Assessing the role of the graphene family nanomaterials (GFNs: Graphene, GO, rGO) in modifying the toxicity potential and environmental risk of flame retardant, tetrabromobisphenol-A (TBBPA) in the marine microalgae Chlorella sp.

In recent years, a growing concern has emerged regarding the environmental implications of flame retardants (FRs) like tetrabromobisphenol-A (TBBPA) and graphene family nanomaterials (GFNs), such as graphene, graphene oxide (GO), and reduced graphene oxide (rGO), on marine biota. Despite these substances' well-established individual toxicity profiles, there is a notable gap in understanding the physicochemical interactions within the binary mixtures and consequent changes in the toxicity potential. Therefore, our research focuses on elucidating the individual and combined toxicological impacts of TBBPA and GFNs on the marine alga Chlorella sp. Employing a suite of experimental methodologies, including Raman spectroscopy, contact angle measurements, electron microscopy, and chromatography, we examined the physicochemical interplay between the GFNs and TBBPA. The toxicity potentials of individual constituents and their binary combinations were assessed through growth inhibition assays, quantifying reactive oxygen species (ROS) generation and malondialdehyde (MDA) production, photosynthetic activity analyses, and various biochemical assays. The toxicity of TBBPA and graphene-based nanomaterials (GFNs) was examined individually and in combinations. Both pristine TBBPA and GFNs showed dose-dependent toxicity. While lower TBBPA concentrations exacerbated toxicity in binary mixtures, higher TBBPA levels reduced the toxic effects compared to pristine TBBPA treatments. The principal mechanism underlying toxicity was ROS generation, resulting in membrane damage and perturbation of photosynthetic parameters. Cluster heatmap and Pearson correlation were employed to assess correlations between the biological parameters. Finally, ecological risk assessment was undertaken to evaluate environmental impacts of the individual components and the mixture in the algae.

EPS-corona formation on graphene family nanomaterials (GO, rGO and graphene) and its role in mitigating their toxic effects in the marine alga Chlorella sp.

GFNs have widespread applications but can harm marine systems due to excessive use and improper disposal. Algae-secreted EPS can mitigate nanomaterial harm, but their impact on GFN toxicity is understudied. Hence, in the present study, we investigated the toxicity of three GFNs, graphene oxide (GO), reduced graphene oxide (rGO), and graphene, in pristine and EPS-adsorbed forms in the marine alga Chlorella sp. At an environmentally relevant concentration of 1 mgL-1, all three GFNs induced considerable oxidative stress and impeded growth and photosynthetic activity of the algae. The order of the toxic potential followed GO > rGO > graphene. The various facets of adsorption of EPS (1:1 mixture of loosely bound, and tightly bound EPS) on GFNs were investigated through microscopy, surface chemical analyses, fluorescence quenching studies, and isotherm and kinetics studies. Amongst the pristine GFNs treated with algal cells, GO was found to exert the maximum negative effects on algal growth. Upon adsorption of EPS over the GFNs, a significant decline in growth inhibition was observed compared to the respective pristine forms which strongly correlated with reduced oxidative stress and enhanced photosynthetic parameters in the cells. The formation of a layer of eco-corona after interaction of GFNs with EPS possibly caused a barrier effect which in turn diminished their toxic potential. The findings from the present investigation offer valuable insights into the environmental toxicity of GFNs and show that the eco-corona formation may lessen the risk posed by these materials in the marine environment.

Investigating the transport and colloidal behavior of Fe3O4 nanoparticles in aqueous and porous media under varying solution chemistry parameters.

