Perfluoroalkyl carboxylic acids (PFCAs) exhibit high chemical and thermal stability, rendering them versatile for various applications. However, their notable toxicity poses environmental and human health concerns. Detecting trace amounts of these chemicals is crucial to mitigate risks. Electrochemical sensors surpass traditional methods in sensitivity, selectivity, and cost-effectiveness. In this study, a graphene nanosheet-based sensor was developed for detecting perfluorooctanoic acid (PFOA) and perfluorodecanoic acid (PFDA). Using the Hummer method, graphene nanosheets were synthesized and characterized in terms of morphology, structural ordering, and surface topology. Ab initio molecular dynamics simulations determined the molecular interaction of per- and poly-fluoroalkyl substances (PFASs) with the sensor material. The sensor exhibited high sensitivity (50.75 µA·µM-1·cm-2 for PFOA and 29.58 µA·µM-1·cm-2 for PFDA) and low detection limits (10.4 nM for PFOA and 16.6 nM for PFDA) within the electrode dynamic linearity range of 0.05-500.0 µM (PFOA) and 0.08-500.0 µM (PFDA). Under optimal conditions, the sensor demonstrated excellent selectivity and recovery in testing for PFOA and PFDA in environmental samples, including spiked soil, water, spoiled vegetables, and fruit samples.
Natural organic matter (NOM) plays a critical role in the mobilization and bioavailability of metals and metalloids in the aquatic environment. Selenium (Se), an environmental contaminant of aquatic systems, has drawn increasing attention over the years. While Se is a vital micronutrient to human beings, animals and plants, excess Se intake may pose serious long-term risks. However, the interaction between Se and dissolved organic matter (DOM) remains relatively unexplored, especially the reaction mechanisms and interactions of specific NOM components of certain molecular weight and the corresponding functional group change. Herein, we report an investigation on the interactions between Se and DOM by focusing on the mass distribution profile change of operationally defined molecular weight fractions of humic acid (HA) and fulvic acid (FA). The results showed that across all molecular weights studied, HA fractions were more prone to enhanced aggregation upon introduction of Se into the system. For FA, the presence of Se species results in aggregation, dissociation, and redox reactions with the first two being the major mechanisms. Total organic carbon analysis (TOC), UV-vis spectroscopy (UV-vis), and Orbitrap MS data showed that [10, 30] kDa MW fraction had the largest aromatic decrease (CRAM-like, lignin-like and tannin-like) upon addition of SeO2 via dissociation as the dominant mechanism. Fourier transform infrared spectroscopy (FT-IR) revealed that Se based bridging or chelation of functional groups from individual DOM components through hydrogen bonding in the form of SeOâ¯H and possibly Seâ¯H and/or attractive electrostatic interactions lead to aggregated DOM1â¯Seâ¯DOM2. It was concluded from two-dimensional correlation analyses of excitation emission matrix (EEM) and FT-IR that the preferred Se-binding follows lipid â peptide â tannin â aromatic functionalities. These results provide new understanding of Se interactions with various NOM components in aquatic environments and provide insight for Se assessing health risk and/or treatment of Se contaminated water.
The synthetic dye discharge is responsible for nearly one-fifth of the total water pollution from textile industry, which poses both environmental and public health risks. Herein, a solid substrate inoculated with fungi is proposed as an effective and environmentally friendly approach for catalyzing organic dye degradation. Pleurotus ostreatus was inoculated onto commercially available solid substrates such as sorghum, bran, and husk. Among these, P. ostreatus grown on sorghum (PO-SORG) produced the highest enzyme activity and was further tested for its dye biodegradation ability. Four dye compounds, Reactive Blue 19 (RB-19), Indigo Carmine, Acid Orange 7, and Acid Red 1 were degraded by PO-SORG with removal efficiencies of 93%, 95%, 95%, and 78%, respectively. Under more industrially relevant conditions, PO-SORG successfully degraded dyes in synthetic wastewater and in samples collected from a local textile factory, which reveals its potential for practical usage. Various biotransformation intermediates and end-products were identified for each dye. PO-SORG exhibited high stability even under relatively extreme temperatures and pH conditions. Over 85% removal of RB-19 was achieved after three consecutive batch cycles, demonstrating reusability of this approach. Altogether, PO-SORG demonstrated outstanding reusability and sustainability and offers considerable potential for treating wastewater streams containing synthetic organic dyes.
