Determination of organic fluorinated compounds content in complex samples through combustion ion chromatography methods: a way to define a "Total Per- and Polyfluoroalkyl Substances (PFAS)" parameter?

Emerging contaminants are a growing concern for scientists and public authorities. The group of per-polyfluoroalkyl substances (PFAS), known as 'forever chemicals', in complex environmental liquid and solid matrices was analysed in this study. The development of global analytical methods based on combustion ion chromatography (CIC) is expected to provide accurate picture of the overall PFAS contamination level via the determination of extractable organic fluorine (EOF) and adsorbable organic fluorine (AOF). The obtained results may be put into perspective with other methods such as targeted analyses (LC-MS/MS). The impact of pH, the presence of dissolved organic carbon and suspended particles on AOF measurements were explored. The effectiveness of the washing step to remove adsorbed inorganic fluorine (IF) has been proven for samples containing up to 8 mgF.L-1. CIC-based methods showed good repeatability and reproducibility for the complex matrices studied. Environmental applications of these methods have been tested. AOF and EOF analyses could explain between 1 % and 23 % and 0.1 % to 2 % of total organic fluorine (TOF), respectively. The sum of PFAS compounds expressed as fluorine could explain from 0.2 % to 11 % and from 0.003 % to 5 % for AOF and EOF, respectively. These results also suggest that some fluorinated compounds are not adsorbed or extractable and/or lost by volatilisation during the application of AOF and EOF analytical procedure. These findings highlight that AOF and EOF are not entirely efficient as proxy to assess "total PFAS" for assessing environmental contamination by PFAS. However, these methods could still be applied to gain a better understanding of the sources and fate of PFAS in the environment.

Selective leaching of indium from spent LCD screens by siderophore desferrioxamine E.

Given the criticality of indium (In) in high-tech applications, spent LCD screens can represent a viable secondary In resource. In this work, an innovative and alternative technology to selectively leach In from spent LCD screens using a microbial chelating agent, desferrioxamine E (DFOE), was developed. Indium was concentrated from spent LCD screens by implementing an adapted pre-treatment procedure, allowing the isolation of an indium-rich glassy fraction. During leaching, the competition between aluminum (Al) and In for complexation with DFOE leads to the precipitation of In(OH)3 at low DFOE concentrations (12-240 µM). After adjusting the optimal conditions (fraction size: 0-36 µM, pH: 5.5, S/L ratio: 1 g/L, 25 °C), the In leaching yield reached 32%, ten times higher than Al over 90 days with 5 mM DFOE. Thus, achieving high In recovery is possible through i) prolonging leaching durations, ii) selective leaching, and iii) minimizing Al interference. This is the first attempt to selectively leach In using a selected siderophore from end-of-life products with high concentrations of non-targeted elements (i.e. Al, Si, and Ca). This study demonstrates the potential of generating indium-rich leachates, which can be subsequently processed through the GaLIophore technology for In refining.

Molecular interactions of paraben family of pollutants with embryonic neuronal proteins of Danio rerio: A step ahead in computational toxicity towards adverse outcome pathway.

