Insight into the wheat residues-derived adsorbents for the remediation of organic and inorganic aquatic contaminants: A review.

Wheat is a major grain crop of the world that provides a stable food for human consumption. Large amounts of by-products/waste materials are produced after the harvesting and processing of wheat crop. Such materials can cause an environmental issue if not disposed of properly. Several studies have shown that wheat residues can be efficient precursors for adsorbents because of their availability, renewability, lignocellulosic composition, and surface active groups enriched structure. In the literature, there are few review articles that address wheat residues-based adsorbents. For instance, the use of raw wheat straw and bran as adsorbents for heavy metals and wheat bran-based adsorbents against dyes. However, these reviews were specific in terms of adsorbate or adsorbent and did not provide detailed information about the modification, properties, and regeneration of these adsorbents. This article extensively reviews the utilization of wheat biomass/waste including straw, bran, husk, and stalk as precursors for raw or untreated, chemically treated, carbonaceous, and composite adsorbents against various environmental pollutants. The influences of inlet pollutant amount, adsorbent dose, pH, temperature, and time on the performance of adsorbents against pollutants were considered. The maximum uptakes, equilibrium time, and adsorption nature were identified from isotherms, kinetic, and thermodynamic studies. The highest adsorbed amounts of most tested contaminants were 448.20, 322.58, and 578.13 mg/g for lead, chromium, and copper, 1374.6 and 1449.4 mg/g for methylene blue and malachite green, and 854.75, 179.21, and 107.77 mg/g for tetracycline, phosphate, and nitrate, respectively. For the studied adsorbate/adsorbent systems the adsorption mechanism and regeneration were also discussed. Significant results and future directions are finally presented.

A review of remediation technologies for uranium-contaminated water.

Uranium is a naturally existing radioactive element present in the Earth's crust. It exhibits lithophilic characteristics, indicating its tendency to be located near the surface of the Earth and tightly bound to oxygen. It is ecotoxic, hence the need for its removal from the aqueous environment. This paper focuses on the variety of water treatment processes for the removal of uranium from water and this includes physical (membrane separation, adsorption and electrocoagulation), chemical (ion exchange, photocatalysis and persulfate reduction), and biological (bio-reduction and biosorption) approaches. It was observed that membrane filtration and ion exchange are the most popular and promising processes for this application. Membrane processes have high throughput but with the challenge of high power requirements and fouling. Besides high pH sensitivity, ion exchange does not have any major challenges related to its application. Several other unique observations were derived from this review. Chitosan/Chlorella pyrenoidosa composite adsorbent bearing phosphate ligand, hydroxyapatite aerogel and MXene/graphene oxide composite has shown super-adsorbent performance (>1000 mg/g uptake capacity) for uranium. Ultrafiltration (UF) membranes, reverse osmosis (RO) membranes and electrocoagulation have been observed not to go below 97% uranium removal/conversion efficiency for most cases reported in the literature. Heat persulfate reduction has been explored quite recently and shown to achieve as high as 86% uranium reduction efficiency. We anticipate that future studies would explore hybrid processes (which are any combinations of multiple conventional techniques) to solve various aspects of the process design and performance challenges.

A comprehensive characterisation of phaeochromocytoma and paraganglioma tumours through histone protein profiling, DNA methylation and transcriptomic analysis genome wide.