Arsenic (As) is abundant in the environment and can be found in both organic (e.g., methylated) and inorganic (e.g., arsenate and arsenite) forms. The source of As in the environment is attributed to both natural reactions and anthropogenic activities. As can also be released naturally to groundwater through As-bearing minerals including arsenopyrites, realgar, and orpiment. Similarly, agricultural and industrial activities have elevated As levels in groundwater. High levels of As in groundwater pose serious health risks and have been regulated in many developed and developing countries. In particular, the presence of inorganic forms of As in drinking water sources gained widespread attention due to their cellular and enzyme disruption activities. The research community has primarily focused on reviewing the natural occurrence and mobilization of As. Yet, As originating from anthropogenic activities, its mobility, and potential treatment techniques have not been covered. This review summarizes the origin, geochemistry, occurrence, mobilization, microbial interaction of natural and anthropogenic-As, and common remediation technologies for As removal from groundwater. In addition, As remediation methods are critically evaluated in terms of practical applicability at drinking water treatment plants, knowledge gaps, and future research needs. Finally, perspectives on As removal technologies and associated implementation limitations in developing countries and small communities are discussed.
The mother earth is a source of natural resources that, in conjunction with anthropogenic activities, generates a wide spectrum of different biowastes. These biomaterials can be used as low-cost raw feedstock to produce bioenergy, value-added products, and other commodities. However, the improper management and disposal of these biowastes can generate relevant environmental impacts. Consequently, it is imperative to explore alternative technologies for the valorization and exploitation of these wastes to obtain benefits for the society. This review covers different aspects related to valorization of biowastes and their applications in water pollution, soil fertility and green energy generation. The classification and characteristics of different biowastes (biosolids, animal wastes and effluents, plant biomass, wood and green wastes) including their main generation sources are discussed. Different technologies (e.g., pyrolysis, hydrothermal carbonization, anaerobic digestion, gasification, biodrying) for the transformation and valorization of these residues are also analyzed. The application of biowastes in soil fertility, environmental pollution and energy production are described and illustrative examples are provided. Finally, the challenges related to implement low-cost and sustainable biowaste management strategies are highlighted. It was concluded that reliable simulation studies are required to optimize all the logistic stages of management chain of these residues considering the constraints generated from the economic, environmental and social aspects of the biowaste generation sources and their locations. The recollection and sorting of biowastes are key parameters to minimize the costs associated to their management and valorization. Also, the concepts of Industry 4.0 can contribute to achieve a successful commercial production of the value-added products obtained from the biowaste valorization. Overall, this review provides a general outlook of biowaste management and its valorization in the current context of circular economy.
Soil , Technology , Animals , Soil/chemistry
This paper reviews the currently used pretreatment methods for microplastics (MPs) analysis in soil and freshwater sediments, primarily sample processing, pretreatment, and characterization methods for MPs analysis. In addition, analytical tools (e.g., lab instruments), MPs characteristics, and MPs quantity, are included in this review. Prior to pretreatment, soil and sediment samples are typically processed using sieving and drying methods, and a sample quantity of <50 g was mostly used for the pretreatment. Density separation was commonly performed before organic matter removal. Sodium chloride (NaCl) and zinc chloride (ZnCl2) were most often used for density separation, and hydrogen peroxide (H2O2) oxidation was most frequently used to remove organic matter. Although advantages of each pretreatment method have been investigated, it is still challenging to determine a universal pretreatment method due to sample variability (e.g., sample characteristics). Furthermore, it is highly required to establish standard pretreatment methods that can be used for various environmental matrices, including air, water, and wastes as well as soil and sediment.