The paraben family of endocrine disruptors exhibit persistent behaviours in aquatic matrices, having bio-accumulative effects and necessitating toxicity analysis and safe use, as well as prevention of food web penetration. In this study, the toxicity effects of 9 different parabens (Methyl, Ethyl, Propyl, Butyl, Heptyl, Isopropyl, Isobutyl, benzyl parabens and p-hydroxybenzoic acid) were studied against 17 neuronal proteins (Neurog1, Ascl1a, DLA, Syn2a, Ntn1a, Pitx2, and SoxB1, Her/Hes, Zic family) expressed during the early embryonic developmental stage of Danio rerio. The neuronal genes were selected as a biomarker to study the inhibitory effects on the cascade of genes expressed in the early developmental stage. The study uses trRossetta software to predict protein structures of neuronal genes, followed by structural refinement, energy minimisation, and active site prediction, evaluated using energy value, RC plot and ERRAT scores of PROCHECK and ERRAT programs. Compared to raw structures, highly confident predicted structures and quality scores were observed for refined protein with few exceptions. Based on the polarity and charge of the aminoacids, the probable pockets were identified using active site prediction, which were then used for molecular docking analysis. Further, the ADMET analysis, ligand likeliness and toxicological test revealed the paraben family of compounds as one of the most susceptible toxic and mutagenic compounds. The molecular docking results showed an interesting pattern of increasing binding affinity with increase in the carbon chains of paraben molecules. Benzyl Paraben showed higher binding affinities across all 17 neuronal proteins. Finally, gene co-occurrence/co-expression and protein-protein interaction studies using the STRING database depict that all proteins are functionally related and play essential roles in standard biological processes or pathways, conserved and expressed in diverse organisms. The interaction between paraben compounds and neuronal genes indicates high risks of inhibiting reactions in embryonic stages, emphasising the need for effective treatment measures and strict regulations.

Recovery technologies for indium, gallium, and germanium from end-of-life products (electronic waste) - A review.

Advanced high-tech applications for communication, renewable energy, and display, heavily rely on technology critical elements (TCEs) such as indium, gallium, and germanium. Ensuring their sustainable supply is a pressing concern due to their high economic value and supply risks in the European Union. Recovering these elements from end-of-life (EoL) products (electronic waste: e-waste) offers a potential solution to address TCEs shortages. The review highlights recent advances in pre-treatment and hydrometallurgical and biohydrometallurgical methods for indium, gallium, and germanium recovery from EoL products, including spent liquid crystal displays (LCDs), light emitting diodes (LEDs), photovoltaics (PVs), and optical fibers (OFs). Leaching methods, including strong mineral and organic acids, and bioleaching, achieve over 95% indium recovery from spent LCDs. Recovery methods emphasize solvent extraction, chemical precipitation, and cementation. However, challenges persist in separating indium from other non-target elements like Al, Fe, Zn, and Sn. Promising purification involves solid-phase extraction, electrochemical separation, and supercritical fluid extraction. Gallium recovery from spent GaN and GaAs LEDs achieves 99% yield via leaching with HCl after annealing and HNO3, respectively. Sustainable gallium purification techniques include solvent extraction, ionic liquid extraction, and nanofiltration. Indium and gallium recovery from spent CIGS PVs achieves over 90% extraction yields via H2SO4 with citric acid-H2O2 and alkali. Although bioleaching is slower than chemical leaching (several days versus several hours), indirect bioleaching shows potential, achieving 70% gallium extraction yield. Solvent extraction and electrolysis exhibit promise for pure gallium recovery. HF or alkali roasting leaches germanium with a high yield of 98% from spent OFs. Solvent extraction achieves over 90% germanium recovery with minimal silicon co-extraction. Solid-phase extraction offers selective germanium recovery. Advancements in optimizing and implementing these e-waste recovery protocols will enhance the circularity of these TCEs.

Significance of MOF adsorbents in uranium remediation from water.

Uranium is considered as one of the most perilous radioactive contaminants in the aqueous environment. It has shown detrimental effects on both flora and fauna and because of its toxicities on human beings, therefore its exclusion from the aqueous environment is very essential. The utilization of metal-organic frameworks (MOFs) as an adsorbent for the removal of uranium from the aqueous environment could be a good approach. MOFs possess unique properties like high surface area, high porosity, adjustable pore size, etc. This makes them promising adsorbents for the removal of uranium from contaminated water. In this paper, sources of uranium in the water environment, human health disorders, and application of the different types of MOFs as well as the mechanisms of uranium removal have been discussed meticulously.

Current challenges and future perspectives for the full circular economy of water in European countries.

