A Novel Sustainable Process for Multilayer Graphene Synthesis Using CO2 from Ambient Air.

Graphene produced by different methods can present varying physicochemical properties and quality, resulting in a wide range of applications. The implementation of a novel method to synthesize graphene requires characterizations to determine the relevant physicochemical and functional properties for its tailored application. We present a novel method for multilayer graphene synthesis using atmospheric carbon dioxide with characterization. Synthesis begins with carbon dioxide sequestered from air by monoethanolamine dissolution and released into an enclosed vessel. Magnesium is ignited in the presence of the concentrated carbon dioxide, resulting in the formation of graphene flakes. These flakes are separated and enhanced by washing with hydrochloric acid and exfoliation by ammonium sulfate, which is then cycled through a tumble blender and filtrated. Raman spectroscopic characterization, FTIR spectroscopic characterization, XPS spectroscopic characterization, SEM imaging, and TEM imaging indicated that the graphene has fifteen layers with some remnant oxygen-possessing and nitrogen-possessing functional groups. The multilayer graphene flake possessed particle sizes ranging from 2 µm to 80 µm in diameter. BET analysis measured the surface area of the multilayer graphene particles as 330 m2/g, and the pore size distribution indicated about 51% of the pores as having diameters from 0.8 nm to 5 nm. This study demonstrates a novel and scalable method to synthesize multilayer graphene using CO2 from ambient air at 1 g/kWh electricity, potentially allowing for multilayer graphene production by the ton. The approach creates opportunities to synthesize multilayer graphene particles with defined properties through a careful control of the synthesis parameters for tailored applications.

Microplastics with adsorbed contaminants: Mechanisms and Treatment.

Plastic pollution has been a significant and widespread global issue, and the recent COVID-19 pandemic has been attributed to its worsening effect as plastics have been contaminated with the deadly infectious virus. Microplastics (MPs) may have played a role as a vector that carries hazardous microbes such as emerging bacterial threats (i.e. antibiotic resistant bacteria) and deadly viruses (e.g., coronavirus); this causes great concern over microplastics contaminated with emerging contaminants. Mitigation and treatment of MPs are challenging because of a range of factors including but not limited to physicochemical properties and composition of MPs and pH and salinity of the solution. Despite the heterogeneous nature of aquatic systems, research has overlooked interactions between contaminants and MPs under environmental conditions, degradation pathways of MPs with adsorbed contaminants, and, especially, the role of adsorbed contaminants in the efficiency of MP treatment through membrane filtration, in comparison with other treatment methods. This review aims to (1) analyze an assortment of factors that could influence the removal of MPs and mechanisms of contaminant adsorption on MPs, (2) identify mechanisms influencing membrane filtration of MPs, (3) examine the fate and transport of MPs with adsorbed contaminants, (4) evaluate membrane filtration of contaminant-adsorbing MPs in comparison to other treatment methods, and (5) draw conclusions and the future outlook based on a literature analysis.

Field grand challenge with emerging superbugs and the novel coronavirus (SARS-CoV-2) on plastics and in water.

This opinion paper reports field grand challenges associated with plastic and water contaminated with the novel coronavirus (severe acute respiratory syndrome coronavirus 2, SARS-CoV-2) and superbugs, given the emergency of public health and environmental protection from the presence of lethal viruses and bacteria. Two primary focuses of detection and treatment methods for superbugs and the novel coronavirus (SARS-CoV-2) are investigated, and the future outlook is provided based on grand challenges identified in the water field. Applying conventional treatment technologies to treat superbugs or the novel coronavirus (SARS-CoV-2) has brought negative results, including ineffective treatment, formation of toxic byproducts, and limitation of long-term performance. Existing detection methods are not feasible to apply in terms of sensitivity, difficulty of applications in field samples, speed, and accuracy at the time of sample collection. Few studies are found on superbugs or adsorption of the novel coronavirus (SARS-CoV-2) on plastic, as well as effects of superbugs or the novel coronavirus (SARS-CoV-2) on treatment of plastic waste and wastewater. With the need for and directions of further research and challenges discussed in this paper, we believe that this opinion paper offers information useful to a wide audience, including scientists, policy makers, consultants, public health workers, and field engineers in the water sector.

