Algal mediated intervention for the retrieval of emerging pollutants from aqueous media.

Water is a crucial elemental contributor for all sectors; however, the agricultural sector alone accounts for 70% of the world's total water withdrawal. The anthropogenic activity from various industries including agriculture, textiles, plastics, leather, and defence has resulted in the release of contaminants into water systems, resulting harm to the ecosystem and biotic community. Algae-based organic pollutant removal uses several methods, such as biosorption, bioaccumulation, biotransformation, and biodegradation. The adsorption of methylene blue by algal species Chlamydomonas sp. showed a maximum adsorption capacity of 2744.5 mg/g with 96.13% removal efficiency; on the other hand, Isochrysis galbana demonstrated a maximum of 707 µg/g nonylphenol accumulation in the cell with 77% removal efficiency indicating the potential of algal systems as efficient retrieval system for organic contaminants. This paper is a compilation of detailed information about biosorption, bioaccumulation, biotransformation, biodegradation, and their mechanism, along with the genetic alteration of algal biomass. Where the genetic engineering and mutations on algae can be advantageously utilized for the enhancement of removal efficiency without any secondary toxicity.

Article Application of neural network in metal adsorption using biomaterials (BMs): a review.

With growing environmental consciousness, biomaterials (BMs) have garnered attention as sustainable materials for the adsorption of hazardous water contaminants. These BMs are engineered using surface treatments or physical alterations to enhance their adsorptive properties. The lab-scale methods generally employ a One Variable at a Time (OVAT) approach to analyze the impact of biomaterial modifications, their characteristics and other process variables such as pH, temperature, dosage, etc., on the removal of metals via adsorption. Although implementing the adsorption procedure using BMs seems simple, the conjugate effects of adsorbent properties and process attributes implicate complex nonlinear interactions. As a result, artificial neural networks (ANN) have gained traction in the quest to understand the complex metal adsorption processes on biomaterials, with applications in environmental remediation and water reuse. This review discusses recent progress using ANN frameworks for metal adsorption using modified biomaterials. Subsequently, the paper comprehensively evaluates the development of a hybrid-ANN system to estimate isothermal, kinetic and thermodynamic parameters in multicomponent adsorption systems.

Sustainable conversion of saturated adsorbents (SAs) from wastewater into value-added products: future prospects and challenges with toxic per- and poly-fluoroalkyl substances (PFAS).

Following circular economy principles, the reuse or recycling of saturated adsorbents (SAs or adsorbate-laden adsorbents) into a low-cost engineered product is a valuable alternative to eliminate secondary pollution after adsorption. This review evaluates the application of SAs for the generation of products that can serve as (i) antimicrobial agents or disinfectants, (ii) materials for civil construction, (iii) catalysts, (iv) fertilizers, and (v) secondary adsorbents. The importance of SAs configuration in terms of functional groups, surface area and pore morphology played a crucial role in their reutilization. The SAs-laden silver ions (Ag+) strongly inhibit (~ 99%) the growth of Escherichia coli and Staphylococcus aureus microbes found in drinking and wastewaters. The intra-solidification of SAs containing toxic metal pollutants (As3+ and F-) with cementitious materials can effectively reduce their leaching below permissible limits of USEPA standards for their utility as additives in construction work. The existence of transition metal ions (Cu2+, Cr3+/6+, Ni2+) on the surface of SAs boosted activity and selectivity towards the desired product during catalytic oxidation, degradation, and conversion processes. The thermally recycled SAs can assist in the secondary adsorption of pollutants from another waste solution due to a larger surface area (> 1000 m2g-1). However, there are chances that the SAs discussed above will contain traces of PFAS. The article summarizes the challenges, performance efficacy, and future prospects at the end of each value-added product. We also highlight critical challenges for managing PFAS-laden SAs and stimulate new perspectives to minimize PFAS in air, water, and soils.

Removal of Zwitterionic PFAS by MXenes: Comparisons with Anionic, Nonionic, and PFAS-Specific Resins.