This paper reviews the current problems and prospects to overcome circular water economy management challenges in European countries. The geopolitical paradigm of water, the water economy, water innovation, water management and regulation in Europe, environmental and safety concerns at water reuse, and technological solutions for water recovery are all covered in this review, which has been prepared in the frame of the COST ACTION (CA, 20133) FULLRECO4US, Working Group (WG) 4. With a Circular Economy approach to water recycling and recovery based on this COST Action, this review paper aims to develop novel, futuristic solutions to overcome the difficulties that the European Union (EU) is currently facing. The detailed review of the current environmental barriers and upcoming difficulties for water reuse in Europe with a Circular Economy vision is another distinctive aspect of this study. It is observed that the biggest challenge in using and recycling water from wastewater treatment plants is dealing with technical, social, political, and economic issues. For instance, geographical differences significantly affect technological problems, and it is effective in terms of social acceptance of the reuse of treated water. Local governmental organizations should support and encourage initiatives to expand water reuse, particularly for agricultural and industrial uses across all of Europe. It should not also be disregarded that the latest hydro politics approach to water management will actively contribute to addressing the issues associated with water scarcity.

Dynamic modelling the effects of ionic strength and ion complexation on trace metal speciation during anaerobic digestion.

Dosing trace metals into anaerobic digestors is proven to improve biogas production rate and yield by stimulating microorganisms involved in the metabolic pathways. Trace metal effects are governed by metal speciation and bioavailability. Though chemical equilibrium speciation models are well-established and widely used to understand metal speciation, the development of kinetic models considering biological and physicochemical processes has recently gained attention. This work proposes a dynamic model for metal speciation during anaerobic digestion which is based on a system of ordinary differential equations aimed to describe the kinetics of biological, precipitation/dissolution, gas transfer processes and, a system of algebraic equations to define fast ion complexation processes. The model also considers ion activity corrections to define effects of ionic strength. Results from this study shows the inaccuracy in predicting trace metal effects on anaerobic digestion by typical metal speciation models and the significance of considering non-ideal aqueous phase chemistry (ionic strength and ion pairing/complexation) to define speciation and metal labile fractions. Model results show a decrease in metal precipitation and increase in metal dissolved fraction and methane production yield with increase in ionic strength. Capability of the model to dynamically predict trace metal effects on anaerobic digestion under different conditions, like changing dosing conditions and initial iron to sulphide ratio, was also tested and verified. Dosing iron increases methane production and decreases hydrogen sulphide production. However, when iron to sulphide ratio is greater than 1, methane production decreases due to increase in dissolved iron which reaches inhibitory concentration levels.

Systematic computational toxicity analysis of the ozonolytic degraded compounds of azo dyes: Quantitative structure-activity relationship (QSAR) and adverse outcome pathway (AOP) based approach.

The present study identifies and analyses the degraded products of three azo dyes (Reactive Orange 16, Reactive Red 120, and Direct Red 80) and proffers their in silico toxicity predictions. In our previously published work, the synthetic dye effluents were degraded using an ozonolysis-based Advanced Oxidation Process. In the present study, the degraded products of the three dyes were analysed using GC-MS at endpoint strategy and further subjected to in silico toxicity analysis using Toxicity Estimation Software Tool (TEST), Prediction Of TOXicity of chemicals (ProTox-II), and Estimation Programs Interface Suite (EPI Suite). Several physiological toxicity endpoints, such as hepatotoxicity, carcinogenicity, mutagenicity, cellular and molecular interactions, were considered to assess the Quantitative Structure-Activity Relationships (QSAR) and adverse outcome pathways. The environmental fate of the by-products in terms of their biodegradability and possible bioaccumulation was also assessed. Results of ProTox-II suggested that the azo dye degradation products are carcinogenic, immunotoxic, and cytotoxic and displayed toxicity towards Androgen Receptor and Mitochondrial Membrane Potential. TEST results predicted LC50 and IGC50 values for three organisms Tetrahymena pyriformis, Daphnia magna, and Pimephales promelas. EPISUITE software via the BCFBAF module surmises that the degradation products' bioaccumulation (BAF) and bioconcentration factors (BCF) are high. The cumulative inference of the results suggests that most degradation by-products are toxic and need further remediation strategies. The study aims to complement existing tests to predict toxicity and prioritise the elimination/reduction of harmful degradation products of primary treatment procedures. The novelty of this study is that it streamlines in silico approaches to predict the nature of toxicity of degradation by-products of toxic industrial affluents like azo dyes. These approaches can assist the first phase of toxicology assessments for any pollutant for regulatory decision-making bodies to chalk out appropriate action plans for their remediation.