Advanced catalysts are crucial for a wide range of chemical, pharmaceutical, energy, and environmental applications. They can reduce energy barriers and increase reaction rates for desirable transformations, making many critical large-scale processes feasible, eco-friendly, energy-efficient, and affordable. Advances in nanotechnology have ushered in a new era for heterogeneous catalysis. Nanoscale catalytic materials are known to surpass their conventional macro-sized counterparts in performance and precision, owing it to their ultra-high surface activities and unique size-dependent quantum properties. In water treatment, nanocatalysts can offer significant promise for novel and ecofriendly pollutant degradation technologies that can be tailored for customer-specific needs. In particular, nano-palladium catalysts have shown promise in degrading larger molecules, making them attractive for mitigating emerging contaminants. However, the applicability of nanomaterials, including nanocatalysts, in practical deployable and ecofriendly devices, is severely limited due to their easy proliferation into the service environment, which raises concerns of toxicity, material retrieval, reusability, and related cost and safety issues. To overcome this limitation, matrix-supported hybrid nanostructures, where nanocatalysts are integrated with other solids for stability and durability, can be employed. The interaction between the support and nanocatalysts becomes important in these materials and needs to be well investigated to better understand their physical, chemical, and catalytic behavior. This review paper presents an overview of recent studies on matrix-supported Pd-nanocatalysts and highlights some of the novel emerging concepts. The focus is on suitable approaches to integrate nanocatalysts in water treatment applications to mitigate emerging contaminants including halogenated molecules. The state-of-the-art supports for palladium nanocatalysts that can be deployed in water treatment systems are reviewed. In addition, research opportunities are emphasized to design robust, reusable, and ecofriendly nanocatalyst architecture.
The simultaneous presence of hazardous chemicals and pathogenic microorganisms in wastewater is tremendously endangering the environment and human health. Therefore, developing a mitigation strategy for adequately degrading toxic compounds and inactivating/killing microorganisms is urgently needed to protect ecosystems. In this paper, the synergetic effects of the photocatalytic activity of TiO2 and Cu-TiO2 nanoparticles (NPs) and the oxidation processes of non-thermal atmospheric pressure plasma (NTAPP) were comprehensively investigated for both the inactivation/killing of common water contaminating bacteria (Escherichia coli (E. coli)) and the degradation of direct textile wastewater (DTW). The photocatalytic NPs were synthesized using the hydrothermal method and further characterized employing field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), ultraviolet-visible diffuse reflection spectroscopy (UV-Vis DRS) and photoluminescence (PL). Results revealed the predominant presence of the typical anatase phase for both the flower-like TiO2 and the multipod-like Cu-TiO2 structures. UV-Vis DRS and PL analyses showed that the addition of Cu dopants reduced the bandgap and increased oxygen defect vacancies of TiO2. The inactivation of E. coli in suspension and degradation of DTW were then examined upon treating the aqueous media with various plasma alone and plasma/NPs conditions (Ar plasma, Ar + O2 plasma and Ar + N2 plasma, Ar plasma + TiO2 NPs and Ar plasma + Cu-TiO2 NPs). Primary and secondary excited species such as OHË, O, H and N2* generated in plasma during the processes were recognized by in situ optical emission spectrometry (OES) measurements. Several other spectroscopic analyses were further employed to quantify some reactive oxygen species (ROS) such as OH, H2O2 and O3 generated during the processes. Moreover, the changes in the pH and electrical conductivity (EC) of the solutions were also assessed. The inactivation of bacteria was examined by the colony-forming unit (CFU) method after plating the treated suspensions on agar, and the degradation of organic compounds in DTW was further validated by measuring the total organic carbon (TOC) removal efficiency. All results collectively revealed that the combinatorial plasma-photocatalysis strategy involving Cu-TiO2 NPs and argon plasma jet produced higher concentrations of ROS and proved to be a promising one-step wastewater treatment effectively killing microorganisms and degrading toxic organic compounds.
Municipal wastewater has been identified as a potential source of natural phosphorus (P) that is projected to become depleted in a few decades based on current exploitation rates. This paper focuses on combining a bench-scale anaerobic/anoxic/aerobic membrane bioreactor (MBR) and magnesium carbonate (MgCO3)-based pellets to effectively recover P from municipal wastewater. Ethanol was introduced into the anoxic zone of the MBR system as an external carbon source to improve P release via the enhanced biological phosphorus removal (EBPR) mechanism, making it available for adsorption by the continuous-flow MgCO3 pellet column. An increase in the concentration of P in the MBR effluent led to an increase in the P adsorption capacity of the MgCO3 pellets. As a result, the anaerobic/anoxic/aerobic MBR system, combined with a MgCO3 pellet column and ethanol, achieved 91.6% P recovery from municipal wastewater, resulting in a maximum P adsorption capacity of 12.8 mg P/g MgCO3 through the continuous-flow MgCO3 pellet column. Although the introduction of ethanol into the anoxic zone was instrumental in releasing P through the EBPR, it could potentially increase membrane fouling by increasing the concentration of extracellular polymeric substances (EPSs) in the anoxic zone.
