Adsorption of uranyl ion on hexagonal boron nitride for remediation of real U-contaminated soil and its interpretation using random forest.

Acid leaching has been widely applied to treat contaminated soil, however, it contains several inorganic pollutants. The decommissioning of nuclear power plants introduces radioactive and soluble U(VI), a substance posing chemical toxicity to humans. Our investigation sought to ascertain the efficacy of hexagonal boron nitride (h-BN), an highly efficient adsorbent, in treating U(VI) in wastewater. The adsorption equilibrium of U(VI) by h-BN reached saturation within a mere 2 h. The adsorption of U(VI) by h-BN appears to be facilitated through electrostatic attraction, as evidenced by the observed impact of pH variations, acidic agents (i.e., HCl or H2SO4), and the presence of background ions on the adsorption performance. A reusability test demonstrated the successful completion of five cycles of adsorption/desorption, relying on the surface characteristics of h-BN as influenced by solution pH. Based on the experimental variables of initial U(VI) concentration, exposure time, temperature, pH, and the presence of background ions/organic matter, a feature importance analysis using random forest (RF) was carried out to evaluate the correlation between performances and conditions. To the best of our knowledge, this study is the first attempt to conduct the adsorption of U(VI) generated from real contaminated soil by h-BN, followed by interpretation of the correlation between performance and conditions using RF. Lastly, a. plausible adsorption mechanism between U(VI) and h-BN was explained based on the experimental results, characterizations, and a. comparison with previous adsorption studies on the removal of heavy metals by h-BN.

A novel approach to measure carbonate alkalinity in aqueous solutions using a total organic carbon analyzer.

Carbonate alkalinity is crucial in regulating the pH and buffering capacity of natural water systems. Thus, its accurate measurement is essential to understand various water environments that affect water quality and ecosystem health. However, conventional potentiometric titration has some limitations. It results in inaccurate measurements of carbonate alkalinity when the alkalinity levels are low or when high dissolved organic matter or inorganic ion levels exist. Herein, we propose a novel approach to accurately measure carbonate alkalinity using a total organic carbon (TOC) analyzer. An extensive study comparing the accuracy and reliability of the conventional potentiometric titration method with those of the newly developed TOC method was conducted to develop and verify highly accurate measurements of carbonate alkalinity. The TOC method has several advantages over the conventional potentiometric titration methods, such as its ability to accurately measure carbonate alkalinity in the presence of high dissolved organic matter or inorganic ion levels and its ability to provide rapid and automated measurements with high reproducibility. Because, the limit of detection, limit of quantification, and the variation coefficient of the measurements was 0.016 mM (0.2 mgC/L), 0.050 mM (0.6 mgC/L), and 3.68 % respectively. Thus, the development of a novel TOC method has significant environmental implications as it provides a reliable and accurate means to measure carbonate alkalinity in solutions containing various organic matter types.

An autopsy study of hollow fiber and multibore ultrafiltration membranes from a pilot-scale ultra high-recovery filtration system for surface water treatment.

The organic fouling characteristics of hollow fiber ultrafiltration (HFUF) and multibore ultrafiltration (MBUF) membranes from long-term ultrafiltration (UF) membrane systems were systemically investigated in this study. The objective was to obtain insights into the fouling behavior of dissolved organic matter (DOM) in a pilot-scale ultra-high-recovery membrane filtration system (p-UHMS) used for surface water treatment. The pilot system consisted of a series of two different UF membranes (1st stage: polyvinylidene fluoride (PVDF) HFUF and 2nd stage: polyethersulfone (PES) MBUF). It was designed to feed the HFUF concentrate to the MBUF membranes to achieve ≥99.5 % total water recovery for surface water treatment, as these advances might enhance the production efficiencies of drinking water. The experimental results confirmed that hydrophobic DOM controlled the formation of HFUF membrane organic fouling, whereas hydrophilic DOM, including polysaccharide-like and protein-like matter, promoted MBUF membrane fouling. These opposing trends were attributed to the hydrophilic characteristics of the MBUF membrane surfaces (contact angle: PVDF = 90-130° and PES ≤ 80°), which reduced the hydrophobic interactions between the UF membrane surfaces and foulants. The performance declines of the MBUF membrane due to fouling layer formation was considerably severer than those of the HFUF membrane, decreasing total permeate water in the p-UHMS. Moreover, the quantity of the desorbed MBUF membrane foulants via 0.1 N NaOH was roughly 7.2 times larger than that of the desorbed HFUF membrane foulants through 0.1 N NaOH, indicating that alkaline-based cleaning agent could much more efficiently recover the performance of the fouled MBUF membranes. Hence, adequate cleaning strategies using alkaline-based agent for the MBUF membrane appeared to be essential for preventing the performance deterioration of the p-UHMS.

