. As(III) can be effectively oxidized to As(V) and adsorbed by GFMCO with a theoretical maximum As adsorption capacity of 72.88 mg/g. The As removal performance remained stable within a wide pH range of 3–9. Phosphate and silicate anions inhibited As removal, whereas chloride ions, sulfate anions, calcium ions, and magnesium ions had little effect. In addition, GFMCO could be successfully regenerated and reused with almost no loss in adsorption capacity during four consecutive cycles. Moreover, the GFMCO-packed column used as an adsorption reactor could produce approximately 969 bed volumes of treated water with the effluent arsenic concentration below 10 μg/l. Although divalent manganese ions (Mn(II)) were released from the GFMCO-packed column, efficient Mn(II) removal could be achieved with the combination of sodium hypochlorite dosing and the manganese sand filtration. Overall, this work provides a promising adsorbent for As(III) removal with satisfactory efficiency and good security.

Complexation-based selectivity of organic phosphonates adsorption from high-salinity water by neodymium-doped nanocomposite

Organic phosphonates have been widely used in various industries and are ubiquitous in wastewaters, and efficient removal of phosphonates is still a challenge for the conventional processes because of the severe interferences from the complex water constitutions. Herein, an Nd-based nanocomposite (HNdO@PsAX) was fabricated by immobilizing hydrated neodymium oxide (HNdO) nanoparticles inside a polystyrene anion exchanger (PsAX) to remove phosphonates from high-salinity aqueous media. Batch experiments demonstrated that HNdO@PsAX had an excellent adsorption capacity (∼90.5 mg P/g-Nd) towards a typical phosphonate (1-hydrox-yethylidene-1,1-diphosphonic acid, HEDP) from the background of 8 g/L NaCl, whereas negligible HEDP adsorption was achieved by PsAX. Attractively, various coexisting substances (humic acid, phosphate, citrate, EDTA, metal ligands, and anions) exerted negligible effects on the HEDP adsorption by HNdO@PsAX under high salinity. FT-IR and XPS analyses revealed that the inner-sphere complexation between HEDP and the immobilized HNdO nanoparticles is responsible for HEDP adsorption. Fixed-bed experiments further verified that HNdO@PsAX was capable of successively treating more than 4500 bed volumes (BV) of a synthetic high-salinity wastewater (1.0 mg P/L of HEDP), whereas only ∼2 BV of effective treatment capacity was received by PsAX. The exhausted HNdO@PsAX was amenable to a complete regeneration by a binary NaOHNaCl solution without significant loss in capacity. The capability in removing other organic phosphonates and treating a real electroplating wastewater by HNdO@PsAX was further validated. Generally, HNdO@PsAX exhibited a great potential in efficiently removing phosphonates from high-salinity wastewater.

Assessment of full-scale 4th treatment step for micro pollutant removal in Sweden: Sand and GAC filter combo

This study focuses on the 4th treatment step in Degeberga WWTP treatment plant, the first full scale GAC filter in Sweden installed in April 2020 for removal of micropollutants. The two GAC filters, containing two different carbon types, has operated flawlessly for three years (30,000 bed volumes) without requiring backwashing. The results indicate that the sand filter provides effective protection to the carbon filters, preventing solids from reaching the carbon and reducing the growth of organic matter. Additionally substantial biodegradation was observed for several substances.During the first year of operation, the two filters (at 8500 and 5700 bed volumes respectively) achieved >98 % removal of 24 substances. By the end of the second year (at 19,000 and 12,600 bed volumes respectively), fluconazole and sulfamethoxazole broke through completely, and the number of compounds below 80 % removal increased. The average removal of micro pollutants decreased over time. Compounds with positive charges generally exhibited higher adsorption capacities, while negatively charged compounds had lower removals. On average the investigated 24 compounds was removed by 89 % in the 4th treatment step over three years. The study suggests that biodegradation may contribute to the removal of some micropollutants in GAC filters, similar to observations made in the sand filter.Both Swiss and suggested EU regulations aim for at least an 80 % removal in micropollutant concentration. The study evaluated the performance of the filters based on this guideline and the presented technique is after a total of eight years of investigation and evaluation a proven performer.Overall, the 4th treatment combination of sand and GAC filters in WWTPs has shown promising results in removing organic micropollutants, addressing the need for efficient treatment strategies targeting these emerging pollutants. Degeberga WWTP serves as an example of successful implementation of advanced treatment for improving water quality and protecting human and aquatic health.