The possible adverse effects of engineered iron oxide nanoparticles, especially magnetite (Fe3O4 NP), on human health and the environment, have raised concerns about their transport and behavior in soil and water systems. Accumulating these NPs in the environment can substantially affect soil and water quality and the well-being of aquatic and terrestrial organisms. Therefore, it is essential to examine the factors that affect Fe3O4 NP transportation and behavior in soil and water systems to determine their possible environmental fate. In this work, experiments were conducted in aqueous and porous media using an environmentally relevant range of pH (5, 7, 9), ionic strength (IS) (10, 50, 100 mM), and humic acid (HA) (0.1, 1, 10 mg L-1) concentrations. Fe3O4 NPs exhibited severe colloidal instability at pH 7 (⁓ = pHPZC) and showed an improvement in apparent colloidal stability at pH 5 and 9 in aquatic and terrestrial environments. HA in the background solutions promoted the overall transport of Fe3O4 NPs by enhancing the colloidal stability. The increased ionic strength in aqueous media hindered the transport by electron double-layer compression and electrostatic repulsion; however, in porous media, the transport was hindered by ionic compression. Furthermore, the transport behavior of Fe3O4 NPs was investigated in different natural waters such as rivers, lakes, taps, and groundwater. The interaction energy pattern in aquatic systems was estimated using the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. This study showed the effects of various physical-chemical conditions on Fe3O4 NP transport in aqueous and porous (sand) media.

Sulfate Radical-Based Degradation of Organic Pollutants: A Review on Application of Metal-Organic Frameworks as Catalysts.

The degradation of organic pollutants present in domestic and industrial effluents is a matter of concern because of their high persistence and ecotoxicity. Recently, advanced oxidation processes (AOPs) are being emphasized for organic pollutant removal from effluents, as they have shown higher degradation efficiencies when compared to conventional activated sludge processes. Sulfate radical-based methods are some of the AOPs, mainly carried out using persulfate (PS) and peroxymonosulfate (PMS), which have gained attention due to the ease of sulfate radical generation and the effective degradation of organic molecules. PMS is gaining more popularity because of its high reactivity and ability to generate excess sulfate radicals. PMS has been the major focus; therefore, its mechanism has been explained, and limitations have been elaborated. The involvement of metal-organic frameworks for PMS/PS activation applied to organic pollutant removal and recent advances in the application of biochar and hydrogel-assisted metal-organic frameworks have been discussed.

Comparative toxicity assessment of individual, binary and ternary mixtures of SiO2, Fe3O4, and ZnO nanoparticles in freshwater microalgae, Scenedesmus obliquus: Exploring the role of dissolved ions.

Metal oxide nanoparticles (NPs) are considered among the most prevalent engineered nanomaterials. To have a deeper understanding of the mode of action of multiple metal oxide nanoparticles in mixtures, we have used a unicellular freshwater microalga Scenedesmus obliquus as a model organism. The toxicity of silicon dioxide (SiO2), iron oxide (Fe3O4), and zinc oxide (ZnO) NPs was studied individually as well as in their binary (SiO2 + Fe3O4, Fe3O4 + ZnO, and ZnO + SiO2) and ternary (SiO2 + Fe3O4 + ZnO) combinations. The effects of metal ions from ZnO and Fe3O4 were investigated as well. The results observed from the study, showed that a significant amount of toxicity was contributed by the dissolved ions in the mixtures of the nanoparticles. Decreases in the cell viability, ROS generation, lipid peroxidation, antioxidant enzyme activity, and photosynthetic efficiency were analyzed. Among all the individual particles, ZnO NPs showed the maximum effects and increased the toxicities of the binary mixtures. The binary and ternary mixtures of the NPs clearly showed increased toxic effects in comparison with the individual entities. However, the ternary combination had lesser toxic effects than the binary combination of Fe3O4 + ZnO. The decline in cell viability and photosynthetic efficiency were strongly correlated with various oxidative stress biomarkers emphasizing the crucial role of reactive oxygen species in inducing the toxic effects. The findings from this study highlight the importance of evaluating the combinatorial effects of various metal oxide NPs as part of a comprehensive ecotoxicity assessment in freshwater microalgae.

Phthalate esters: occurrence, toxicity, bioremediation, and advanced oxidation processes.