Zwitterionic per- and polyfluoroalkyl substances are increasingly detected in aquatic environments. The magnitude of their concentration and increased frequency of detection worldwide raise questions on their presence in drinking water and associated health risk. Scientific knowledge on the identification of treatment technologies to effectively capture such zwitterionic PFAS from contaminated water sources remains largely unknown. In this study, we investigated the application of anionic organic scavenger ion exchange (IX) resins (A860), nonionic IX resins (XAD 4 and XAD 7), PFAS-specific resins (A694 and A592), and Ti3C2 MXenes (novel two-dimensional metal carbides) for the removal of select fluorotelomer zwitterionic PFAS from natural waters. The cumulative removal of zwitterionic PFAS at pH ∼ 7 follows the order: Ti3C2 MXenes > A694 > A592 > A860 > XAD 4 ∼ XAD 7. Ti3C2 MXenes were able to capture >75% of the total influent zwitterionic PFAS and the performance remained consistent in natural and synthetic water. Ti3C2 MXenes also exhibited efficient regeneration (>90% recovery) with 0.4 M Na2SO3 solution, while the regeneration efficacy of other IX resins generally remained below 20%. Treatment with ∼180 J/cm2 UV dosage in the 0.4 M Na2SO3 regenerant brine solution yielded >99.9% reduction in the zwitterionic PFAS concentration indicating that UV-sulfite systems exhibit promising potential for the treatment of zwitterionic PFAS concentrates.

Application of MXenes for water treatment and energy-efficient desalination: A review.

MXenes are a new type of two-dimensional (2D) material which are rapidly gaining traction for a range of environmental, chemical and medical applications. MXenes and MXene-composites exhibit high surface area, superlative chemical stability, thermal conductivity, hydrophilicity and are environmentally compatible. Consequently, MXenes have been successfully employed for hydrogen storage, semiconductor manufacture and lithium ion batteries. In recent years, MXenes have been utilized in numerous environmental applications for treating contaminated surface waters, ground and industrial/ municipal wastewaters and for desalination, often outperforming conventional materials in each field. MXene-composites can adsorb multiple organic and inorganic contaminants, and undergo Faradaic capacitive deionization (CDI) when utilized for electrochemical applications. This approach allows for a significant decrease in the energy demand by overcoming the concentration polarization limitation of conventional CDI electrodes, offering a solution for low-energy desalination of brackish waters. This article presents a state-of-the-art review on water treatment and desalination applications of MXenes and MXene-composites. An investigation into the kinetics and isotherms is presented, as well as the impact of water constituents and operating conditions are also discussed. The applications of MXenes for CDI, pervaporation desalination and solar thermal desalination are also examined based on the reviewed literature. The effects of the water composition and operational protocols on the regeneration efficacy and long-term usage are also highlighted.

COVID-19 pandemic lesson learned- critical parameters and research needs for UVC inactivation of viral aerosols.

The COVID-19 pandemic highlighted public awareness of airborne disease transmission in indoor settings and emphasized the need for reliable air disinfection technologies. This increased awareness will carry in the post-pandemic era along with the ever-emerging SARS-CoV variants, necessitating effective and well-defined protocols, methods, and devices for air disinfection. Ultraviolet (UV)-based air disinfection demonstrated promising results in inactivating viral bioaerosols. However, the reported data diversity on the required UVC doses has hindered determining the best UVC practices and led to confusion among the public and regulators. This article reviews available information on critical parameters influencing the efficacy of a UVC air disinfection system and, consequently, the required dose including the system's components as well as operational and environmental factors. There is a consensus in the literature that the interrelation of humidity and air temperature has a significant impact on the UVC susceptibility, which translate to changing the UVC efficacy of commercialized devices in indoor settings under varying conditions. Sampling and aerosolization techniques reported to have major influence on the result interpretation and it is recommended to use several sampling methods simultaneously to generate comparable and conclusive data. We also considered the safety concerns and the potential safe alternative of UVC, far-UVC. Finally, the gaps in each critical parameter and the future research needs of the field are represented. This paper is the first step to consolidating literature towards developing a standard validation protocol for UVC air disinfection devices which is determined as the one of the research needs.

PFAS removal by ion exchange resins: A review.