BACKGROUND: Phaeochromocytomas and paragangliomas (PPGLs) are rare neuroendocrine tumours. Pathogenic variants have been identified in more than 15 susceptibility genes; associated tumours are grouped into three Clusters, reinforced by their transcriptional profiles. Cluster 1A PPGLs have pathogenic variants affecting enzymes of the tricarboxylic acid cycle, including succinate dehydrogenase. Within inherited PPGLs, these are the most common. PPGL tumours are known to undergo epigenetic reprograming, and here, we report on global histone post-translational modifications and DNA methylation levels, alongside clinical phenotypes. RESULTS: Out of the 25 histone post-translational modifications examined, Cluster 1A PPGLs were distinguished from other tumours by a decrease in hyper-acetylated peptides and an increase in H3K4me2. DNA methylation was compared between tumours from individuals who developed metastatic disease versus those that did not. The majority of differentially methylated sites identified tended to be completely methylated or unmethylated in non-metastatic tumours, with low inter-sample variance. Metastatic tumours by contrast consistently had an intermediate DNA methylation state, including the ephrin receptor EPHA4 and its ligand EFNA3. Gene expression analyses performed to identify genes involved in metastatic tumour behaviour pin-pointed a number of genes previously described as mis-regulated in Cluster 1A tumours, as well as highlighting the tumour suppressor RGS22 and the pituitary tumour-transforming gene PTTG1. CONCLUSIONS: Combined transcriptomic and DNA methylation analyses revealed aberrant pathways, including ones that could be implicated in metastatic phenotypes and, for the first time, we report a decrease in hyper-acetylated histone marks in Cluster 1 PPGLs.

Bamboo-derived adsorbents for environmental remediation: A review of recent progress.

The bamboo family of plants is one of the fastest-growing species in the world. As such, there is an abundance of bamboo residues available for exploitation, especially in southeast Asian, central African and south American regions. The preparation of efficient adsorbents from bamboo residues is an emerging exploitation pathway. Biochars, activated carbons or raw bamboo fibers embedded with nanoparticles, each class of materials has been shown to be highly efficient in adsorption processes. This review aims to summarize recent findings in the application of bamboo-based adsorbents in the removal of organic, inorganic, or gaseous pollutants. Therefore, this review first discusses the preparation methods and surface modification methodologies and their effects on the adsorbent elemental content and other basic properties. The following sections assess the recent progress in the adsorption of heavy metals, organics, and gaseous substances by bamboo-based adsorbents, focusing on the optimum adsorption capacities, adsorption mechanisms and the optimum-fitting kinetic models and isotherms. Finally, research gaps were identified and directions for future research are proposed.

Uranium Removal from Aqueous Solutions by Aerogel-Based Adsorbents-A Critical Review.

Aerogels are a class of lightweight, nanoporous, and nanostructured materials with diverse chemical compositions and a huge potential for applications in a broad spectrum of fields. This has led the IUPAC to include them in the top ten emerging technologies in chemistry for 2022. This review provides an overview of aerogel-based adsorbents that have been used for the removal and recovery of uranium from aqueous environments, as well as an insight into the physicochemical parameters affecting the adsorption efficiency and mechanism. Uranium removal is of particular interest regarding uranium analysis and recovery, to cover the present and future uranium needs for nuclear power energy production. Among the methods used, such as ion exchange, precipitation, and solvent extraction, adsorption-based technologies are very attractive due to their easy and low-cost implementation, as well as the wide spectrum of adsorbents available. Aerogel-based adsorbents present an extraordinary sorption capacity for hexavalent uranium that can be as high as 8.8 mol kg−1 (2088 g kg−1). The adsorption data generally follow the Langmuir isotherm model, and the kinetic data are in most cases better described by the pseudo-second-order kinetic model. An evaluation of the thermodynamic data reveals that the adsorption is generally an endothermic, entropy-driven process (ΔH0, ΔS0 > 0). Spectroscopic studies (e.g., FTIR and XPS) indicate that the adsorption is based on the formation of inner-sphere complexes between surface active moieties and the uranyl cation. Regeneration and uranium recovery by acidification and complexation using carbonate or chelating ligands (e.g., EDTA) have been found to be successful. The application of aerogel-based adsorbents to uranium removal from industrial processes and uranium-contaminated waste waters was also successful, assuming that these materials could be very attractive as adsorbents in water treatment and uranium recovery technologies. However, the selectivity of the studied materials towards hexavalent uranium is limited, suggesting further developments of aerogel materials that could be modified by surface derivatization with chelating agents (e.g., salophen and iminodiacetate) presenting high selectivity for uranyl moieties.