Inhibition of biofouling on reverse osmosis membrane surfaces by germicidal ultraviolet light side-emitting optical fibers.

Biofouling of membrane surfaces poses significant operational challenges and costs for desalination and wastewater reuse applications. Ultraviolet (UV) light can control biofilms while reducing chemical usage and disinfection by-products, but light deliveries to membrane surfaces in spiral wound geometries has been a daunting challenge. Thin and flexible nano-enabled side-emitting optical fibers (SEOFs) are novel light delivery devices that enable disinfection or photocatalytic oxidation by radiating UV light from light-emitting diodes (LEDs). We envision SEOFs as an active membrane spacer to mitigate biofilm formation on reverse osmosis (RO) membranes. A lab-scale RO membrane apparatus equipped with SEOFs allowed comparison of UV-A (photocatalysis-enabled) versus UV-C (direct photolysis disinfection). Compared against systems without any light exposure, systems with UV-C light formed thinner-but denser-biofilms, prevented permeate flux declines due to biofouling, and maintained the highest salt rejection. Results were corroborated by in-situ optical coherence tomography and ex-situ measurements of biofilm growth on the membranes. Transcriptomic analysis showed that UV-C SEOFs down-regulated quorum sensing and surface attachment genes. In contrast, UV-A SEOFs upregulated quorum sensing, surface attachment, and oxidative stress genes, resulting in higher extracellular polymeric substances (EPS) accumulation on membrane surfaces. Overall, SEOFs that deliver a low fluence of UV-C light onto membrane surfaces are a promising non-chemical approach for mitigating biofouling formation on RO membranes.

Status and future trends of hollow fiber biogas separation membrane fabrication and modification techniques.

With the increasing global demand for energy, renewable and sustainable biogas has attracted considerable attention. However, the presence of various gases such as methane, carbon dioxide (CO2), nitrogen, and hydrogen sulfide in biogas, and the potential emission of acid gases, which may adversely influence the environment, limits the efficient application of biogas in many fields. Consequently, researchers have focused on the upgrade and purification of biogas to eliminate impurities and obtain high-quality and high-purity biomethane with an increased combustion efficiency. In this context, the removal of CO2 gas, which is the most abundant contaminant in biogas, is of significance. Compared to conventional biogas purification processes such as water scrubbing, chemical absorption, pressure swing adsorption, and cryogenic separation, advanced membrane separation technologies are simpler to implement, easier to scale, and incur lower costs. Notably, hollow fiber membranes enhance the gas separation efficiency and decrease costs because their large specific surface area provides a greater range of gas transport. Several reviews have described biogas upgrading technologies and gas separation membranes composed of different materials. In this review, five commonly used commercial biogas upgrading technologies, as well as biological microalgae-based techniques are compared, the advantages and limitations of polymeric and mixed matrix hollow fiber membranes are highlighted, and methods to fabricate and modify hollow fiber membranes are described. This will provide more ideas and methods for future low-cost, large-scale industrial biogas upgrading using membrane technology.

Effects of two-step cleaning sequences on foulant extraction from multibore ultrafiltration membranes in a pilot-scale membrane filtration system for surface water treatment.

The cleaning efficiencies of fouled multibore ultrafiltration membrane (UFMB) operated from a pilot-scale UF process for surface water treatment were systemically investigated according to the sequences of two different cleaning solutions. The experimental results decisively confirmed that HPI DOM and HPO DOM/multivalent ions complexation significantly resulted in the fouling formations on UFMB due to their neutral charge characteristic. The basic cleaning agent effectively extracted the organic foulants attached on UFMB, indicating that the type of cleaning agent was a critical factor influencing on the cleaning efficiency of fouled UFMB. However, the cleaning sequence 1 (CS-1: 0.1 M NaOH >0.1 M HCl; the total DOC = 725.77 mgC∙m-2; the total TN = 146.35 mgN∙m-2, total inorganic contents = 132.62 mg m-2) much more effectively extracted the foulants on the UFMB surfaces than the cleaning sequence 2 (CS-2: 0.1 M HCl >0.1 M NaOH; the total DOC = 604.49 mgC∙m-2; the total of TN = 121.79 mgN∙m-2, total inorganic contents = 73.43 mg m-2). The morphological results also clearly showed that the cleaned UFMB surface using CS-1 were effectively recovered, as compared with those using CP-2. Overall, this study implied that the hydroxide ions from the basic cleaning agent promoted the infiltration of the acidic cleaning agent into the densely formed fouling layers on the UFMB surfaces and demonstrated that the cleaning sequences strategy could significantly govern the restoration of UFMB performance during the pilot-scale surface water treatment system operation.