Per- and polyfluoroalkyl substances (PFAS) are a set of synthetic chemicals which contain several carbon-fluorine (C-F) bonds and have been in production for the past eight decades. PFAS have been used in several industrial and consumer products including nonstick pans, food packaging, firefighting foams, and carpeting. PFAS require proper investigations worldwide due to their omnipresence in the biotic environment and the resulting pollution to drinking water sources. These harmful chemicals have been associated with adverse health effects such as liver damage, cancer, low fertility, hormone subjugation, and thyroid illness. In addition, these fluorinated compounds show high chemical, thermal, biological, hydrolytic, photochemical, and oxidative stability. Therefore, effective treatment processes are required for the removal and degradation of PFAS from wastewater, drinking water, and groundwater. Previous review papers have provided excellent summaries on PFAS treatment technologies, but the focus has been on the elimination efficiency without providing mechanistic understanding of removal/degradation pathways. The present review summarizes a comprehensive examination of various thermal and non-thermal PFAS destruction technologies. It includes sonochemical/ultrasound degradation, microwave hydrothermal treatment, subcritical or supercritical treatment, electrical discharge plasma technology, thermal destruction methods/incinerations, low/high-temperature thermal desorption process, vapor energy generator (VEG) technology and mechanochemical destruction. The background, degradation mechanisms/pathways, and advances of each remediation process are discussed in detail in this review.
Per- and polyfluoroalkyl substances (PFAS) are a family of fluorinated organic compounds of anthropogenic origin. Due to their unique chemical properties, widespread production, environmental distribution, long-term persistence, bioaccumulative potential, and associated risks for human health, PFAS have been classified as persistent organic pollutants of significant concern. Scientific evidence from the last several decades suggests that their widespread occurrence in the environment correlates with adverse effects on human health and ecology. The presence of PFAS in the aquatic environment demonstrates a close link between the anthroposphere and the hydrological cycle, and concentrations of PFAS in surface and groundwater range in value along the ng L-1-µg L-1 scale. Here, we critically reviewed the research published in the last decade on the global occurrence and distribution of PFAS in the aquatic environment. Ours is the first paper to critically evaluate the occurrence of PFAS at the continental scale and the evolving global regulatory responses to manage and mitigate the adverse human health risks posed by PFAS. The review reports that PFAS are widespread despite being phased out-they have been detected in different continents irrespective of the level of industrial development. Their occurrence far from the potential sources suggests that long-range atmospheric transport is an important pathway of PFAS distribution. Recently, several studies have investigated the health impacts of PFAS exposure-they have been detected in biota, drinking water, food, air, and human serum. In response to the emerging information about PFAS toxicity, several countries have provided administrative guidelines for PFAS in water, including Canada, the United Kingdom, Sweden, Norway, Germany, and Australia. In the US, additional regulatory measures are under consideration. Further, many PFAS have now been listed as persistent organic pollutants. This comprehensive review provides crucial baseline information on the global occurrence, distribution, and regulatory framework of PFAS.
Alkanesulfonic Acids , Drinking Water , Fluorocarbons , Water Pollutants, Chemical , Alkanesulfonic Acids/analysis , Drinking Water/analysis , Fluorocarbons/analysis , Humans , Wastewater , Water Pollutants, Chemical/analysis
Per- and polyfluoroalkyl substances (PFAS), which are present in many waters, have detrimental impacts on human health and the environment. Reverse osmosis (RO) and nanofiltration (NF) have shown excellent PFAS separation performance in water treatment; however, these membrane systems do not destroy PFAS but produce concentrated residual streams that need to be managed. Complete destruction of PFAS in RO and NF concentrate streams is ideal, but long-term sequestration strategies are also employed. Because no single technology is adequate for all situations, a range of processes are reviewed here that hold promise as components of treatment schemes for PFAS-laden membrane system concentrates. Attention is also given to relevant concentration processes because it is beneficial to reduce concentrate volume prior to PFAS destruction or sequestration. Given the costs and challenges of managing PFAS in membrane concentrates, it is critical to evaluate both established and emerging technologies in selecting processes for immediate use and continued research.