A Critical Review on the Recovery of Base and Critical Elements from Electronic Waste-Contaminated Streams Using Microbial Biotechnology.

Pollution by end-of-life electronics is a rapid ever-increasing threat and is a universal concern with production of million metric tons of these wastes per annum. Electronic wastes (E-waste) are rejected electric or electronic equipment which have no other applications. The aggrandized unproper land filling of E-waste may generate hazardous effects on living organisms and ecosystem. At present, millions of tons of E-waste await the advancement of more efficient and worthwhile recycling techniques. Recovery of base and critical elements from electronic scraps will not only reduce the mining of these elements from natural resources but also reduces the contamination caused by the hazardous chemicals (mostly organic micropollutants) released from these wastes when unproperly disposed of. Bioleaching is reported to be the most eco-friendly process for metal recycling from spent electronic goods. A detailed investigation of microbial biodiversity and a molecular understanding of the metabolic pathways of bioleaching microorganisms will play a vital function in extraction of valuable minerals from the end-of-life scraps. Bioleaching technique as an economic and green technology costs around 7 USD per kg for effective reusing of E-waste as compared to other physical and chemical techniques. This review provides a summary of worldwide scenario of electronic pollutants; generation, composition and hazardous components of electronic waste; recycling of valuable elements through bioleaching; mechanism of bioleaching; microorganisms involved in base and critical element recovery from E-waste; commercial bioleaching operations; and upcoming aspects of this eco-friendly technique.

The biofilm matrix: multitasking in a shared space.

The biofilm matrix can be considered to be a shared space for the encased microbial cells, comprising a wide variety of extracellular polymeric substances (EPS), such as polysaccharides, proteins, amyloids, lipids and extracellular DNA (eDNA), as well as membrane vesicles and humic-like microbially derived refractory substances. EPS are dynamic in space and time and their components interact in complex ways, fulfilling various functions: to stabilize the matrix, acquire nutrients, retain and protect eDNA or exoenzymes, or offer sorption sites for ions and hydrophobic substances. The retention of exoenzymes effectively renders the biofilm matrix an external digestion system influencing the global turnover of biopolymers, considering the ubiquitous relevance of biofilms. Physico-chemical and biological interactions and environmental conditions enable biofilm systems to morph into films, microcolonies and macrocolonies, films, ridges, ripples, columns, pellicles, bubbles, mushrooms and suspended aggregates - in response to the very diverse conditions confronting a particular biofilm community. Assembly and dynamics of the matrix are mostly coordinated by secondary messengers, signalling molecules or small RNAs, in both medically relevant and environmental biofilms. Fully deciphering how bacteria provide structure to the matrix, and thus facilitate and benefit from extracellular reactions, remains the challenge for future biofilm research.

Effects of foliar application of humic acid extracts and indole acetic acid on important growth indices of canola (Brassica napus L.).

Vermicompost (VC) is a rich source of HA that improves plant growth and yield indices such as fresh and dry weights, plant height, stem diameter, leaf area, and chlorophyll index value. In this study, the effect of foliar application of HA extracted from different types of VC enriched with bacteria and/or fertilizers, commercial HA (CHA) and indole acetic acid (IAA) on the growth characteristics of canola (Brassica napus) in greenhouse conditions were compared. According to the results, the foliar application of HA extracted from VC had complete superiority over CHA and IAA in most traits except for the leaf number. Furthermore, the highest level of foliar application of HA (600 mg L-1) enriched with Azotobacter chroococcum (21Az) + Pseudomonas fluorescens (Ps 59) (HA-AS) generated the highest height, diameter, leaf area, and chlorophyll index value. Also, the highest stomatal conductance and photosynthesis rate were observed with the application of 600 mg L-1 HA extracted from VC enriched with nitrogen, sulfur, and phosphorus (HA-NSP) compared to the other treatments. Besides, dry and fresh weights and seed yield under HA-NSP and HA-AS treatments were at their highest rate. Among the extracted HAs, the one extracted from the nitrogen enriched VC had the lowest efficiency. Based on the present study, the HA extracted from VC enriched with Azotobacter, Pseudomonas and NSP is recommended to increase canola growth and production.