Per- and poly-fluoroalkyl substances (PFAS) represent a large family of anthropogenic organic compounds with a wide range of industrial and commercial applications. PFAS have become a global concern due to their toxicity and bio-accumulative properties. PFAS species have been ubiquitously detected in natural waters, wastewaters, sludge, and aquatic and terrestrial species which are anionic, zwitterionic and neutral. The ion exchange (IX) process for PFAS removal is an efficient technology for the remediation of PFAS-laden surface, ground and effluent wastewaters. This approach is more effective towards eliminating emerging short-chain PFAS which are not removed by carbon-based adsorption processes. This article presents a state-of-the-art review of PFAS removal from water via IX process. The evaluation and comparison of various IX resins in terms of kinetics and isotherms is presented. Literature data indicates that IX isotherm uptake capacity for perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) can range up to 5 mmol/g on commercially available IX resins such as IRA 958 and IRA 67. The mechanism involved in the PFAS uptake process, such as diffusion, electrostatic interactions and hydrophobic effects are discussed. The effects of the eluent variability on the regeneration efficacy are also highlighted and the effect of single-use vs reuse for newly developed PFAS-specific IX resins are also examined based on the reviewed literature.

PFAS and DOM removal using an organic scavenger and PFAS-specific resin: Trade-off between regeneration and faster kinetics.

Treatment technologies such as ion exchange (IX) process exhibit promising potentials for the removal of toxic per- and poly-fluoroalkyl substances (PFAS) from natural waters. In recent years, industries have started manufacturing PFAS-specific resins which are typically operated in a single use-and-dispose mode until exhaustion. However, this increases the resin demand and the consequent operational cost and environmental burden of the IX process. In this study, the performance of a PFAS-specific resin (A592) was compared with that of a regenerative organic scavenger resin (A860) which is traditionally employed for dissolved organic matter (DOM) and micorpollutant removal. Comparative studies were performed to examine the removal of multiple long- and short-chain carboxylic, sulfonic, precursor and emerging PFAS (including GenX) from synthetic and natural waters. The A592 resin exhibited faster uptake kinetics for PFAS while simultaneously removing 10-15% of DOM. The A860 resin removed ~60-70% of DOM; however, it required approximately 3-fold higher contact times for achieving the same degree of PFAS removal when compared to the PFAS-specific resin. The resin breakthrough (Ctreated (PFAS) > 70 ng/L) was observed around 125,000 ± 5000 bed volumes (BVs) for the PFAS-specific resin (via multiple loading tests), while it ranged between 15,000-27,000 BVs for the organic scavenger. Yet, a mass balance on PFAS and DOM removal indicated ~90-98% site saturation (in milli-equivalents (meqs)) on both IX resins before exhaustion. More importantly, the regenerated organic scavenger resin (A860) exhibited PFAS and DOM removal capabilities for longer operational BVs when compared to A592 operated in a single-use-mode in natural waters.

Removal of legacy PFAS and other fluorotelomers: Optimized regeneration strategies in DOM-rich waters.

We present the first study investigating optimized regeneration strategies for anionic ion exchange (IX) resins during the removal of persistent per- and poly-fluoroalkyl substances (PFAS, including GenX) from surface and treated wastewater effluents. IX regeneration studies are of critical importance from environmental perspectives. Specifically, the knowledge is essential for water utilities who presently operate IX (for PFAS removal) in a single use-and-dispose mode. In this study, legacy PFAS such as PFOA/PFOS were tested along with other harmful short-chained PFAS (PFBA/PFBS) and other toxic perfluorinated substitutes (GenX). Studies were performed on synthetic water (spiked with Suwannee River Natural Organic Matter (SRNOM), Fulvic Acid (SRFA) and Humic Acid (SRHA)), surface water, and wastewater effluents, and the regeneration was performed in batch stirred reactors. The resin service life with and without regeneration was investigated in the presence of background organic matter. In ultra-pure waters, all PFAS (C0 ∼10 µg/L, concentrations similar to that of natural waters) were effectively removed for >100,000 Bed Volume (BV) of operation. This was reduced to ∼23,500 BV in the presence of SRNOM (C0 = 5 mg C/L), 20,500 BV in SRFA and 8500 BV in SRHA, after which the saturated resins required regeneration. More importantly, all resin breakthrough (PFAS> 70 ng/L) corresponded to > 90% resin site saturation (in meqs), an essential information for optimizing IX loading. The competitive dissolved organic matter (DOM) fractions were estimated to be approximately 5-9% of the initial DOC, as estimated by the IAST-EBC model. Finally, it was identified that IX regeneration efficiency improved with increasing brine contact time but effectiveness plateaued for brine concentrations above 10% (W/V). Nonetheless, a regeneration with 10% NaCl solution with a contact time of 2 h was found to be optimal for IX operations in synthetic and natural waters. Therefore, this study provides key knowledge essential for the scientific community and the water industry on optimizing IX operational parameters for DOM and PFAS removal and would be highly valuable for systems which presently operate IX in a use-and-dispose mode.