Unified Metallic Catalyst Aging Strategy and Implications for Water Treatment.

Heterogeneous catalysis holds great promise for oxidizing or reducing a range of pollutants in water. A well-recognized, but understudied, barrier to implement catalytic treatment centers around fouling or aging over time of the catalyst surfaces. To better understand how to study catalyst fouling or aging, we selected a representative bimetallic catalyst (Pd-In supported on Al2O3), which holds promise to reduce nitrate to innocuous nitrogen gas byproducts upon hydrogen addition, and six model solutions (deionized water, sodium hypochlorite, sodium borohydride, acetic acid, sodium sulfide, and tap water). Our novel aging experimental apparatus permitted single passage of each model solution, separately, through a small packed-bed reactor containing replicate bimetallic catalyst "beds" that could be sacrificed weekly for off-line characterization to quantify impacts of fouling or aging. The composition of the model solutions led to the following gradual changes in surface composition, morphology, or catalytic reactivity: (i) formation of passivating species, (ii) decreased catalytic sites due to metal leaching under acid conditions or sulfide poisoning, (iii) dissolution and/or transformation of indium, (iv) formation of new catalytic sites by the introduction of an additional metallic element, and (v) oxidative etching. The model solution water chemistry captured a wide range of conditions likely to be encountered in potable or industrial water treatment. Aging-induced changes altered catalytic activity and provided insights into potential strategies to improve long-term catalyst operations for water treatment.

Facile Surface Modification of Polyamide Membranes Using UV-Photooxidation Improves Permeability and Reduces Natural Organic Matter Fouling.

A new optimized ultraviolet (UV) technique induced a photooxidation surface modification on thin-film composite (TFC) polyamide (PA) brackish water reverse osmosis (BWRO) membranes that improved membrane performance (i.e., permeability and organic fouling propensity). Commercial PA membranes were irradiated with UV-B light (285 nm), and the changes in the membrane performance were assessed through dead-end and cross-flow tests. UV-B irradiation at 12 J·cm-2 enhanced the pure water permeability by 34% in the dead-end tests without decreasing the mono- or divalent ion rejections, as compared with the pristine PA membrane, and led to less fouling by natural organic matter in the cross-flow tests. Scanning electron microscopy (SEM), attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS) confirmed that UV-B irradiation opened the pore structure and created carboxylic and amine groups on the PA surface, leading to increased membrane surface charge and hydrophilicity. Thus, an optimal UV-B dose appears to modify only a thin layer of the PA membrane surface, which favorably enhances the membrane performance. UV-B did not alter the structure, flux, or salt rejection for cellulose triacetate (CTA)-based membranes. While other membrane surface modifications include oxidants, strong acids, and bases, the UV-B facile treatment is chemical-free, thus reducing chemical wastes, and easy to apply in roll-to-roll fabrication processes of PA membranes. The results also showed that a low UV irradiation dose could be applied to PA or CTA membranes for disinfection or photocatalytic oxidation.

Ultrasound-assisted Ti3C2Tx MXene adsorption of dyes: Removal performance and mechanism analyses via dynamic light scattering.

Herein, ultrasonication (US)-assisted novel nanomaterial Ti3C2Tx MXene was utilized as a selective adsorbent for treatment of synthetic dyes in model wastewater. Two types of US frequencies, 28 and 580 kHz, were applied to disperse MXene to evaluate the feasibility of US-assisted MXene for wastewater treatment. The physico-chemical properties of MXene after US were characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and zeta potential. According to FTIR and XPS, 28 kHz US-assisted MXene had a greater amount of oxygenated functional groups and dispersion compared to 580 kHz US-assisted and pristine MXene. Subsequently, US-assisted MXene was utilized as an adsorbent for the removal of positively charged methylene blue (MB) and negatively charged methyl orange. Both 28 and 580 kHz US-assisted MXene showed better adsorption performance for only MB compared to stirring-assisted MXene based on kinetics, isotherms, and several water chemistry factors including solution pH, temperature, ionic strength, and humic acid. Advantages of US-assisted MXene for water treatment are its fast kinetics at low dose and high selectivity for positively charged target compounds (i.e., MB). The main adsorption mechanism between MXene and MB was electrostatic interaction (attraction); however, physical properties (i.e., aggregation kinetics and hydrodynamic diameter), measured via dynamic light scattering, were also found to be critical factors in controlling the adsorption performance of the system. Lastly, US-assisted MXene exhibited a high regeneration property, based on 4th adsorption-desorption cycles.