Differential adsorption of vanadium(V) and tungsten(W) on ion exchange resins: A novel approach for separation and recovery of spent catalyst leachate

Vanadium (V) and tungsten (W) are essential metals for various industries, but separating them is challenging due to the molecular similarity of the two metal ions. A highly concentrated mixed solution of V and W is obtained from spent selective catalytic reduction (SCR) catalysts, but their complete recycling is impeded by the difficulty of separating V and W. In this study, we investigate the ion exchange resin (IXR) technique's effectiveness for separating V and W from the leaching solution of spent catalysts. We evaluated the performance of three IXRs: Lewatit MP800 (strong basic), MP62WS (medium basic), and TP260 (weak acidic) for the separation of V and W ions in the solution. Among these IXRs, MP800 exhibits V and W ion separation behavior at pH 14. It selectively adsorbs W ions, while V ions demonstrate low affinity for adsorption on MP800. The primary mechanism for the adsorption of V and W ions appears to be an ion exchange reaction on the quaternary ammonium group of MP800. Conversely, MP62WS, which adsorbs V and W ions through both ion exchange and chelation mechanisms, does not separate V and W ions effectively when the solution's pH is controlled. The adsorbed W ions on MP800 can be completely regenerated with 2 M NaCl solution through re-ion exchange. We also conducted dynamic column operations using a simulated spent catalyst leaching solution (V = 600 mg/L, W = 4000 mg/L) with MP800 at pH 14. The successful separation of V and W was achieved for up to 15 bed volumes (BV). Finally, we performed V and W separation using an actual spent catalyst leaching solution. MP800 displayed a notably high separation factor (αVW) of 19.59, highlighting its effectiveness in separating V and W.

Selective capture of palladium from acid wastewater by thiazole-modified activated carbon: Performance and mechanism

As a kind of scarce metal, palladium is widely used in many chemical industries. It essential to recover palladium from secondary resources, especially acidic media, owing to high content of palladium in secondary wastes and widespread extraction of palladium via strong acids. Chemically modified carbon materials not only have the advantage of activated carbon but also achieve the precise removal of specific pollutants, which is a kind of adsorption material with broad application prospects. In this direction, we report a solid carbon material named AT-C, which is obtained by one-step synthesis of 2-aminothiazoles grafted to the carbon surface by amidation. The present adsorbent delivers a high palladium adsorption capacity of 178.9 mg g−1, and desirable thermal and chemical stability. The uniform presence of abundant sulfur atoms and CO in the porous network enables AT-C to achieve selective absorption and rapid adsorption kinetics of Pd2+ in the complex water mixture containing many competing ions in the acidic pH range. For the strongly acidic leachates of catalysts, AT-C exhibits outstanding stability in cyclic experiments. Meanwhile, the fixed-bed column test indicates that 1076 bed volumes of the feeding streams can be effectively treated. In addition, AT-C exhibits superior adsorption selectivity, and the recovery efficiency of Pd2+ in actual industrial wastewater is 96.6%. This work realizes an efficient, rapid, and selective removal of palladium under acidic conditions, and provides a reference for complex industrial water treatment and resource recovery of precious metals.

A Comprehensive Deep Learning Framework for Automatic Target Volumes Segmentation in Post-Operative Stereotactic Partial Breast Irradiation (S-PBI)