Differential response of N2O emissions, N2O-producing and N2O-reducing bacteria to varying tetracycline doses in fertilized soil.

Tetracyclines are the most widely used antibiotics worldwide. Their presence in soils could affect nutrient cycling, but our knowledge regarding how they affect soil microbial communities involved in greenhouse gas emissions is limited. The objective of the current study was to evaluate how tetracycline is affecting N2O emissions and the abundance of denitrifiers in fertilized soil. For this purpose, soil mesocosms were treated with only NH4NO3 (100 mg/kg) or NH4NO3 (100 mg/kg) plus three different doses of tetracycline (0.1, 0.5 and 2 mg/kg). Soils that did not receive tetracycline or NH4NO3 were used as controls. Nitrous oxide fluxes were monitored daily for 16 days. The total bacterial (16S rRNA), the abundance of N2O-reducing and -producing bacteria were quantified by qPCR at the end of the experiment. The application of NH4NO3 caused a significant increase of N2O emissions and AOB abundance but did not affect the abundance of denitrifiers and AOA compared to control soils. Different doses of tetracycline in fertilized soils did not mitigate these N2O emissions; instead, higher cumulative emissions were noticed in soils treated with the lowest dose. In these soils the total bacterial abundance was higher compared to soils received higher tetracycline concentration. The abundances of the N2O-producing and N2O-reducing communities were also differently affected by the addition of tetracycline, which was dose-dependent. Higher doses of tetracycline favored N2O-reducers within the total bacterial community, which could be important for mitigating N2O emissions in the long term.

Correction: Anastopoulos et al. Multi-Drug Featurization and Deep Learning Improve Patient-Specific Predictions of Adverse Events. Int. J. Environ. Res. Public Health 2021, 18, 2600.

In the original publication [...].

Catalytic Neutralization of Water Pollutants Mediated by Dendritic Polymers.

Radially polymerized dendritic compounds are nowadays an established polymer category next to their linear, branched, and cross-linked counterparts. Their uncommon tree-like architecture is characterized by adjustable internal cavities and external groups. They are therefore exceptional absorbents and this attainment of high concentrations in their interior renders them ideal reaction media. In this framework, they are applied in many environmentally benign implementations. One of the most important among them is water purification through pollutant decomposition. Simple and composite catalysts and photo-catalysts containing dendritic polymers and applied in water remediation will be discussed jointly with some unconventional solutions and prospects.

Recent trends in the use of fly ash for the adsorption of pollutants in contaminated wastewater and soils: Effects on soil quality and plant growth.

Fly ash is one of the largest types of industrial wastes produced during the combustion of coal for energy generation. Finding efficient and sustainable solutions for its reuse has been the subject of substantial research worldwide. Here, we review the recent research data related to (i) the use of fly ash as a low-cost adsorbent for pollutants in wastewater and soils and (ii) its implications in soil-plant system. Fly ash showed prominent adsorption capacity for pollutants in water especially when it was activated or applied in composites. In addition to direct pollutant binding in soils, fly ash can enhance the soil pH indirectly increasing metals' immobilization reducing their plant uptake. Its non-selective adsorptive nature may lead to the co-adsorption of nutrients with pollutants which merits to be considered. Owing to its considerable nutrient contents, fly ash can also improve soil fertility and plant growth. The effects of fly ash on soil physico-chemical properties, microbial population and plant growth are critically evaluated. Fly ash can also contain potentially toxic contaminants (toxic metals, hydrocarbons, etc.) which could have harmful impacts on soil health and plant growth. Identifying the levels of inherent pollutants in fly ash is crucial to evaluate its suitability as a soil amendment. Negative effects of fly ash can also be addressed by using co-amendments, biological agents, and most importantly by an adequate calibration (dose and type) of fly ash based on site-specific conditions. Research directions are identified to promote the research regarding its use in wastewater treatment and agriculture.