Phthalic acid esters are emerging pollutants, commonly used as plasticizers that are categorized as hazardous endocrine-disrupting chemicals (EDCs). A rise in anthropogenic activities leads to an increase in phthalate concentration in the environment which leads to various adverse environmental effects and health issues in humans and other aquatic organisms. This paper gives an overview of the research related to phthalate ester contamination and degradation methods by conducting a bibliometric analysis with VOS Viewer. Ecotoxicity analysis requires an understanding of the current status of phthalate pollution, health impacts, exposure routes, and their sources. This review covers five toxic phthalates, occurrences in the aquatic environment, toxicity studies, biodegradation studies, and degradation pathways. It highlights the various advanced oxidation processes like photocatalysis, Fenton processes, ozonation, sonolysis, and modified AOPs used for phthalate removal from the environment.

Comparative ecotoxicity of graphene, functionalized multi-walled CNTs, and their mixture in freshwater microalgae, Scenedesmus obliquus: analyzing the role of oxidative stress.

Due to their remarkable properties, the applications of carbon-based nanomaterials (CNMs) such as graphene and functionalized multi-walled carbon nanotubes (f-MWCNTs) are increasing. These CNMs can enter the freshwater environment via numerous routes, potentially exposing various organisms. The current study assesses the effects of graphene, f-MWCNTs, and their binary mixture on the freshwater algal species Scenedesmus obliquus. The concentration for the individual materials was kept at 1 mg L-1, while graphene and f-MWCNTs were taken at 0.5 mg L-1 each for the combination. Both the CNMs caused a decrease in cell viability, esterase activity, and photosynthetic efficiency in the cells. The cytotoxic effects were accompanied by increased hydroxyl and superoxide radical generation, lipid peroxidation, antioxidant enzyme activity (catalase and superoxide dismutase), and mitochondrial membrane potential. Graphene was more toxic compared to f-MWCNTs. The binary mixture of the pollutants demonstrated a synergistic enhancement of the toxic potential. Oxidative stress generation played a critical role in toxicity responses, as noted by a strong correlation between the physiological parameters and the biomarkers of oxidative stress. The outcomes from this study emphasize the significance of considering the combined effects of various CNMs as part of a thorough evaluation of ecotoxicity in freshwater organisms.

Nano-SiO2 transport and retention in saturated porous medium: Influence of pH, ionic strength, and natural organics.

Nano silica (nSiO2), induces potential harmful effects on the living environment and human health. It is well established that SiO2 facilitates the co-transport of a variety of other contaminants, including heavy metals and pesticides. The current study focused on the systematic evaluation of the effects of multiple physicochemical parameters such as pH (5, 7, and 9), ionic strength (10, 50, and 100 mM), and humic acid (0.1, 1, and 10 mg/L) on the transport and retention of nSiO2 in saturated porous medium. Additionally, the influent concentration of nSiO2 (10, 50, and 100 mg/L) was also varied. Our experimental findings indicate that the size of nSiO2 aggregates was directly related to the pH, ionic strength, HA, and particle concentration had a significant impact on the breakthrough curves (BTCs). The stability provided by the varying concentrations of pH and humic acid had a significant effect on the size of nSiO2 aggregates and transport (C/C0 > 0.7). The presence of a greater magnitude of negative charge on the surface of both nSiO2 and quartz sand resulted in less aggregation and enhanced flow of nSiO2 through the sand column. The Electrostatic and steric repulsion forces were the primary governing mechanisms in relation to the size of nSiO2 aggregates, affecting the single-collector efficiency and attachment efficiency, which determined the maximal transport of nSiO2. Conversely, a probable increase in Van der Waals force of attraction exacerbated the particle deposition and reduced their mobility for high ionic strength, and particle concentrations (C/C0 < 0.1). The formation of large nSiO2 aggregates, in particular, was principally responsible for the enhancement of nSiO2 retention in sand columns over a broad range of IS and particle concentration. The interaction energy profiles based on the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory were determined to understand the mechanism of nSiO2 deposition. Aditionally, all the experimental BTCs were mathematically simulated and justified by the colloidal filtration theory (CFT). Considering the environmental ramifications, the transport behavior of nSiO2 was further evaluated in various natural matrices such as river, lake, ground, and tap water. The nSiO2 suspended in the river, lake, and tap water had significantly higher mobility (C/C0 > 0.7), whereas groundwater indicated higher retention (C/C0 < 0.3). The study advances our collective knowledge of physicochemical and environmental parameters that can affect particle mobility.