In S-PBI, accurate delineation of post-surgical tumor bed volume (TBV) and clinical target volume (CTV) are crucial tasks to achieve effective radiotherapy outcomes. However, manual contouring is labor intensive, time consuming, and largely relies on the experience of clinicians. We aimed to propose a deep learning (DL) approach which mimics physicians' contouring practice to accurately segment target volumes in post-operative breast CT images. Our approach incorporated domain knowledge into a 3D U-Net based DL model for breast target volumes (TBV and CTV) delineation. Our TBV segmentation approach was inspired by the marker-guidance procedure in manual delineation, where the visual clues provided by the markers assist physicians in defining TBV. For this purpose, a distance-transformation coupled with a Gaussian filter was adopted to convert markers' locations on the CT images to saliency maps. Subsequently, the CT images and the corresponding saliency maps formed a two-channel input for the segmentation model. For CTV segmentation, TBV was incorporated as an input in addition to the CT images, guiding the model to encode the location-related image features. The architecture allowed the network to emulate the oncologist's manual delineation where CTV is derived from TBV via a margin expansion, followed by correcting the extensions for anatomical barriers of tumor invasion (e.g., skin, chest wall). We retrospectively collected 175 prone CT images from 35 post-operative breast cancer patients who received 5-fraction partial breast irradiation (PBI) regimen on a Co-60 prone based S-PBI unit. The 35 patients were randomly split into 25, 5, and 5 for model training, validation, and testing respectively. We evaluated the performance of the developed DL model on the testing dataset by comparing the predicted volumes with the manually delineated contours (ground truth) using Dice similarity coefficient (DSC), 95th percentile Hausdorff distance (HD95), and average symmetric surface distance (ASD). For TBV segmentation, our model achieved mean (standard deviation) of 0.76 (±2.7), 6.76 (±1.83) mm, and 1.9 (±0.66) mm for DSC, HD95, and ASD respectively. For CTV segmentation, our model achieved 0.94 (±0.02), 2.46 (±0.5) mm, and 0.53 (±0.14) mm for DSC, HD95, and ASD respectively. The proposed auto-segmentation approach generated TBV and CTV masks in ∼11 seconds per CT volume, implying significantly improved efficiency compared to manual contouring. We developed a comprehensive DL framework mimicking clinical contouring practice for auto-segmentation of target volumes in S-PBI. The results demonstrated high levels of agreement between the predicted contours and physicians' manual contours. The approach is promising for improving the efficiency and accuracy of the on-line treatment planning workflow, such as adaptive based S-PBI.

Computational Fluid Dynamics of Ammonia Synthesis in Axial-Radial Bed Reactor

Ammonia synthesis by the Haber–Bosch method is a typical and effective implementation of the chemical process in the large-scale fertiliser industry. Due to the growing demand for fertilisers and food, it is desirable to study this process thoroughly using modern numerical methods to improve the operation of existing devices and facilitate the design of new devices in industrial installations. This manuscript focuses on the influence of the catalyst bed parameters on the ammonia synthesis process. Variants with different sizes of catalyst particles and modifications of the geometry of catalytic beds were considered. The axial-radial Topsoe converter with magnetite as a catalyst, commonly used in modern fertiliser industry beds, was investigated using Computational Fluid Dynamics. As a result, contours of velocity, pressure, concentration, and rate of ammonia formation were obtained. The analysis of the obtained results made it possible to determine the gradient of ammonia production rate in the catalyst bed and designate zones with negligible reaction rates. The authors also proposed possible bed geometry modifications to reduce bed volumes without affecting the converter’s performance.

Integrating biological ion exchange with biological activated carbon treatment for drinking water: A novel approach for NOM removal, trihalomethane formation potential, and biological stability

Ion exchange resins (IEX) are used in drinking water utilities to remove natural organic matter (NOM) from surface water; however, the disposal of used brine can be a major drawback. Recently, biological ion exchange (BIEX) has been proposed as an alternative to biological activated carbon (BAC) for removing natural organic matter (NOM). The present study is, to the best of our knowledge, the first attempt to use a hybrid BIEX and BAC (BIEX+BAC) system for drinking water treatment. The removal of NOM, assimilable organic carbon, and trihalomethane formation potential was investigated by operating four columns comprising IEX, BIEX, BAC, and BIEX+BAC with 18,000 bed volumes. The BIEX+BAC system was the most effective at removing dissolved organic carbon (59.9%). Based on fluorescence excitation-emission matrix spectroscopy, the BIEX+BAC column showed the maximum removal rates in all peak regions of T1, T2, and A. Using liquid chromatography-organic carbon detection, resin-containing columns were found to effectively remove humic substances, which are the principal precursors of trihalomethanes. The lowest potential for trihalomethane formation was observed in BIEX+BAC. BIEX+BAC also had the highest assimilable organic carbon removal efficiency (61.2%) followed by BIEX (52.3%), BAC (49.5%), and IEX (47.1%). The BIEX+BAC hybrid was found to be the most effective method for removing NOM fractions and reducing the formation of disinfection byproducts.