Toxicity of ZnO/TiO2 -conjugated carbon-based nanohybrids on the coastal marine alga Thalassiosira pseudonana.

Increasing consumption of metal-oxide nanoparticles (NPs) and carbon-based nanomaterials has caused significant concern about their potential hazards in aquatic environments. The release of NPs into aquatic environments could result in adsorption of NPs on microorganisms. While metal-oxide NP-conjugated carbon-based nanohybrids (NHs) may exhibit enhanced toxicity toward microorganisms due to their large surface area and the generation of reactive oxygen species (ROS), there is a lack of information regarding the ecotoxicological effects of NHs on marine diatom algae, which are an indicator of marine pollution. Moreover, there is scant information on toxicity mechanisms of NHs on aquatic organisms. In this study, four NHs (ie, ZnO-conjugated graphene oxide [GO], ZnO-conjugated carbon nanotubes [CNTs], TiO2 -conjugated GO, and TiO2 -conjugated CNT) that were synthesized by a hydrothermal method were investigated for their toxicity effects on a Thalassiosira pseudonana marine diatom. The in vitro cellular viability and ROS formation employed at the concentration ranges of 50 and 100 mg/L of NHs over 72 hours revealed that ZnO-GO had the most negative effect on T. pseudonana. The primary mechanism identified was the generation of ROS and GO-induced dispersion that caused electrostatic repulsion, preventing aggregation, and an increase in surface areas of NHs. In contrast to GO-induced dispersion, large aggregates were observed in ZnO/TiO2 -conjugated CNT-based NHs. The scanning electron microscopy images suggest that NHs covered algae cells and interacted with them (shading effects); this reduced light availability for photosynthesis. Detailed in vitro toxicity effects and mechanisms that cause high adverse acute toxicity on T. pseudonana were unveiled; this implied concerns about potential hazards of these mechanisms in aquatic ecosystems.

Antibacterial effects of graphene- and carbon-nanotube-based nanohybrids on Escherichia coli: Implications for treating multidrug-resistant bacteria.

Some nanomaterials including Fe0, Ag0, and ZnO are well known for their antibacterial effects. However, very few studies have examined antibacterial effects of nanohybrids. Given that metal oxides, mainly ZnO and TiO2, are known to increase mobility, surface area, and photocatalysis when combined with carbon-based nanomaterials, ZnO- and TiO2-conjugated carbon nanotube and graphene oxide nanohybrids were investigated for their antibacterial effects on Escherichia coli (DH5α, a multidrug-resistant coliform bacterium). Graphene-oxide (GO)-based nanohybrids (ZnO-GO and TiO2-GO) induced increased dispersion compared to carbon-nanotube (CNT)-based nanohybrids (ZnO-CNT and TiO2-CNT). Among the four types of nanohybrids, ZnO-conjugated nanohybrids exhibited a higher antibacterial property, resulting in the antibacterial effect (measured with growth inhibition of cells) in the order ZnO-GO > ZnO-CNT > TiO2-GO > TiO2-CNT. Among four possible antibacterial mechanisms (generation of reactive oxygen species (ROS), physicochemical characteristics, the steric effect, and release of metal ions), a primary mechanism-ROS generation-was identified; whereas, physicochemical characteristics and the steric effect were part of contributing mechanisms. The increasing dispersion of TiO2/ZnO on GO may have contributed to the antibacterial effects due to increasing surface areas. Similarly, significant damages to E. coli cell membranes were found by the GO sheet with its sharp edges. Our results suggest that applying GO-based ZnO or TiO2 could be an effective antibacterial method, especially for the treatment of multidrug-resistant bacteria in the water.

Treatment of antibiotic-resistant bacteria by encapsulation of ZnO nanoparticles in an alginate biopolymer: Insights into treatment mechanisms.