Process Parameters Optimization, Characterization, and Application of KOH-Activated Norway Spruce Bark Graphitic Biochars for Efficient Azo Dye Adsorption.

In this work, Norway spruce bark was used as a precursor to prepare activated biochars (BCs) via chemical activation with potassium hydroxide (KOH) as a chemical activator. A Box-Behnken design (BBD) was conducted to evaluate and identify the optimal conditions to reach high specific surface area and high mass yield of BC samples. The studied BC preparation parameters and their levels were as follows: pyrolysis temperature (700, 800, and 900 °C), holding time (1, 2, and 3 h), and ratio of the biomass: chemical activator of 1: 1, 1.5, and 2. The planned BBD yielded BC with extremely high SSA values, up to 2209 m2·g-1. In addition, the BCs were physiochemically characterized, and the results indicated that the BCs exhibited disordered carbon structures and presented a high quantity of O-bearing functional groups on their surfaces, which might improve their adsorption performance towards organic pollutant removal. The BC with the highest SSA value was then employed as an adsorbent to remove Evans blue dye (EB) and colorful effluents. The kinetic study followed a general-order (GO) model, as the most suitable model to describe the experimental data, while the Redlich-Peterson model fitted the equilibrium data better. The EB adsorption capacity was 396.1 mg·g-1. The employment of the BC in the treatment of synthetic effluents, with several dyes and other organic and inorganic compounds, returned a high percentage of removal degree up to 87.7%. Desorption and cyclability tests showed that the biochar can be efficiently regenerated, maintaining an adsorption capacity of 75% after 4 adsorption-desorption cycles. The results of this work pointed out that Norway spruce bark indeed is a promising precursor for producing biochars with very promising properties.

Fenton oxidation for soil remediation: A critical review of observations in historically contaminated soils.

Fenton-based treatments have received tremendous attention in recent decades as viable strategies for soil decontamination. Historically contaminated soils are characterized by particular contamination types, pollution composition patterns, soil constituents, and complex soil-pollutant interactions arising due to long-term pollutant aging. These major pitfalls dictate the remediation efficiency in a significantly different way in soils with a history of contamination than that in a spiked soil. It becomes, therefore, highly challenging to treat historically contaminated soils. Despite the immense amount of collected research data in these soils, to our knowledge, no comprehensive review of this topic has been published. This article is intended to provide a critical review of the applications, limitations, and implications of various Fenton-based processes exclusively in these soils. These processes are differentiated on the basis of experimental conditions, reaction chemistry, efficiency, and impacts on soil biota. These processes are critically evaluated to illustrate the promising techniques with a brief description of related challenges and their potential solutions. Moreover, coupling Fenton oxidation with other remediation techniques such as bioremediation, chemical reduction, and soil washing has also been discussed. The last part of this review describes the effects of these processes onto soil quality and native biota, and how they can be addressed. It is also highly demanding to identify the processes which are not likely to evolve in practice either due to their poor efficiency, treatment cost, or environmental impacts. Future critical research directions have been identified to promote research for the upscaling of this technique for real field application.

Towards inferring nanopore sequencing ionic currents from nucleotide chemical structures.

The characteristic ionic currents of nucleotide kmers are commonly used in analyzing nanopore sequencing readouts. We present a graph convolutional network-based deep learning framework for predicting kmer characteristic ionic currents from corresponding chemical structures. We show such a framework can generalize the chemical information of the 5-methyl group from thymine to cytosine by correctly predicting 5-methylcytosine-containing DNA 6mers, thus shedding light on the de novo detection of nucleotide modifications.

VEGA is an interpretable generative model for inferring biological network activity in single-cell transcriptomics.