Silica-supported thiourea resin for efficient recovery of Pd(II): Batch, column and mechanism study

Palladium is versatile in many industrial applications due to its distinct physicochemical properties. Due to the scarcity of natural resources and the growing market demand, palladium recovery from wastes such as spent catalysts is receiving increasing attention. Here, a silica-supported thiourea resin (SiPS-TU) was prepared and applied to separate Pd(II) from spent catalysts. The SiPS-TU was fabricated through in situ polymerization and post modification method using amorphous macroporous silica as the matrix. Experimental results suggested that the optimal acidity for the adsorption process was 0.1 M under selected range, and the uptake of SiPS-TU was affected by H+ and Cl−. The adsorbent showed rapid sorption kinetics with an equilibrium attained in 30 min, while more than 3 h was required for the commercial D840 resin. Column tests showed that SiPS-TU had excellent dynamic separation property for Pd(II) in continuous process. Around 215 bed volumes (430 mL) of Pd(II) solution could be effective treated by the SiPS-TU bed before breakthrough at 4 mL/min, while D840 resin bed was less effective under equivalent conditions (20 mL). In view of its satisfactory adsorption performances, palladium was successfully separated from the catalyst leaching solution by SiPS-TU. XPS spectra and DFT calculations indicated that the adsorption mechanism of SiPS-TU for Pd(II) mainly involved anion exchange and coordination. In conclusion, this study provides a feasible material for palladium recovery from practical leachate.

Long-term removal of perfluoroalkyl substances via activated carbon process for general advanced treatment purposes

Granular or powdered activated carbon (GAC/PAC) processes are installed in full-scale drinking water treatment plants (DWTPs) to reduce disinfection byproduct precursors, odor, ammonia, and pesticides. This study investigated the ability of GAC/PAC processes in 23 DWTPs to remove per- and polyfluoroalkyl substances (PFASs). In the GAC process, filter breakthrough of perfluoroalkyl carboxylic acids (PFCAs) occurred faster as the PFCA chain length is decreased. During periods of high water temperatures (20−29 °C), the effluent concentration of two short-chain PFCAs (C4 and C5) surpassed that of the influent after the throughput reached 5,000−7,500 bed volumes (equivalent to 2−3 months) due to desorption. However, such desorption was not observed during periods of low water temperatures (5−19 °C). Meanwhile, long-chain PFCAs were consistently removed, as the GAC was replaced before breakthrough became noticeable. PFAS removal deteriorated at a remarkably fast rate after a partial breakthrough of several tens of percent. Biological activated carbon was proved ineffective in removing PFASs due to its diminished adsorption capacity after long-term use. The PAC process, however, exhibited a slight decrease in PFCA residual (10%) at higher water temperatures (15−30 °C). The PAC dose required for a certain residual ratio was lower with an increase in the hydrophobicity of PFAS; C8-PFCA only required 20 mg/L of PAC for 50% removal, while C4-PFCA required a significantly higher dose of 100−700 mg/L. Consequently, the activated carbon process, which removes organic contaminants in surface water, was inadequate in removing PFASs, particularly those with short chains. Thus, it is recommended that GAC filters be replaced more frequently (within two months) for short-chain PFAS removal. Further, the adsorption performance of PAC must be enhanced.

Erosion and Transport of Dry Soil Bed by Collisional Granular Flow: Insights From a Combined Experimental–Numerical Investigation

AbstractCollision‐induced stresses on soil beds under granular geophysical flows have been demonstrated to be highly erosive. However, it remains mostly elusive as to how a collisional granular flow erodes and transports soil bed material. This paper presents a combined experimental and numerical investigation into the mechanisms underlying collision‐induced erosion and transport of dry soil beds. A series of flume experiments are conducted where collisional granular flows erode dry sand beds under varied conditions. The experiments are then back‐analyzed using a hybrid continuum–discrete simulator to gain physical insight into the erosion and transport processes. Results show that the key mechanism of collision‐induced erosion and transport is the retexturing of the soil bed surface. This implies that bed morphology, which has often been overlooked in mobility and hazard assessments, has profound effects on erosion and transport potential. Further, contrary to most existing models that assume all the eroded bed volume is carried away by granular flow, it is found that only up to 80% of the eroded material is transported. Also found is that the collisional stresses of the monodisperse grains in this study follow the Pareto distribution in which 80% of differences in the outcomes are due to 20% of causes. This finding suggests that there is measurable certainness in a seemingly random process of coarse grain collisions with an erodible soil bed.