Effective recovery of phosphorus from municipal wastewater could be one of the best practical alternatives to protect aquatic environments from eutrophication and save natural phosphorus resources. This paper focuses on validating magnesium carbonate (MgCO3)-based pellets combined with a bench-scale anoxic/aerobic membrane bioreactor (MBR) system for advanced phosphorus recovery from municipal wastewater. As the flow rate of wastewater into the MgCO3 column decreased from 10 L/d to 2.5 L/d, the phosphorus recovery rate of the MgCO3-based pellets increased from 54.3 to 93.5%. However, the column's severe clogging was found after a 13-days operation due to the high removal of total suspended solids (TSS) (~82%) through the MgCO3 column. The anoxic/aerobic MBR introduction provided efficient removal of TSS, organic matter, and ammonia nitrogen before the MgCO3 column. The combination of MBR with the MgCO3 column achieved 73.1% phosphorus recovery from municipal wastewater without physical clogging. The P recovery capacity of the MgCO3-based pellets was maintained at 0.47 mg ortho-P/g MgCO3-based pellet during the continuous operation. Physical and chemical properties of MgCO3-based pellets before and after the experiment were characterized using scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and Brunauer-Emmett-Teller (BET) surface area analyzer.
Microplastics (MPs) and nanoplastics (NPs) have gained much attention in recent years because of their ubiquitous presence, which is the widely acknowledged threat to the environment. MPs can be <5 mm size, while NPs are <100 nm, and both can be detected in various forms and shapes in the environment to alleviate their harmful effects on aquatic species, soil organisms, birds, and humans. In efforts to address these issues, the present review discusses about sampling methods for water, sediments, and biota along with their merits and demerits. Various identification techniques such as FTIR, Raman, ToF-SIMS, MALDI TOF MS, and ICP-MS are critically discussed. The detrimental effects caused by MPs and NPs are discussed critically along with the efficient and cost-effective treatment processes including membrane technologies in order to remove plastics particles from various sources to mitigate their environmental pollution and risk assessment.
Magnetic graphene catalysts were prepared for the removal of antibiotics (sulfamethoxazole, norfloxacin, tetracycline and flumequine) from water. Different proportions of magnetite-graphene from 1:0 to 0:1 were considered to study the catalytic activation of inorganic peroxides, i.e. peroxymonosulfate (PMS), peroxydisulfate and hydrogen peroxide. The presence of graphene was mainly responsible for the activation, which was most effective in the presence of PMS. A ratio of 20% of magnetite in the solid was enough to achieve complete degradation of antibiotics with high recovery by application of a magnetic field. The performance of the catalyst was further evaluated in a simulated urban wastewater, studying the main parameters affecting the process and the stability in sequential reuses. The non-radical mechanism during the catalytic activation of PMS was hypothesized from kinetic scavenging probes tests. The electron transfer was suggested as the mechanism of the reaction from electron paramagnetic resonance analysis in the presence of D2O. The prepared magnetic catalyst showed high catalytic activity and stability to remove antibiotics from water.
Per- and polyfluoroalkyl substances (PFAS) are synthetic organic molecules used to manufacture various consumer and industrials products. In PFAS, the CF bond is stable, which renders these compounds chemically stable and prevents their breakdown. Several PFAS treatment processes such as adsorption, photolysis and photocatalysis, bioremediation, sonolysis, electrochemical oxidation, etc., have been explored and are being developed. The present review article has critically summarized degradative technologies and provides in-depth knowledge of photodegradation, electrochemical degradation, chemical oxidation, and reduction mineralization mechanism. Also, novel non-degradative technologies, including nano-adsorbents, natural and surface-modified clay minerals/zeolites, calixarene-based polymers, and molecularly imprinted polymers and adsorbents derived from biomaterials are discussed in detail. Of these novel approaches photocatalysis combined with membrane filtration or electrochemical oxidation via a treatment train approach shows promising results in removing PFAS in natural waters. The photocatalytic mineralization mechanism of PFOA is discussed, leading to recommendations for future research on novel remediation strategies for removing PFAS from water.