Deep learning architectures such as variational autoencoders have revolutionized the analysis of transcriptomics data. However, the latent space of these variational autoencoders offers little to no interpretability. To provide further biological insights, we introduce a novel sparse Variational Autoencoder architecture, VEGA (VAE Enhanced by Gene Annotations), whose decoder wiring mirrors user-provided gene modules, providing direct interpretability to the latent variables. We demonstrate the performance of VEGA in diverse biological contexts using pathways, gene regulatory networks and cell type identities as the gene modules that define its latent space. VEGA successfully recapitulates the mechanism of cellular-specific response to treatments, the status of master regulators as well as jointly revealing the cell type and cellular state identity in developing cells. We envision the approach could serve as an explanatory biological model for development and drug treatment experiments.

Single-stage production of miscanthus hydrochar at low severity conditions and application as adsorbent of copper and ammonium ions.

In the framework of bio-circular economy, miscanthus biomass was valorized through a single-stage, low severity hydrothermal carbonization process. The produced hydrochars were characterized using elemental and spectroscopic methodologies. It was determined that as the temperature increased so did the C content (47.9 and 68.9% for the samples prepared at 180 and 260 °C, respectively), whereas the O content decreased (from 44.2 to 25.5%, respectively). The adsorption behaviour of the hydrochars was investigated in the adsorption of Cu2+ and NH4+ and MIS-180 was determined as the optimum sample, achieving qmax values of 310 and 71 mg g-1, respectively. Isotherm and kinetic analysis indicated the higher number of O-containing functional groups of MIS-180 as the main reason for its higher adsorption capacities. Furthermore, Cu2+ adsorption followed the 2nd-order kinetic model, whereas NH4+ adsorption followed the 1st-order kinetic model, due to the different mechanisms involved, inner-sphere and outer-sphere complex formation, respectively.

Multi-Drug Featurization and Deep Learning Improve Patient-Specific Predictions of Adverse Events.

While the clinical approval process is able to filter out medications whose utility does not offset their adverse drug reaction profile in humans, it is not well suited to characterizing lower frequency issues and idiosyncratic multi-drug interactions that can happen in real world diverse patient populations. With a growing abundance of real-world evidence databases containing hundreds of thousands of patient records, it is now feasible to build machine learning models that incorporate individual patient information to provide personalized adverse event predictions. In this study, we build models that integrate patient specific demographic, clinical, and genetic features (when available) with drug structure to predict adverse drug reactions. We develop an extensible graph convolutional approach to be able to integrate molecular effects from the variable number of medications a typical patient may be taking. Our model outperforms standard machine learning methods at the tasks of predicting hospitalization and death in the UK Biobank dataset yielding an R2 of 0.37 and an AUC of 0.90, respectively. We believe our model has potential for evaluating new therapeutic compounds for individualized toxicities in real world diverse populations. It can also be used to prioritize medications when there are multiple options being considered for treatment.

Enhanced uranium removal from acidic wastewater by phosphonate-functionalized ordered mesoporous silica: Surface chemistry matters the most.

The removal of uranium species from aqueous phases using non-hazardous chemicals is still an open challenge, and remediation by adsorption is a prosperous strategy. Among the most crucial concerns regarding the design of an efficient material as adsorbent are, except the cost and the green character, the feasibility to be stable and effective under acidic pH, and to selectively adsorb the desired metal ion (e.g. uranium). Herein, we present a phosphonate functionalized ordered mesoporous silica (OMS-P), prepared by a one-step co-condensation synthesis. The physicochemical features of the material were determined by HR-TEM, XPS, EDX, N2 sorption, and solid NMR, while the surface zeta potential was also measured. The removal efficiency was evaluated at two different temperatures (20 and 50 °C) in acidic environment to avoid interferences like solid phase formation or carbonate complexation and the adsorption isotherms, including data fitting with Langmuir and Freundlich models and thermodynamic parameters are presented and discussed. The high and homogeneous dispersion of the phosphonate groups within the entire silica's structure led to the greatest reported up-todays capacity (345 mg/g) at pH = 4, which was achieved in less than 10 min. Additionally, OMS-P showed that the co-presence of other polyvalent cation like Eu(III) did not affect the efficiency of adsorption, which occurs via inner-sphere complex formation. The comparison to the non-functionalized silica (OMS) revealed that the key feature towards an efficient, stable, and selective removal of the U(VI) species is the specific surface chemistry rather than the textural and structural features. Based on all the results and spectroscopic validations of surface adsorbed U(VI), the main interactions responsible for the elevated uranium removal were proposed.