A Review on Biotechnological Approaches Applied for Marine Hydrocarbon Spills Remediation.

The increasing demand for petroleum products generates needs for innovative and reliable methods for cleaning up crude oil spills. Annually, several oil spills occur around the world, which brings numerous ecological and environmental disasters on the surface of deep seawaters like oceans. Biological and physico-chemical remediation technologies can be efficient in terms of spill cleanup and microorganisms-mainly bacteria-are the main ones responsible for petroleum hydrocarbons (PHCs) degradation such as crude oil. Currently, biodegradation is considered as one of the most sustainable and efficient techniques for the removal of PHCs. However, environmental factors associated with the functioning and performance of microorganisms involved in hydrocarbon-degradation have remained relatively unclear. This has limited our understanding on how to select and inoculate microorganisms within technologies of cleaning and to optimize physico-chemical remediation and degradation methods. This review article presents the latest discoveries in bioremediation techniques such as biostimulation, bioaugmentation, and biosurfactants as well as immobilization strategies for increasing the efficiency. Besides, environmental affecting factors and microbial strains engaged in bioremediation and biodegradation of PHCs in marines are discussed.

Sorption vs adsorption: The words they are a-changin', not the phenomena.

In this discussion, we highlight that the terms sorption and adsorption are often confused and misused in many articles. Even if one thought their formal definition is well known, this does not appear to be the case. We recommend encouragement to adopt the word adsorption only when fully supported by appropriate data and using the sorption terminology when it is more speculative, typically in complex solid/fluid natural systems.

Nano-biochar: A novel solution for sustainable agriculture and environmental remediation.

Currently, the applications of biochar (BC) in agricultural practices and for environmental remediation purposes have demonstrated multifaceted advantages despite a few limitations. Nano-BC offers considerable opportunities especially for the remediation of hazardous contaminants as well as the improvement of crop productivity. Positive outcomes of nano-BC on soil physico-chemical and biological characteristics have indicated its suitability for agricultural applications. Nano-BC may effectively regulate the mobilization and sorption of important micro- and macro-nutrients, along with the hazardous contaminants including potentially toxic metals, pesticides, etc. Additionally, the sorption characteristics of nano-BC depends substantially on feedstock materials and pyrolysis temperatures. Nevertheless, the conducted investigations regarding nano-BC are in infant stages, requiring extensive field investigations. The nano-enhanced properties of BC on one hand dramatically improve its effectiveness and sustainability, on the other hand, there may be associated with toxicity development in diverse aquatic and/or terrestrial environments. Therefore, risk assessment on soil organisms and its indirect impact on human health is another area of concern linked with the field application of nano-BC. The present review delineates the potentiality of nano-BC as an emerging sorbent for sustainable agriculture and environmental applications.

Effect of Different Enriched Vermicomposts, Humic Acid Extract and Indole-3-Acetic Acid Amendments on the Growth of Brassica napus.