A comprehensive estimate of the aggregation and transport of nSiO2 in static and dynamic aqueous systems.

Silicon dioxide nanoparticles (nSiO2) are extensively used in diverse fields and are inevitably released into the natural environment. Their overall aggregation behaviour in the environmental matrix can determine their fate and ecotoxicological effect on terrestrial and aquatic life. The current study systematically evaluates multiple parameters that can influence the stability of colloidal nSiO2 (47 nm) in the natural aquatic environment. At first, the influence of several hydrochemical parameters such as pH (5, 7, and 9), ionic strength (IS) (10, 50, and 100 mM), and humic acid (HA) (0.1, 1, and 10 mg L-1) was examined to understand the overall aggregation process of nSiO2. Furthermore, the synergistic and antagonistic effects of ionic strength and humic acid on the transport of nSiO2 in the aqueous environment were examined. Our experimental findings indicate that pH, ionic strength, and humic acid all had a profound influence on the sedimentation process of nSiO2. The experimental observations were corroborated by calculating the DLVO interaction energy profile, which was shown to be congruent with the transport patterns. The present study also highlights the influence of high and low shear forces on the sedimentation process of nSiO2 in the aqueous medium. The presence of shear force altered the collision efficiency and other interactive forces between the nanoparticles in the colloidal suspension. Under the experimental stirring conditions, a higher abundance of dispersed nSiO2 in the upper layer of the aqueous medium was noted. Additionally, the transport behaviour of nSiO2 was studied in a variety of natural water systems, including rivers, lakes, ground, and tap water. The study significantly contributes to our understanding of the different physical, chemical, and environmental aspects that can critically impact the sedimentation and spatial distribution of nSiO2 in static and dynamic aquatic ecosystems.

Development of biogenic bimetallic Pd/Fe nanoparticle-impregnated aerobic microbial granules with potential for dye removal.

The objective of this study was to develop bimetallic core-shell Pd/Fe nanoparticles on the surface of aerobic microbial granules (Bio-Pd/Fe) and to evaluate their dye removal potential using a representative dye, methyl orange (MO). The aerobic microbial granules (1.5 ± 0.32 mm) were grown for 70 days in a 3-L glass sequencing batch reactor (SBR) with a 12-h cycle time. The Bio-Pd/Fe formation was catalyzed by the Bio-H2 gas produced by the granules. The developed Bio-Pd/Fe was further used for MO removal from aqueous solutions, and the reaction parameters were optimized by response surface methodology (RSM). The XRD, SEM, EDAX, elemental mapping, and XPS studies confirmed the formation of Bio-Pd/Fe. Under the optimized removal conditions, 99.33% MO could be removed by Bio-Pd/Fe, whereas removal by Bio-Pd, Bio-Fe, aerobic microbial granules, and heat-killed granules were found to be quite low (68.91 ± 0.2%, 76.8 ± 0.3%, 19.8 ± 0.6%, and 6.59 ± 0.2%, respectively). The mechanism of removal was investigated by UV-visible spectroscopy, redox potential analysis, HR-LCMS analyses of the solution phase, and XRD and XPS analyses of the solid sorbent. The degradation products of MO exhibited m/z values corresponding to 292, 212, and 160 m/z. The remnant toxicity of the intermediate degradation products was analysed using freshwater algae, Scenedesmus sp. And Allium cepa, as indicator organisms. These assays suggested that after the treatment with Bio-Pd/Fe, MO was transformed to a lesser toxic form.

Modulatory effects of Zn2+ ions on the toxicity of citrate- and PVP-capped gold nanoparticles towards freshwater algae, Scenedesmus obliquus.