Enhancing cadmium extraction potential of Brassica napus: Effect of rhizosphere interactions.

Brassica napus L. (oilseed rape) was grown with daikon and white lupin in a polyvinyl chloride split pot experiment (with no barrier between the compartments or by a nylon mesh barrier (37 µm) to license partial root interaction, or a solid barrier to stop any root interactions) to examine the effect of rhizosphere interaction on the cadmium uptake. The results showed that shoot and root biomasses of oilseed rape were 40.66% and 26.94% less than that of the monocropped treatment (solid barrier) when intercropping with daikon under the rhizosphere complete interaction. However, the intermingling of roots between oilseed rape and white lupin notably enhanced the dry biomass of oilseed rape by 40.23% and decreased with the reduction of root contact. Oilseed rape intercropping with daikon enhanced the shoot Cd concentration of oilseed rape. The shoot Cd concentration (44.8 mg/kg) of oilseed rape when intercropped white lupin under complete rhizosphere interaction were greater than those of other treatments. Additionally, the intermingling of roots played a positive role in the content of citric and malic acids when intercropping with white lupin. In all systems, the BCF values of oilseed rape >5. Therefore, intercropping with white lupin may contribute to higher biomass and increased uptake Cd by oilseed rape. We can toward sustainable positive effects on phytoremediation that based on a better understanding of rhizosphere processes.

Single-use surgical face masks, as a potential source of microplastics: Do they act as pollutant carriers?

Millions of people are using face coverings (including single-use surgical face masks) as a result of the COVID-19 pandemic and a large number of used masks, particularly single-use masks enter uncontrolled the environment since most of the users have little information on how to dispose of them safely. This new important waste is a potential source of microplastics, which is found nowadays in many parks, streets, and coastlines. Discarded masks will be finally drained to the ocean polluting the marine environment and threatening marine life. This short communication examines the role of face masks and subsequently mask-derived microplastics as pollutant carriers in environmental compartments (e.g. hydrosphere, biosphere, etc.) by investigating their sorption characteristics regarding dye molecules. In this context, batch-type equilibrium experiments were performed and the effect of different sorption parameters has been explored (i.e. contact time and temperature). The results show that single-use surgical face masks can act as dye carriers (Methylene Blue, Crystal Violet and Malachite Green) in the aquatic environment. In addition, preliminary experiments on the thermal treatment of face masks and the use of the resulting carbonaceous material as efficient adsorbent have been performed, pointing out a possibility for used mask disinfection and recycling.

A nappies management by-product for the treatment of uranium-contaminated waters.

The direct disposal of municipal solid waste such as nappies to the environment may create serious pollution problems. Based on the circular economy and waste management concepts, the conversion of nappies and/or their ingredients (such as super absorbent polymer (SAP)) to high added value products is of great importance. In this work, a modified SAP (MSAP) was examined as an adsorbent for treatment of contaminated waters and uranium recovery. Batch experiments and spectroscopic techniques were used to examine the effect of various parameters (pH, contact time, temperature, initial concentration, and ionic strength), and the mechanism of adsorption U(VI) and desorption process. The U(VI) concentration was determined by alpha spectroscopy after addition of 232U standard tracer solution to account for possible interferences during electrodeposition and alpha particle counting. The maximum adsorption monolayer capacity was found to be 217.4 mg/g at pH 4.0 and at 298 K. The adsorption of U(VI) on MSAP seems to occur mainly via the formation of inner-sphere surface complexes between U(VI) and the carboxylic surface moieties of MSAP. The MSAP could satisfactorily be regenerated with 0.1 M Na2CO3 (>90%) and it also shows a promising applicability to real wastewaters contaminated with U(VI).