Fluorocarbons , Water Pollutants, Chemical , Adsorption , Clay , Fluorocarbons/analysis , Water , Water Pollutants, Chemical/analysis
Corrosion of copper material in drinking water systems causes public health concerns and plumbing failures. This study investigated the early corrosion of new copper surfaces in situ using a novel technique: quartz crystal microbalance with dissipation (QCMD). The QCMD results showed that increasing the water pH from 6.5 to 9.0 and the addition of 6 mg/L orthophosphate at pH 6.5 and 9.0 slowed down the copper surface mass changes as indicated by the reduced changes in frequency (Δf5) at 51-89% and total copper release at 29-72%. The water pH 9.0 without orthophosphate was the most likely to induce localized corrosion relative to other conditions at pH 6.5 and pH 9.0 with orthophosphate. Based on the changes in dissipation values (ΔD5) from QCMD and the morphology, microstructure, and composition of the deposited copper corrosion byproducts, digital microscopy, field-emission scanning electron microscopy with energy dispersive spectroscopy, and X-ray photoelectron spectrometry analyses confirmed that the pH and orthophosphate inhibited copper corrosion with different mechanisms. QCMD provided sensitive, rapid, and continuous responses to mass and surface changes and can be useful for evaluating early water corrosivity to new copper.
Per- and polyfluoroalkyl substances (PFAS) are a large group of perfluorinated organic molecules that have been in use since the 1940s for industrial, commercial, and consumer applications. PFAS are a growing concern because some of them have shown persistent, bioaccumulative and toxic effects. Herein, we demonstrate an innovative technology of UV-vis/ZnxCu1-xFe2O4/oxalic acid for the degradation of perfluorooctanoic acid (PFOA) in water. The magnetically retrievable nanocrystalline heterogeneous ferrite catalysts, ZnxCu1-xFe2O4 were synthesized using a sol-gel auto-combustion process followed by calcination at 400 °C. The combination of ZnxCu1-xFe2O4 and oxalic acid generate reactive species under UV light irradiation. These reactive species are then shown to be capable of the photodegradation of PFOA. The degree of degradation is tracked by identifying transformation products using liquid chromatography coupled with quadrupole time-of-flight mass spectroscopy (LC-QTOF-MS).
Fluorocarbons , Caprylates , Oxalic Acid , Technology , Ultraviolet Rays , Zinc
Microplastics (MPs) with sizes < 5 mm are found in various compositions, shapes, morphologies, and textures that are the major sources of environmental pollution. The fraction of MPs in total weight of plastic accumulation around the world is predicted to be 13.2% by 2060. These micron-sized MPs are hazardous to marine species, birds, animals, soil creatures and humans due to their occurrence in air, water, soil, indoor dust and food items. The present review covers discussions on the damaging effects of MPs on the environment and their removal techniques including biodegradation, adsorption, catalytic, photocatalytic degradation, coagulation, filtration and electro-coagulation. The main techniques used to analyze the structural and surface changes such as cracks, holes and erosion post the degradation processes are FTIR and SEM analysis. In addition, reduction in plastic molecular weight by the microbes implies disintegration of MPs. Adsorptive removal by the magnetic adsorbent promises complete elimination while the biodegradable catalysts could remove 70-100% of MPs. Catalytic degradation via advanced oxidation assisted by S O 4 ⢠- or O H ⢠radicals generated by peroxymonosulfate or sodium sulfate are also adequately covered in addition to photocatalysis. The chemical methods such as sol-gel, agglomeration, and coagulation in conjunction with other physical methods are discussed concerning the drinking water/wastewater/sludge treatments. The efficacy, merits and demerits of the currently used removal approaches are reviewed that will be helpful in developing more sophisticated technologies for the complete mitigation of MPs from the environment.