Treating multidrug-resistant bacteria has been a challenging task, although the bacteria have been reported as a trace contaminant present in tap water. Given emerging issues on antibiotic-resistant bacteria, the present study investigated a novel treatment method in which ZnO nanoparticles (NPs) are encapsulated in an alginate biopolymer solution to explore primary antibacterial mechanisms. The antibacterial effects of this technology on two model antibiotic-resistant bacteria (Escherichia coli DH5-α and Pseudomonas aeruginosa) were found to be highly effective, with the removal rates of 98% and 88%, respectively, at the initial bacteria concentration of 108 CFU mL-1 over 6 h. The inactivation of antibiotic-resistant bacteria by ZnO NP-alginate beads was improved by increasing the nanocomposite amount (4, 10, and 20 mg) and contact time. The primary mechanism involved the generation of reactive oxygen species (ROS). The ZnO NP-alginate beads were demonstrated to be highly promising for different applications in water treatment, especially for point-of-use in the perspectives of reusability, antibacterial property of ZnO, immobilizing NPs, and utilizing high surface area of NPs, with a slight release of zinc ions.

Factors impacting the interactions of engineered nanoparticles with bacterial cells and biofilms: Mechanistic insights and state of knowledge.

Since their advent a few decades ago, engineered nanoparticles (ENPs) have been extensively used in consumer products and industrial applications and their use is expected to continue at the rate of thousands of tons per year in the next decade. The widespread use of ENPs poses a potential risk of large scale environmental proliferation of ENPs which can impact and endanger environmental health and safety. Recent studies have shown that microbial biofilms can serve as an important biotic component for partitioning and perhaps storage of ENPs released into aqueous systems. Considering that biofilms can be one of the major sinks for ENPs in the environment, and that the field of biofilms itself is only three to four decades old, there is a recent and growing body of literature investigating the ENP-biofilm interactions. While looking at biofilms, it is imperative to consider the interactions of ENPs with the planktonic microbial cells inhabiting the bulk systems in the vicinity of surface-attached biofilms. In this review article, we attempt to establish the state of current knowledge regarding the interactions of ENPs with bacterial cells and biofilms, identifying key governing factors and interaction mechanisms, as well as prominent knowledge gaps. Since the context of ENP-biofilm interactions can be multifarious-ranging from ecological systems to water and wastewater treatment to dental/medically relevant biofilms- and includes devising novel strategies for biofilm control, we believe this review will serve an interdisciplinary audience. Finally, the article also touches upon the future directions that the research in the ENP-microbial cells/biofilm interactions could take. Continued research in this area is important to not only enhance our scientific knowledge and arsenal for biofilm control, but to also support environmental health while reaping the benefits of the 'nanomaterial revolution'.

Effects of coating materials on antibacterial properties of industrial and sunscreen-derived titanium-dioxide nanoparticles on Escherichia coli.

Organic or inorganic stabilizers are often used for coating nanoparticles (NPs) in consumer products. However, upon release of stabilized NPs into the environment, uncertainty exists as to the antimicrobial properties of NPs due to stabilizers and the resultant bioaccumulation in organisms. This study investigates antibacterial effects and subsequent mechanisms of TiO2 NPs on Escherichia coli (E. coli) in the presence and absence of stabilizers (CMC, PVP, and SiO2) commonly used in consumer products. Compared with uncoated TiO2 NPs, the presence of any stabilizers tested in this study increased toxicity of NPs and enhanced growth inhibition in E. coli. While the particle sizes of TiO2 were smaller as the result of coating with PVP or CMC and appeared to contribute to E. coli cell damage, the generation of reactive oxygen species (ROS) was independent of stabilizer type. In fact, coating with PVP and CMC exerted ROS scavenging properties. In contrast, increased ROS production was observed at higher concentrations of TiO2 and upon coating with SiO2. This impact of SiO2 can be related to the formation of a TiOSi chemical bond. The results of the present study emphasize the importance of nanoparticle coating to their anti-bacterial activity and toxicity.

Pilot-scale application of shotblast dust for phosphorus removal.