Gold nanoparticles (GNPs) are widely used for medical purposes, both in diagnostics as well as drug delivery, and hence are prone to release and distribution in the environment. Thus, we have explored the effects of GNPs with two distinct surface capping (citrate and PVP), and three different sizes (16, 27, and 37 nm) at 0.01-, 0.1-, and 1-mg L-1 concentrations on a predominant freshwater alga Scenedesmus obliquus in the sterile freshwater matrix. We have also investigated how an abundant metal ion from freshwater, i.e., Zn2+ ions may modulate the effects of the selected GNPs (40 nm, citrate, and PVP capped). Preliminary toxicity results revealed that gold nanoparticles were highly toxic in comparison to zinc ions alone. A significant modulation in the toxicity of Zn ions was not noticed in the presence of GNPs. In contrast, zinc ions minimized the toxicity produced by GNPs (both CIT-37 and PVP-37), despite its individual toxicity. Approximately, about 42, 33, and 25% toxicity reduction was noted at 0.05-, 0.5-, and 5-mg L-1 Zn ions, respectively, for CIT-37 GNPs, while 31% (0.05 mg L-1), 24% (0.5 mg L-1), and 9% (5 mg L-1) of toxicity reduction were noted for PVP-37 GNPs. Maximum toxicity reduction was seen at 0.05 mg L-1 of Zn ions. Abbott modeling substantiated antagonistic effects offered by Zn2+ ions on GNPs. Stability and sedimentation data revealed that the addition of zinc ions gradually induced the aggregation of NPs and in turn significantly reduced the toxicity of GNPs. Thus, the naturally existing ions like Zn2+ have an ability to modulate the toxicity of GNPs in a real-world environment scenario.

Individual and Co Transport Study of Titanium Dioxide NPs and Zinc Oxide NPs in Porous Media.

The impact of pH and ionic strength on the mobility (individual and co-transport) and deposition kinetics of TiO2 and ZnO NPs in porous media was systematically investigated in this study. Packed column experiments were performed over a series of environmentally relevant ionic strengths with both NaCl (0.1-10 mM) and CaCl2 (0.01-0.1mM) solutions and at pH 5, 7, and 9. The transport of TiO2 NPs at pH 5 was not significantly affected by ZnO NPs in solution. At pH 7, a decrease in TiO2 NP transport was noted with co-existence of ZnO NPs, while at pH 9 an increase in the transport was observed. At pH 5 and 7, the transport of ZnO NPs was decreased when TiO2 NPs was present in the solution, and at pH 9, an increase was noted. The breakthrough curves (BTC) were noted to be sensitive to the solution chemistries; the decrease in the breakthrough plateau with increasing ionic strength was observed under all examined pH (5, 7, and 9). The retention profiles were the inverse of the plateaus of BTCs, as expected from mass balance considerations. Overall, the results from this study suggest that solution chemistries (ionic strength and pH) are likely the key factors that govern the individual and co-transport behavior of TiO2 and ZnO NPs in sand.

Cytotoxicity of TiO2 nanoparticles towards freshwater sediment microorganisms at low exposure concentrations.

There is a persistent need to assess the effects of TiO2 nanoparticles on the aquatic ecosystem owing to their increasing usage in consumer products and risk of environmental release. The current study is focused on TiO2 nanoparticle-induced acute toxicity at sub-ppm level (≤1ppm) on the three different freshwater sediment bacterial isolates and their consortium under two different irradiation (visible light and dark) conditions. The consortium of the bacterial isolates was found to be less affected by the exposure to the nanoparticles compared to the individual cells. The oxidative stress contributed considerably towards the cytotoxicity under both light and dark conditions. A statistically significant increase in membrane permeability was noted under the dark conditions as compared to the light conditions. The optical and fluorescence microscopic images showed aggregation and chain formation of the bacterial cells, when exposed to the nanoparticles. The electron microscopic (SEM, TEM) observations suggested considerable damage of cells and bio-uptake of nanoparticles. The exopolysaccrides (EPS) production and biofilm formation were noted to increase in the presence of the nanoparticles, and expression of the key genes involved in biofilm formation was studied by RT-PCR.