Highly effective adsorption for both As(III) and As(V) in aqueous medium via magnetic chitosan-based composite microparticles: Low arsenic concentration, high column efficiency and adaptability

To improve the arsenic adsorption efficiency at low concentration and the adaptability of the adsorbents, magnetic composite microparticles based on Fe3O4, TiO2 and chitosan/quaternary ammonium salt chitosan derivatives were prepared. The composites were systematically characterized, and their arsenic removal efficiency was investigated towards several factors. The results showed that MTHCNPs-2 with the highest substitution degree showed the best selectivity and adsorption efficiency towards arsenic even in low concentration, and still had high adsorption efficiency even after 10 cycles, making it an effective and adaptable adsorbent for both As(III) and As(V). Adsorption kinetics showed that MTHCNPs-2 could fast adsorb As(Ⅲ) and As(V), and chemical adsorption played the main role. The maximal adsorption capacities of MTHCNPs-2 for As(Ⅲ) and As(V) were 33.68 mg/g and 34.61 mg/g, respectively. Furthermore, the adsorption mechanism was explored by XPS, and the practical applicability of MTHCNPs-2 was tested towards the removal of both As(III) and As(V) from arsenic-contaminated real effluent using fixed bed column. It is shown that the breakdown volumes for As(Ⅲ) and As(V) reached up to 660 and 600 bed volumes, respectively. 0.1 M NaOH could effectively regenerate the column, and the adsorption capacities for As(Ⅲ) and As(V) only reduced by 0.53% and 0.74% for the second cycle, indicating the excellent regenerative capacity of the column. Furthermore, MTHCNPs-2 still had high removal efficiency towards As(Ⅲ) and As(V) even in the presence of phosphate and iron ions in the column study.

Sorption of cesium from strongly alkaline solutions on a modi ed ferrocyanide sorbent «fersal»

The sorption of cesium from solutions of sodium and potassium nitrates, sodium hydroxide, and also from a model solution simulating alkaline high-level waste (HLW) of FSUE PO «Mayak» on various resorcinolformaldehyde sorbents (RFS), on sorbent based on a boron-containing polymer of the Clevasol brand and on sorbent of the Fersal brand based on modi ed nickel ferrocyanide was studied under batch conditions. It is shown that in all the media studied, the Fersal sorbent has the best sorption-selective characteristics with respect to cesium. During the sorption of cesium from a model solution of HLW under dynamic conditions, the volume of the passed solution to 1% breakthrough for the Fersal sorbent is 127 bed volumes (b.v.). The puri cation resource of the other studied sorbents is 3-4 times less. Desorption of cesium from the Fersal sorbent can be carried out by passing 9-10 b.v. 7.5 mol/dm3 HNO3, however, in this case, the sorbent granules are destroyed, which does not allow it to be reused. It is concluded that the Fersal sorbent is the most promising for the treatment of alkaline HLW.

Efficient removal of electroneutral carbonyls by combined vacuum–UV oxidation and anion-exchange resin adsorption: mechanism, model simulation, and optimization

Electroneutral carbonyls (ENCs) with low molecular weights (e.g., aldehydes and ketones) are recalcitrant to single water treatment process to achieve ultralow concentration. Residual ENCs are present in reverse osmosis permeate and pose risks to human health during potable use or industrial application in manufacturing processes. Herein, a combined vacuum–UV (VUV) oxidation and anion-exchange resin (AER) adsorption method was developed to treat the ENCs and reduce total organic carbon (TOC) to an ultralow concentration (< 5 μg/L) with high efficiency and at low cost. VUV-AER was 2.1–2.4 times more efficient than VUV alone for the removal of TOC. VUV oxidized the ENCs to electronegative carboxylic acids, which were adsorbed by the AER through electrostatic interactions and hydrogen bonding. When the VUV fluence was lower than 643 mJ cm−2, the AER could not achieve ultralow TOC removal of ENCs. The treat capacity of 1500–2900 valid bed volume (BVs) was achieved after increasing the VUV fluence to 1929 mJ cm−2. The AER could more efficiently adsorb carboxylic acids that contained more carboxylic groups or shorter carbon chain. Acetate was identified as the primary breakthrough product at relatively low VUV fluence, and oxalate was the main byproduct at relatively high VUV fluence. A mathematical model to predict TOC breakthrough was developed considering the VUV–oxidation kinetics and the AER breakthrough curve. The model was used to optimize the method to maximize TOC removal and minimize energy consumption. These results imply that VUV-AER is technically feasible and economically applicable to eliminate recalcitrant ENCs to ultralow concentration for the production of water requires high quality (e.g., potable water or electronic-grade ultrapure water).