Phosphorus contamination is a global issue, and cost-effective remediation is sought for removing phosphorus from water. We applied a novel use of waste material called shotblast dust in a pilot-scale reactor to remove phosphorus from water. Results indicate that shotblast dust was effective in treating phosphorus-laden water with 132 kg of the material treating 568 liters of 220 µg/L total phosphorus (T-P) water on a daily basis, achieving approximately 60% removal of T-P in 7 days.

Environmental dynamics of metal oxide nanoparticles in heterogeneous systems: A review.

Metal oxide nanoparticles (MNPs) have been used for many purposes including water treatment, health, cosmetics, electronics, food packaging, and even food products. As their applications continue to expand, concerns have been mounting about the environmental fate and potential health risks of the nanoparticles in the environment. Based on the latest information, this review provides an overview of the factors that affect the fate, transformation and toxicity of MNPs. Emphasis is placed on the effects of various aquatic contaminants under various environmental conditions on the transformation of metal oxides and their transport kinetics - both in homogeneous and heterogeneous systems - and the effects of contaminants on the toxicity of MNPs. The presence of existing contaminants decreases bioavailability through hetero-aggregation, sorption, and/or complexation upon an interaction with MNPs. Contaminants also influence the fate and transport of MNPs and exhibit their synergistic toxic effects that contribute to the extent of the toxicity. This review will help regulators, engineers, and scientists in this field to understand the latest development on MNPs, their interactions with aquatic contaminants as well as the environmental dynamics of their fate and transformation. The knowledge gap and future research needs are also identified, and the challenges in assessing the environmental fate and transport of nanoparticles in heterogeneous systems are discussed.

Effects of titanium dioxide nanoparticles derived from consumer products on the marine diatom Thalassiosira pseudonana.

Increased manufacture of TiO2 nanoproducts has caused concern about the potential toxicity of these products to the environment and in public health. Identification and confirmation of the presence of TiO2 nanoparticles derived from consumer products as opposed to industrial TiO2 NPs warrant examination in exploring the significance of their release and resultant impacts on the environment. To this end, we examined the significance of the release of these particles and their toxic effect on the marine diatom algae Thalassiosira pseudonana. Our results indicate that nano-TiO2 sunscreen and toothpaste exhibit more toxicity in comparison to industrial TiO2 and inhibited the growth of the marine diatom T. pseudonana. This inhibition was proportional to the exposure time and concentrations of nano-TiO2. Our findings indicate a significant effect, and therefore, further research is warranted in evaluation and assessment of the toxicity of modified nano-TiO2 derived from consumer products and their physicochemical properties.

Influence of siloxane on the transport of ZnO nanoparticles from different release pathways in saturated sand.

The production of nanomaterials (NMs) is expected to grow continuously, yet their transformation, transport, release mechanisms, and interactions with contaminants under environmental conditions remain poorly understood. Few studies have investigated the effects of contaminants on fate and transport of NMs, especially siloxanes that are widely found in products. It is hypothesized that the model contaminant, siloxane (e.g., 1,1,3,3-tetramethyldisiloxane (TMDS)) may influence the mechanisms and transport kinetics of NMs under different release pathways. Sand column experiments were carried out under two different scenarios: the release from a mixed TMDS and nano-ZnO suspension (A) and the release of nano-ZnO from sand contaminated with TMDS (B). Results show that interparticle reactions are dominant in (A) and particle-porous interactions are responsible for blocking effects governing in (B). Insights, especially the kinetics of nano-ZnO from co-transport by a contaminant and from porous media preloaded with a contaminant, and environmental factors affecting the release and retention of nano-ZnO in saturated sand are unveiled. These two dominant transport mechanisms (e.g., interparticle reactions and blocking effects) were derived. This study indicates that the release of ZnO NPs is influenced by the presence of TMDS; the extent of mobility and their transport pathways depend on the pre-existence of TMDS in porous media.

Sustainable approaches for minimizing biosolids production and maximizing reuse options in sludge management: A review.