Efficient removal of GenX (HFPO-DA) and other perfluorinated ether acids from drinking and recycled waters using anion exchange resins.

Carcinogenic GenX chemicals, heptafluoropropylene-oxide-dimer-acid (HFPO-DA), have been recently detected in surface, ground and recycled water sources worldwide. However, GenX removals under the influence of variable characteristics of the organic and inorganic compounds present in the natural water sources, have often been overlooked in scientific literature. This is critically important given that the ionic composition and characteristics of organic matter in natural waters are spatially and seasonally variable. A strongly basic anion exchange (IX) resin was used to remove GenX and two other perfluorinated ether acids (PFEAS) from natural surface and recycled water sources. Factors influencing the uptake behavior included the PFEAS concentrations, resin dosage, and background anion characteristics. The equivalent background compound was employed to evaluate the competitive uptake between natural organic matter (NOM), inorganic ions and PFEAS in natural water matrices. Experimental data were compared with different mathematical and physical models and it was depicted that approximately 4-6% of the initial NOM competed with PFEAS for active exchange sites. Further, IX was able to achieve complete PFEAS removal (Cfinal<10 ng/L) with simultaneous removal of>60% NOM and >80% inorganic ions. Results of this study indicate that IX exhibits great potential for PFEAS removal from natural drinking water sources.

Microcystin-LR removal by ion exchange: Investigating multicomponent interactions in natural waters.

Microcystin-LR (MCLR) is the most commonly encountered toxic microcystin variant. MCLR is usually present along with common surface water constituents such as inorganic ions and natural organic matter (NOM) which compete with MCLR for active sites during ion exchange (IX) process. Consequently, development of a multicomponent competitive model is essential for practical IX applications. This is critically important given that the NOM characteristics (charge density and molecular weight distribution) and inorganic ions concentrations are spatially variable and can change seasonally. In the present study, a systematic study was carried out into the multicomponent interactions of IX resin with inorganic ions and NOM during the MCLR removal process. This involved evaluation of MCLR removal in a single component system (i.e., MCLR only), a dual component system (MCLR and one other contaminant such as NOM), and a multiple component system (MCLR with NOM and different inorganic ions present in natural waters). A comprehensive understanding of the dynamic adsorption behavior showed that the experimental data for single component systems agree well with a Freundlich isotherm. For multicomponent interactions, the Equivalent Background Concentration (EBC) model which is derived from the Ideal Adsorption Solution Theory (IAST) provided the best correlation with the experimental data in natural waters. The concentrations of competing NOM and inorganic ions estimated by the EBC model were <10% of their initial concentrations. Sulphates are the most competitive inorganic ions followed by nitrates and bicarbonates and the multicomponent interactions could be well predicted by using the IAST-EBC model. However, the EBC model failed in the presence of higher molecular weight Suwannee River Humic Acid (SRHA) molecules due to neglecting of the pore blocking phenomenon. In the presence of higher molecular weight SRHA molecules, the Redlich-Peterson Isotherm (RP) model exhibited a better performance than the Sheindorf-Rebuhn-Sheintuch (SRS) and the EBC models.

Removal of Microcystin-LR from spiked natural and synthetic waters by anion exchange.