Batch and continuous flow studies of adsorptive removal of Cr(VI) by adapted bacterial consortia immobilized in alginate beads.

The adsorptive removal of Cr(VI) by alginate beads containing Cr(VI)-adapted Acinetobacter junii, Escherichia coli and Bacillus subtilis in batch and continuous packed bed column reactors was investigated. Under optimized conditions (pH 3.0; contact time, 180 min; 30 °C; initial Cr(VI) concentration of 100 mg/L), 65.86 mg/g adsorption capacity was recorded in the batch study. When an adsorbent dosage of 1g/L, a flow rate of 5 mL/min, a bed height of 20 cm, an initial Cr(VI) concentration of 300 mg/L was employed, a capacity of 657 mg/g was noted for the continuous column assay. The batch sorption data followed the Langmuir isotherm and pseudo second order kinetics. Five sorption/desorption cycles yielded 100%, 99.63%, 95.31%, 80.7% and 74.22% regeneration, respectively. Cr(VI) adsorption studies using spiked ground water, freshwater and domestic wastewater in a packed bed reactor demonstrated Cr(VI) removals of 64.8%, 55.08%, 56.86% respectively. Cr(VI) sorption on immobilized bacteria was confirmed with Fourier-transform infrared and Energy dispersive X-ray spectroscopy.

Enhancing the hexavalent chromium bioremediation potential of Acinetobacter junii VITSUKMW2 using statistical design experiments.

The Cr(VI) removal capability of Acinetobacter junii VITSUKMW2 isolated from the Sukinda chromite mine site was evaluated and enhanced using statistical design techniques. The removal capacity was evaluated at different pH values (5-11) and temperatures (30-40 degrees C) and with various carbon and nitrogen sources. Plackett- Burman design was used to select the operational parameters for bioremediation of Cr(VI). Three parameters (molasses, yeast extract, and Cr(VI) concentration) were chosen for further optimization using central composite design. The optimal combination of parameters was found to be 14.85 g/l molasses, 4.72 g/l yeast extract, and 54 mg/l initial Cr(VI), with 99.95% removal of Cr(VI) in 12 h. A. junii VITSUKMW2 was shown to have significant potential for removal of Cr(VI).

Potential drug targets in Mycobacterium tuberculosis through metabolic pathway analysis.

The emergence of multidrug resistant varieties of Mycobacterium tuberculosis has led to a search for novel drug targets. We have performed an insilico comparative analysis of metabolic pathways of the host Homo sapiens and the pathogen M. tuberculosis. Enzymes from the biochemical pathways of M. tuberculosis from the KEGG metabolic pathway database were compared with proteins from the host H. sapiens, by performing a BLASTp search against the non-redundant database restricted to the H. sapiens subset. The e-value threshold cutoff was set to 0.005. Enzymes, which do not show similarity to any of the host proteins, below this threshold, were filtered out as potential drug targets. We have identified six pathways unique to the pathogen M. tuberculosis when compared to the host H. sapiens. Potential drug targets from these pathways could be useful for the discovery of broad spectrum drugs. Potential drug targets were also identified from pathways related to lipid metabolism, carbohydrate metabolism, amino acid metabolism, energy metabolism, vitamin and cofactor biosynthetic pathways and nucleotide metabolism. Of the 185 distinct targets identified from these pathways, many are in various stages of progress at the TB Structural Genomics Consortium. However, 67 of our targets are new and can be considered for rational drug design. As a case study, we have built a homology model of one of the potential drug targets MurD ligase using WHAT IF software. The model could be further explored for insilico docking studies with suitable inhibitors. The study was successful in listing out potential drug targets from the M. tuberculosis proteome involved in vital aspects of the pathogen's metabolism, persistence, virulence and cell wall biosynthesis. This systematic evaluation of metabolic pathways of host and pathogen through reliable and conventional bioinformatic methods can be extended to other pathogens of clinical interest.