Sludge generation during wastewater treatment is inevitable even with proper management and treatment. Yet proper handling and disposal of sludge are still challenging in terms of treatment cost, presence of recalcitrant contaminants of concern, sanitary issues, and public acceptance. Conventional disposal methods (i.e. landfilling, incineration) have created concerns in terms of legislative restrictions and community perception, incentivizing consideration of substitute sludge management options. Furthermore, with proper treatment, biosolids from sludge, rich in organic materials and nutrients, could be utilizable as fertilizer. Despite the challenges of dealing with sludge, no review has dealt with integrated source reduction and reuse as the best sustainable management practices for sludge treatment. In this review, we present two main approaches as potentially sustainable controls: (i) pretreatment for minimizing extensive sludge treatment, and (ii) recycling and reuse of residual sludge. Drawing on these approaches, we also suggest strategies for efficient pretreatment mechanisms and residual reuse, presenting ideas for prospective future research.

Novel technologies for reverse osmosis concentrate treatment: a review.

Global water shortages due to droughts and population growth have created increasing interest in water reuse and recycling and, concomitantly, development of effective water treatment processes. Pressured membrane processes, in particular reverse osmosis, have been adopted in water treatment industries and utilities despite the relatively high operational cost and energy consumption. However, emerging contaminants are present in reverse osmosis concentrate in higher concentrations than in the feed water, and have created challenges for treatment of the concentrate. Further, standards and guidelines for assessment and treatment of newly identified contaminants are currently lacking. Research is needed regarding the treatment and disposal of emerging contaminants of concern in reverse osmosis concentrate, in order to develop cost-effective methods for minimizing potential impacts on public health and the environment. This paper reviews treatment options for concentrate from membrane processes. Barriers to emerging treatment options are discussed and novel treatment processes are evaluated based on a literature review.

Influence of carboxymethyl cellulose for the transport of titanium dioxide nanoparticles in clean silica and mineral-coated sands.

The transport properties of titanium dioxide (anatase polymorph) nanoparticles encapsulated by carboxymethyl cellulose (CMC) were evaluated as a function of changes in the solute chemical properties in clean quartz, amorphous aluminum, and iron hydroxide-coated sands. While pristine anatase TiO2 nanoparticles (ANTNPs) were completely immobile, the presence of CMC significantly enhanced their mobility. The magnitude of the surface charge exhibited by the CMC-coated anatase TiO2 nanoparticles (CMC-ANTNPs) significantly exceeded that of the uncoated ANTNPs, thereby leading to a negative surface charge over the pH range investigated (2-10). The mobility of CMC-ANTNPs was retarded by the presence of amorphous Fe and Al hydroxide, Na+ (30 mM), and Ca2+ (30 mM). Removal of CMC-ANTNPs was more significant in the presence of either Ca2+ or Fe-hydroxide. More retardation and incomplete breakthrough of the CMC-ANTNPs was observed in the mineral-coated sands. This is possibly due to an order of magnitude increase in the surface area of mineral-coated sands compared with the clean quartz sand grains and the potential for chelation between CMC bound to ANTNPs and Fe and Al hydroxides. Chemical-colloidal interactions such as chemicomplexation and ligand exchange were the most important factor controlling mobility of CMC-ANTNPs in mineral-coated sands.

Destruction of lindane and atrazine using stabilized iron nanoparticles under aerobic and anaerobic conditions: effects of catalyst and stabilizer.