Intrinsic pKa of Nanofiltration Membrane Surfaces to Assess Fouling and Cleaning Behaviors Induced by Foulant-Membrane Electrostatic Interactions.

The fouling and cleaning behaviors of m-phenylenediamine (MPD), coumarin-3-carboxylic acid (CCA), and d-(+)-glucose (DG) on polyamide nanofiltration (NF) membrane surfaces were investigated with a focus on the two intrinsic equilibrium constants (pKa,intr.) of carboxylic and amine functional groups determined using potentiometric titration. The charged foulants (MPD and CCA) strongly influenced the pKa,intr. of the membrane surface after the fouling layer formed via electrostatic interactions (Virgin = 3.4 and 9.2; MPD-fouled = 4.1 and 8.1; CCA-fouled = 1.5 and 12.4). Moreover, the pKa,intr. of electrostatically fouled membranes substantially recovered when using cleaning agents that released electrostatic interactions (cleaned MPD-fouled = 3.5 and 9.0; cleaned CCA-fouled = 3.3 and 9.6). In contrast, the neutral foulant (DG) did not affect the pKa,intr. (DG-fouled = 3.5 and 9.2); however, the ζ-potential of DG-fouled membrane was closer to zero than the virgin membrane (Virgin = -28.1 mV and DG-fouled = -7.2 mV at pH 7). The pKa,intr. value accurately represented the electrostatic interactions between organic foulants and membrane surfaces. Potentiometric titration is a facile method of determining the pKa,intr. that gives an in-depth understanding of the electrostatic interactions at the membrane surface associated with the membrane fouling and cleaning mechanism.

Germicidal Ultraviolet Light Does Not Damage or Impede Performance of N95 Masks Upon Multiple Uses.

The COVID-19 pandemic is increasing the need for personal protective equipment (PPE) worldwide, including the demand for facial masks used by healthcare workers. Disinfecting and reusing these masks may offer benefits in the short term to meet urgent demand. Germicidal ultraviolet light provides a nonchemical, easily deployable technology capable of achieving inactivation of H1N1 virus on masks. Working with N95-rated masks and nonrated surgical masks, we demonstrated that neither 254 nor 265 nm UV-C irradiation at 1 and 10 J/cm2 had adverse effects on the masks' ability to remove aerosolized virus-sized particles. Additional testing showed no change in polymer structure, morphology, or surface hydrophobicity for multiple layers in the masks and no change in pressure drop or tensile strength of the mask materials. Results were similar when applying 254 nm low-pressure UV lamps and 265 nm light-emitting diodes. On the basis of the input from healthcare workers and our findings, a treatment system and operational manual were prepared to enable treatment and reuse of N95 facial masks. Knowledge gained during this study can inform techno-economic analyses for treating and reusing masks or lifecycle assessments of options to reduce the enormous waste production of single-use PPE used in the healthcare system, especially during pandemics.

Validation of a biotic ligand model on site-specific copper toxicity to Daphnia magna in the Yeongsan River, Korea.

The objective of this study was to determine whether the water effect ratio (WER) or biotic ligand model (BLM) could be applied to efficiently develop water quality criteria (WQC) in Korea. Samples were collected from 12 specific sites along the Yeongsan River (YSR), Korea, including two sewage treatment plants and one estuary lake. A copper toxicity test using Daphnia magna was performed to determine the WER and to compare to the BLM prediction. The results of the WER from YSR samples also indicated significantly different copper toxicities in all sites. The model-based predictions showed that effluent and estuary waters had significantly different properties in regard to their ability to be used to investigate water characteristics and copper toxicity. It was supposed that the slight water characteristics changes, such as pH, DOC, hardness, conductivity, among others, influence copper toxicity, and these variable effects on copper toxicity interacted with the water composition. The 38% prediction was outside of the validation range by a factor of two in all sites, showing a poor predictive ability, especially in STPs and streams adjacent to the estuary, while the measured toxicity was more stable. The samples that ranged from pH 7.3-7.7 generated stable predictions, while other samples, including those with lower and the higher pH values, led to more unstable predictions. The results also showed that the toxicity of Cu in sample waters to D. magna was closely proportional to the amounts of acidity, including the carboxylic and phenolic groups, as well as the DOC concentrations. Consequently, the acceptable prediction of metal toxicity in various water samples needs the site-specific results considering the water characteristics such as pH and DOC properties particularly in STPs and estuary regions.