Transforming Waste into Value: Eco-Friendly Synthesis of MOFs for Sustainable PFOA Remediation

In response to the need for sustainable solutions to address perfluorooctanoic acid (PFOA) contamination, we have developed an eco-friendly approach for synthesizing two types of metal-organic frameworks (MOFs) using waste polyethylene terephthalate (PET) bottles via a one-pot microwave-assisted strategy. Our innovative method not only avoids the initial depolymerization of PET bottles but also promotes environmental conservation by recycling waste materials. The La-MOF and Zr-MOF materials exhibit remarkable surface areas of 76.90 and 293.50 m2/g, respectively, with La-MOF demonstrating greater thermal stability than Zr-MOF. The maximum experimental PFOA adsorption for La-MOF and Zr-MOF was obtained at 310 and 290 mg/g, respectively. Both MOFs follow the Langmuir isotherm closely, with the adsorption of PFOA following a pseudo-2nd-order kinetic model. In packed-bed column tests, breakthrough positions of 174 and 150 min were observed for La-MOF and Zr-MOF, respectively, with corresponding bed volumes of 452 mL and 522 mL based on the PFOA limit of 0.07 µg/L in drinking water. These findings indicate that these MOFs can be used in industrial packed-bed columns to remove PFOA from contaminated water sources in an efficient and cost-effective manner. Importantly, the sorption performance of the fabricated MOFs for PFOA remained stable, decreasing by less than 10% over seven cycles. This study underscores the potential of recycled PET bottles and the one-pot microwave-assisted synthesis of MOFs as an effective and environmentally friendly solution for PFOA remediation. This innovative approach has several managerial implications, such as the use of waste materials as a feedstock, which can reduce the cost of production and minimize environmental impact by promoting recycling and repurposing, enhancing the reputation of companies operating in the chemical industry, and improving their sustainability metrics. By integrating sustainability principles and waste recycling, our approach offers promising avenues for addressing PFOA contamination while promoting resource efficiency and environmental conservation.

In situ growth of metal hexacyanoferrate crystals on alginate beads for effective removal of radioactive cesium (137Cs) from seawater

Metal hexacyanoferrates (Me-HCFs) are highly effective materials for removing radioactive Cs (137Cs) in seawater. For their practical application, granulation of Me-HCFs is necessary. However, conventional granulation techniques using a polymer as a binding material adversely affect the adsorption performance of Me-HCFs by blocking their adsorption sites. In the present work, to minimize the interference of the binding material, Me-HCF crystals were synthesized on an alginate bead surface in situ for the treatment of 137Cs+-contaminated seawater. Three different Me-HCFs immobilized on alginate beads (Fe-HCF, Cu-HCF, and Co-HCF) were prepared via a simple and rapid method involving a reaction between ionophorically crosslinked alginate beads (Fe3+, Cu2+, and Co2+ ions) and HCF solution. Among them, Fe-HCF crystals were successfully grown on the alginate bead surface; the other crystals were hardly synthesized despite a longer reaction time. The Fe-HCF crystals composed 15.0 % (w/w) of the beads and were located on the surface of the beads rather than being embedded in the alginate matrix. Because the Fe-HCF crystals were located at the surface of the alginate beads, Cs+ adsorption onto the Fe-HCF crystals showed fast reaction kinetics (achieving equilibrium in ∼ 3 h) and a high Cs+ adsorption capacity (∼33.5 mg/g). Also, a feasibility test was carried out for the removal of radioactive 137Cs+ in real seawater medium. Finally, a continuous Cs+ removal test was conducted in a packed column of the Fe-HCF beads. It was able to treat 65 bed volume of 50 mg/L of Cs+ solution with a flow rate of 1 mL/min.