Highly stable Fe-Pd bimetallic nanoparticles were prepared with 0.2% (w/w) of sodium carboxylmethylcellulose (CMC) as a stabilizer. The effectiveness of the stabilized Fe-Pd nanoparticles was studied for degradation of two chlorinated pesticides (lindane and atrazine) under aerobic and anaerobic conditions. Batch kinetic tests showed that under anaerobic condition the nanoparticles can serve as strong electron donors and completely reduce 1 mgl(-1) of lindane at an iron dose of 0.5 gl(-1) or 1mg l(-1) of atrazine with 0.05 gl(-1) iron with a trace amount (0.05-0.8% of Fe) of Pd as a catalyst. In contrast, under aerobic condition, the nanoparticles can facilitate Fenton-like reactions, which lead to oxidation of 65% of lindane under otherwise identical conditions. Under aerobic condition, the presence of CMC reduced the level of hydroxyl radicals generated from the nanoparticels by nearly 50%, and thus, inhibited the oxidation of the contaminants. While the particle stabilization greatly enhanced the anaerobic degradation, it did not appear to be beneficial under aerobic condition. The degradation rate was progressively enhanced as the Pd content increased from 0.05% to 0.8% of Fe, and the catalytic effect of Pd was more significant under anaerobic condition. Under anaerobic condition, lindane is degraded via dihaloelimination and dehydrohalogenation, whereas atrazine is by reductive dechlorination followed by subsequent reductive dealkylation. Under aerobic condition, reactive oxygen species and hydroxyl radicals from the iron nanoparticles are responsible for oxidizing the pesticides. Lindane is oxidized via dechlorination/dehydrohalogenation, whereas atrazine is destroyed through dealkylation of the alkylamino side chain.

Nitrile, aldehyde, and halonitroalkane formation during chlorination/chloramination of primary amines.

The decreasing availability of pristine water supplies is prompting drinking water utilities to exploit waters impacted by wastewater effluents and agricultural runoff. As these waters feature elevated organic nitrogen concentrations, the pathways responsible for transformation of organic nitrogen into toxic nitrogenous disinfection byproducts during chlorine and chloramine disinfection are of current concern. Partially degraded biomolecules likely constitute a significant fraction of organic nitrogen in these waters. As primary amines occur in important biomolecules, we investigated formation pathways for nitrile, aldehyde, and halonitroalkane byproducts during chlorination and chloramination of model primary amines. Chlorine and chloramines transformed primary amines to nitriles and aldehydes in significant yields overtime scales relevant to drinking water distribution systems. Yields of halonitroalkanes were less significant yet may be important because of the high toxicity associated with these compounds. Our results indicate that chloramination should reduce nitrile concentrations compared to chlorination but may increase the formation of aldehydes and halonitroalkanes at high oxidant doses.

Quantification of the oxidizing capacity of nanoparticulate zero-valent iron.

Addition of nanoparticulate zero-valent iron (nZVI) to oxygen-containing water results in oxidation of organic compounds. To assess the potential application of nZVI for oxidative transformation of organic contaminants, the conversion of benzoic acid (BA) to p-hydroxybenzoic acid (p-HBA) was used as a probe reaction. When nZVI was added to BA-containing water, an initial pulse of p-HBA was detected during the first 30 min, followed by the slow generation of additional p-HBA over periods of at least 24 h. The yield of p-HBA increased with increasing BA concentration, presumably due to the increasing 'ability of BA to compete with alternate oxidant sinks, such as ferrous iron. At pH 3, maximum yields of p-HBA during the initial phase of the reaction of up to 25% were observed. The initial rate of nZVI-mediated oxidation of BA exhibited a marked reduction at pH values above 3. Despite the decrease in oxidant production rate, p-HBA was observed during the initial reaction phase at pH values up to 8. Competition experiments with probe compounds expected to exhibit different affinities for the nZVI surface (phenol, aniline, o-hydroxybenzoic acid, and synthetic humic acids) indicated relative rates of reaction that were similar to those observed in competition experiments in which hydroxyl radicals were generated in solution. Examination of the oxidizing capacity of a range of Fe0 particles reveals a capacity in all cases to induce oxidative transformation of benzoic acid, but the high surface areas that can be achieved with nanosized particles renders such particles particularly effective oxidants.

Oxidative degradation of the carbothioate herbicide, molinate, using nanoscale zero-valent iron.

Degradation of the carbothiolate herbicide, molinate, has been investigated in oxic solutions containing nanoscale zero-valent iron particles and found to be effectively degraded by an oxidative pathway. Both ferrous iron and superoxide (or, at pH < 4.8, hydroperoxy) radicals appearto be generated on corrosion of the zero-valent iron with resultant production of strongly oxidizing entities capable of degrading the trace contaminant.