Humic acid (HA) is a specific and stable component of humus materials that behaves similarly to growth stimulants, esp. auxin hormones, contributing to improving growth indices and performance of plants. As a rich source of HA, vermicompost (VC) is also a plant growth stimulating bio-fertilizer that can enhance growth indices and performance in plants. The purpose of the present study is to compare the influence of VC enriched with bacterial and/or fertilizer, commercial humic acid (CHA) extract, and indole-3-acetic acid (IAA) on improving growth characteristics and performance of rapeseed under greenhouse conditions. The results showed the complete superiority of VC over the CHA and IAA (approximately 8% increase in the dry weights of root and aerial organ and nearly three times increase in seed weight). The highest values of these indices were obtained with VC enriched with Nitrogen, Sulfur, and Phosphorus, Azotobacter chroococcum and Pseudomonas fluorescens; the lowest value was obtained with VC enriched with urea. Additionally, the application of 3% VC and the control involved the highest and lowest values in all traits, respectively. The SPAD (chlorophyll index) value and stem diameter were not significantly affected by different application levels of VC. Overall, the applications of IAA and the CHA were not found to be suitable and therefore not recommended.

Preparation and applications of chitosan and cellulose composite materials.

Chitosan is a natural fiber, chemically cellulose-like biopolymer, which is processed from chitin. Its use as a natural polymer is getting more attention because it is non-toxic, renewable, and biocompatible. However, its poor mechanical and thermal strength, particle size, and surface area restrict its industrial use. Consequently, to improve these properties, cellulose and/or inorganic nanoparticles have been used. This review discusses the recent progress of chitosan and cellulose composite materials, their preparation, and their applications in different industrial sectors. It also discusses the modification of chitosan and cellulose composite materials to allow their use on a large scale. Finally, the recent development of chitosan composite materials for drug delivery, food packaging, protective coatings, and wastewater treatment are discussed. The challenges and perspectives for future research are also considered. This review suggests that chitosan and cellulose nano-composite are promising, low-cost products for environmental remediation involving a simple production process.

Removal of antimonate (Sb(V)) from aqueous solutions and its immobilization in soils with a novel Fe(III)-modified montmorillonite sorbent.

Over the past decades, contamination of terrestrial environments with antimony (Sb) has aroused a great deal of public concern. In this research, the efficacy of Fe(III)-modified montmorillonite (Mt) (Fe-Mt) for the removal of Sb(V) from aqueous solutions with Sb(V) concentration in the range of 0.2-1 mmol L-1 and immobilization of Sb(V) in soils spiked with 250 mg Sb(V) kg-1 was investigated. The immobilizing mechanisms of the modified clay were assessed by fitting the experimental sorption data with the Langmuir and Freundlich sorption models and a series of single and sequential extraction studies. The results showed that the adsorption data had a better fit with the Langmuir equation (R2: 0.99) and Fe-Mt could efficiently remove up to 95% of Sb(V) at lower concentration ranges. The concentrations of Sb(V) in exchangeable fraction of modified Community Bureau of Reference (BCR) sequential extraction and distilled water extracts of the amended soils decreased dramatically by up to 60% and 92%, respectively. Furthermore, the bioaccessibility of Sb(V) in simulated human gastric juice reduced remarkably by 52% to 60%, depending upon the soil fraction sizes. The results confirmed that Fe-Mt could be a promising candidate for the removal of Sb(V) from aqueous solutions and immobilization of Sb(V) in terrestrial environments.

Surface volatilization modeling of (semi-)volatile hydrophobic organic compounds: The role of reference compounds.

Volatilization of hazardous hydrophobic organic compounds is often observed in many water, wastewater and soil treatment (bio)processes. Several models have been developed to quantify and predict gas-liquid pollutant transfer, being the proportionality coefficient model (PCM) one of the most commonly used, particularly in wastewater treatment. The PCM is based on the use of oxygen as a reference compound, which has a low resistance to the transfer in the gas phase. However, this resistance might be important for (semi-)volatile organic compounds - or (semi-)VOCs, which may render the use of the PCM model inaccurate. This study proposes an experimental methodology and a modeling approach for the use of the two-reference compound model (2RCM) that considers both the liquid-side and the gas-side resistances, by using water and oxygen as references. Results showed that the 2RCM predicts more accurately the overall mass transfer coefficients than the PCM for a VOC and two semi-VOCs tested in this study. In addition, the 2RCM was found to be a more robust method to estimate mass transfer coefficient of any compound and its use can be extrapolated to all substances. Finally, the relevance and limitations of both models was established.