Cyanobacterial blooms are becoming a serious challenge across the globe due to changing climate and rainfall patterns as a consequence of human activities. In the present study, the fundamental interactions involved during the removal of Microcystin-LR (MCLR), one of the most commonly occurring cyanobacterial toxins, were investigated by employing strongly basic anion exchange (IX) resins. Several factors including the stoichiometric coefficients, competitive fractions and solute affinities were determined under various concentrations of inorganic ions and natural organic matter. The results indicated that suphates were the most competitive fractions with high affinity (α (affinity coefficient) values ~ 9) followed by nitrates (α ~ 4.7) and NOM fractions (α ~ 4.5, p < 0.05). The Equivalent Background Concentration Mode (EBC), that arises from the Ideal Adsorption Solution Theory (IAST), indicated a competitive fraction of ~2 µeq/L NOM, which approximates to <10% of the initial NOM concentrations, indicating a small fraction of the NOM resulting in the competitive effect. Further, studies with natural surface waters indicated that the MCLR uptake could be modeled using the IAST-EBC model and the IX resin could simultaneously removal of >90% of NOM, inorganic ions and MCLR at resin dosages of 3.6 meq/L or higher.

Characteristics of competitive uptake between Microcystin-LR and natural organic matter (NOM) fractions using strongly basic anion exchange resins.

Microcystins are the most commonly occurring cyanotoxins, and have been extensively studied across the globe. In the present study, a strongly basic anion exchange resin was employed to investigate the removal of Microcystin-LR (MCLR), one of the most toxic microcystin variants. Factors influencing the uptake behavior included the MCLR and resin concentrations, resin dosage, and natural organic matter (NOM) characteristics, specifically, the charge density and molecular weight distribution of source water NOM. Equivalent background concentration (EBC) was employed to evaluate the competitive uptake between NOM and MCLR. The experimental data were compared with different mathematical and physical models and pore diffusion was determined as the rate-limiting step. The resin dose/solute concentration ratio played a key role in the MCLR uptake process and MCLR removal was attributed primarily to electrostatic attractions. Charge density and molecular weight distribution of the background NOM fractions played a major role in MCLR removal at lower resin dosages (200 mg/L ∼ 1 mL/L and below), where a competitive uptake was observed due to the limited exchange sites. Further, evidences of pore blockage and site reduction were also observed in the presence of humics and larger molecular weight organic fractions, where a four-fold reduction in the MCLR uptake was observed. Comparable results were obtained for laboratory studies on synthetic laboratory water and surface water under similar conditions. Given their excellent performance and low cost, anion exchange resins are expected to present promising potentials for applications involving the removal of removal of algal toxins and NOM from surface waters.

Simultaneous uptake of NOM and Microcystin-LR by anion exchange resins: Effect of inorganic ions and resin regeneration.

This study investigated the efficiency of a strongly basic macroporous anion exchange resin for the co-removal of Microcystin-LR (MCLR) and natural organic matter (NOM) in waters affected by toxic algal blooms. Environmental factors influencing the uptake behavior included MCLR and resin concentrations, NOM and anionic species, specifically nitrate, sulphate and bicarbonate. A860 resin exhibited an excellent adsorption capacity of 3800 µg/g; more than 60% of the MCLR removal was achieved within 10 min with a resin dosage of 200 mg/L (∼1 mL/L). Further, kinetic studies revealed that the overall removal of MCLR is influenced by both external diffusion and intra-particle diffusion. Increasing NOM concentration resulted in a significant reduction of MCLR uptake, especially at lower resin dosages, where a competitive uptake between the charged NOM fractions and MCLR was observed due to limited active sites. In addition, MCLR uptake was significantly reduced in the presence of sulphate and nitrate in the water matrix. Moreover, performance of the resin proved to be stable from one regeneration cycle to another. Approximately 80% of MCLR and 50% of dissolved organic carbon (DOC) were recovered in the regenerated brine. Evidences of resin saturation and site reduction were also observed after 2000 bed volumes (BV) of operation. For all the investigated water matrices, a resin dosage of 1000 mg/L (∼4.5 mL/L) was sufficient to lower MCLR concentration from 100 µg/L to below the World Health Organization guideline of 1 µg/L, while simultaneously providing more than 80% NOM removal.